MXPA99001361A - Procedure to produce a polymer by means of polymerization of a monomer that has a double link ethelin - Google Patents

Abstract

An improved process for producing a polymer is provided by polymerizing a monomer having an ethylenic double bond in a polymerization vessel having a polymer scale preventative coating film on the surfaces of its inner wall, etc.; form by coating a first coating liquid containing a compound selected from the group consisting of an aromatic compound having 5 or more conjugated D bonds and a heterocyclic compound having 5 or more conjugated D bonds, and then coating a second coating liquid on the first layer, the first and second coating liquids are applied by means of steam as a vehicle, the second layer has a surface having a contact angle with respect to water less than 60 ° after its surface has been brought into contact with a solution of mixture of water and a vinyl chloride monomer at a ratio e n weight of l: 1, at 50øC for 1 hour, this procedure can shorten the time to form the coating film to improve productivity, and can also improve the preventive effect of polymer scale adhesion, can make the colored particles Mix less in the polymer products obtained by this process, can reduce fish eyes and initial discoloration of the products formed, and can improve the quality of polymer products and their products formed and molded

Description

PROCEDURE TO PRODUCE A POLYMER BY MEANS OF POLYMERIZATION OF A MONOMER THAT HAS A DOUBLE ETHELINIC LINK FIELD OF THE INVENTION This invention relates to a polymerization production process which can prevent the adhesion of polymer scale on the surfaces of the inner wall of the polymerization vessel and on other surfaces, and can produce good quality polymers in a process for producing a polymer by polymerizing a monomer having an ethylenic double bond, in a polymerization vessel.

DESCRIPTION OF THE PREVIOUS TECHNIQUE As is known, in the processes of polymer production by polymerization of monomers in polymerization vessels, there is a problem that the polymers can adhere to the surfaces of the inner wall of the polymerization vessel, and to other surfaces, in the form of incrustations. These polymer inlays adhered to the surfaces of the inner wall of the polymerization vessel and to other surfaces, can cause a reduction in the performance of the polymers, a reduction in the cooling capacity of the polymerization vessels, and a reduction in the quality of the product when the adhered polymer scale separates to mix in the polymeric products, and can also cause the disadvantage that removing the polymer scale should take a lot of time and work. In addition, since polymer inlays contain unreacted monomers, there is the possibility of exposing operators to them and causing them physical disturbances. Consequently, in the polymerization of monomers having ethylenic double bonds, to prevent the adhesion of polymer scale to the surface of the inner wall of the polymerization vessel and to other surfaces, methods are proposed to prevent the adhesion of polymer scale by means of one-step coating (hereinafter "one-step coating method"), exemplified by a method in which a polar organic compound such as an amine compound, a quinone compound or an aldehyde compound, or a dye or pigment, are coated as a "polymer scale preventative agent" on the surfaces of the inner wall of the polymerization vessel, stirrers, etc. (Japanese Patent Publications (kokoku) Nos. 45-30343 and 45-30835) , a method in which a polar organic compound or colorant treated with a metal salt is applied to the coating (Pate publication). Japanese (kokoku) No. 52-24953, a method in which a mixture of an electron-donor compound and an electron-receiving compound is applied as a coating (Japanese Patent Publication (kokoku) No. 53-28347), a method in which a product of the condensation reaction of 1-naphthol with formaldehyde is applied (Japanese Pre-Examined Patent Publication (kokai) No. 57-164107), a method in which a product is coated of the condensation reaction of a phenol compound with formaldehyde (Patent publication Japanese pre-examined (kikai) No. 57-192413), a method in which a polyaromatic amine is coated (Japanese Patent Publication (kokoku) No. 59-16561), a method in which a self-condensation product of a polyhydric phenol or a self-condensation product of a polyhydric naphthol is applied to the coating (Japanese Patent Publication pre-examined ( kokoi) No. 54-7487), a method in which a product of the condensation reaction of a ketone resin is applied with a phenol compound (Japanese Patent Publication Pre-Examined (Kokai) No. 62- 236804), a method in which a product of the condensation reaction of an aromatic amine with a nitroaromatic compound and a paste material thereof is applied to the coating (Japanese Patent Publication (kokoku) No. 60-30681), and a method in which a product of the condensation reaction of an aromatic amine with a quinone compound is applied (Japanese Pre-Examined Patent Publication (Kokai) No. 61-7309). In the case of the polymer scale preventive coating films, obtained by means of said one-stage coating methods, the scale tends to adhere in the vicinity of a gas-liquid boundary surface in the polymerization vessel during the polymerization or , depending on the composition of the polymerization reaction mixture, the scale tends to adhere to the entire surface of the wall. Accordingly, to avoid this, it is known how to mix in a coating liquid containing the polymer scale preventive agent, a water soluble polymeric compound such as an amphoteric polymeric compound, a cationic polymeric compound or a hydroxyl group-containing polymeric compound.; an inorganic colloid; or a substance that has no affinity for the monomers, exemplified by an inorganic salt such as an alkali metal salt (hereinafter "polymer incrustation preventive auxiliary agent"). These one-step coating methods are effective in preventing the adhesion of polymer scale when polymerizing monomers having ethylenic double bonds in polymerization vessels.

In cases where sufficient polymer scale prevention effect can not be obtained with the one-stage coating method, a method of preventing the adhesion of polymer scale by a two stage coating (hereinafter in the present invention) is proposed. "two-stage coating method"), comprising a) coating with coating liquid containing the polymer scale preventive agent as described above, to form a first layer, and b) coating additionally with a liquid coating containing the precursor auxiliary agent of polymer former, to form a second layer (Japanese Patent Pre-Examined Publication (kokai) Nos. 3-74404, 2-80403, 2-80402, 280401 and 2-47102). In both the prior one-stage coating method and the two-stage coating method for preventing adhesion of polymer scale, spray coating is usually used as a coating process, in view of productivity, including operability. . In the one-step coating method with the polymer scale preventive agent by spray coating, the coating film is formed by a process comprising the following steps 1 to 3.

Step 1: A coating liquid containing the polymer scale preventive agent is coated onto the surface of the inner wall of the polymerization vessel and other surfaces with which the monomers are contacted. Step 2: the coated surfaces are dried to form a dry film. Step 3: The surface of the coating film thus formed is washed to remove any excess coating liquid. In the two-stage coating method comprising coating with the polymer scale preventative and coating with the polymer scale preventative auxiliary, both by spray coating, the formation of coating film comprising the same steps 1 to 3 above, is also operated on the lining of the second stage. When the aforementioned spray coating is used, the surfaces of the baffles and stirring blades which face the surfaces of the inner wall of the polymerization vessel remain within the dead angle of a spray nozzle. Since it is difficult for the coating liquid to reach the surfaces of said portions that remain blind or hidden from the spray nozzle, the polymer scale preventive agent can not coat them in the same manner as surfaces that do not remain hidden. In this way, it is difficult to form a uniform coating film on the surfaces that remain hidden and the surfaces that do not remain hidden. If a coating film in an amount effective enough to prevent adhesion of polymer scale is intended to be formed on the concealed surfaces, the problem can not be avoided by using a coating liquid containing the scale preventive agent. polymer in a larger amount than for the other surfaces. It follows that an unnecessary excess of preventive agent would be applied to surfaces that do not remain hidden. Therefore, the coating film thus formed would have an uneven coating thickness and the coating film would have a greater thickness locally than is necessary. The formation of polymer-embedding preventative coating films by spray coating has also had the following problems. (1) Usually, the coating film comprising the polymer scale preventative is preformed for each polymerization dosage. Since it is common for the polymer scale preventative to have a color, the polymer scale preventive agent is applied as a coating repeatedly as the polymerization is repeatedly dosed into a larger number, so that the coating film may have a large thickness in a certain part. The part having said thick coating film can be separated and become included in the reaction mixture, or the scale preventive agent can be applied as a coating on polymer inlays that have already adhered to the surface of the inner wall of the container. of polymerization and other surfaces, and may be separated together with a portion of the scale to be mixed into the resulting polymerization products. This can cause colored particles or fish eyes in their formed products or can cause a low product quality such as high initial discoloration of the formed products, disadvantageously. (2) As indicated above, the effect of preventing the adhesion of polymer scale on the surfaces that remain hidden in the polymerization vessel, which remain within the dead angle of the spray nozzle, can be said to be not very sufficient considering the polymer scale preventative applied at * a much larger amount than on other surfaces. (3) The spray coating requires a step of drying the coated surfaces, and takes a necessary time to form the coating film of the polymer scale preventative. Consequently, with respect to an improvement in productivity, it is sought to reduce the time necessary to form the coating film. As a measure to eliminate the above disadvantages in the spray coating, a method is proposed in which a coating liquid containing uric polymer scale preventive agent, is applied by coating using steam as a vehicle (hereinafter in the present "vapor coating") (Japanese Patent Publication (kokoku) No. 1-5044.) As the coating liquid in this method, a coating liquid comprised of the polymer scale preventative alone or a coating liquid in the which additionally adds a polymeric precursor auxiliary agent.This vapor coating has the following advantages: (1) a thin and uniform coating film of the polymer scale preventative agent, necessary to effectively prevent scale adhesion, can be formed. , using the coating liquid in a small amount. (2) Pu The coating film of the polymer scale preventative agent necessary to achieve the scale prevention effect by using the coating liquid in a small amount, also on the portions remaining hidden in the polymerization vessel, and remaining within the angle, is formed. dead from the spray nozzle. In this way, the effect of polymer scale prevention can also be achieved on these portions. (3) The drying step is unnecessary in the coating film formation step, so that the time necessary to form the coating film of the polymer scale preventative agent can be reduced. Incidentally, in the vapor coating, the coating liquid and vapor are mixed in such a way that the coating liquid is entrained by the vapor and can be applied to the surfaces of the inner wall of the polymerization vessel and other surfaces. Consequently, the concentration of the polymer scale preventative agent in the coating liquid is established taking into account the fact that the solution is diluted with steam. Usually, it is stated that the concentration of the polymer scale preventative agent in the coating liquid for steam coating, is 4 to 40 times that required for spray coating, although the amount of a polymer fouling agent needed in the vapor coating is approximately equivalent to that required in the spray coating. In contrast to the advantages, the vapor coating has problems in the following points. (1) Although the vapor coating allows uniform coating in a polymerization vessel, the scale deposit can be insufficiently prevented around the interface between the gas and liquid phases. (2) As a result of insufficient prevention of the scale deposit around the interface between the gas and liquid phases, the polymer scale deposit will grow around the interface when the polymerization runs are repeated. A part of the deposited scale developed can be detached from the internal surfaces of the polymerization vessel during the polymerization and incorporated into a polymer product and cause the formation of fish eyes. (3) A polymer scale preventive agent is applied as a coating on the internal surfaces of a polymerization vessel repeatedly as the polymerization runs are repeated. Consequently, the layer of polymer scale preventative agent gradually becomes thicker. A part of the thick layer of the agent can be released during the polymerization and incorporated into the polymer products and cause colored particles. The colored particles will reduce the initial discoloration properties, particularly the luminosity index L of the polymer products.

BRIEF DESCRIPTION OF THE INVENTION An object of the present invention is to provide a process for producing a polymer by polymerizing a monomer having an ethylenic double bond, which can reduce the coating film formation time of polymer scale preventative agents, to improve productivity, which can improve the preventive effect of adhesion of polymer scale, and can cause the colored particles to mix less in the polymer products obtained by this process, can reduce fish eyes and the initial discoloration of the products formed, and also improve the quality of the polymer products and the products formed or molded with them. The above object can be carried out by a process for producing a polymer, by polymerizing in a polymerization vessel, a monomer having an ethylenic double bond, wherein said polymerization vessel has a film of polymer scale preventative coating on its surfaces of the polymer. inner wall and other surfaces with which the monomer contacts during polymerization; said coating film comprises a first layer formed on said surfaces of the inner wall and other surfaces, and a second layer formed on the first layer; said first layer is formed by coating with a coating liquid containing a compound selected from the group consisting of an aromatic compound having 5 or more conjugated D bonds and a heterocyclic compound having 5 or more conjugated D bonds, by means of steam as a vehicle, and said second layer is formed by coating a second coating liquid on the first layer by means of steam as a vehicle; and said second layer has a surface with a contact angle to water of less than 60 ° after its surface makes contact with a solution of a mixture of water and a vinyl chloride monomer in a weight ratio of 1: 1. , at 50 ° C for 1 hour. In accordance with the polymerization process of the present invention, the time to form coating films of polymer scale preventive agents can be reduced to improve productivity and also, when the monomers having an ethylenic double bond polymerize, it can be effectively avoided. that the polymer scale adhere not only to the wall surfaces in the portion of the liquid phase in the polymerization vessel, but also in agitators, blade surfaces facing the surface of the wall, and the vicinity of the surface boundary between the gas phase and the liquid phase. Therefore, the quality of the polymer products can be improved and the colored particles can be made to mix less in the polymers, and also the formed products obtained by the formation of the sheet polymers, can be made to have much less Fish eyes and also have good initial anti-discoloration.

BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings, Figure 1 illustrates schematically the arrangement in a polymerization apparatus; and Figure 2 illustrates schematically the arrangement in another polymerization apparatus.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The present invention will be described below in detail. In the following, the polymer scale preventive agent is often referred to only as "anti-fouling agent". The incrustation preventive coating film formed in the present invention comprises a first layer formed on the surfaces of the inner wall of the polymerization vessel and other surfaces, and a second layer formed on the first layer.

COAT-FIRST FILM LAYER The aromatic compound and the heterocyclic compound used in the coating liquid forming the first layer each have 5 or more conjugated D bonds. In the present specification, the term "D-links" means double bonds and triple bonds, including for example C = C, CI > C, N = N, C = N, C = S and C = 0, and the term "conjugated D-links" means a series of D-links in which each pair of adjacent D-links are linked together through a link simple and all D links have a mutually conjugated relationship with each other. The aromatic compound having 5 or more conjugated D bonds and the heterocyclic compound having 5 or more conjugated D bonds, are herein generically referred to together as the "conjugated D-link compound" in some cases. The 5 or more D bonds present in the conjugated D-link compound can form a single conjugation group or two or more conjugation groups.

Aromatic compound having 5 or more conjugated D bonds: The aromatic compound having 5 or more conjugated D bonds can include benzene derivatives, naphthalene derivatives, polynuclear aromatic compounds, quinones, non-benzene type aromatic compounds, and condensation products of compounds aromatics having a weight average molecular weight of 500 or more, which term means here the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography. First, benzene derivatives may include: phenols and derivatives thereof, such as 3,7-dioxy-10-methylxanthene and oxyanthraquinone; aromatic amines and derivatives thereof such as quinoline, carbazole, o-phenanthroline, p-phenanthroline, 3,6-diaminoacridine, 3-aminophenothiazine, 2-aminophenazine, phenothiazine, 2-oxy-4-methyl-quinoline; nitro and nitroso derivatives such as phenazine, phenazine oxide, 1-phenylazo-2-naphthol, triphenylenedioxadine and 4-nitroxanthone; aromatic aldehydes such as benzoflavin, benzene derivatives which also have a substituent other than the aldehyde group such as l-oxy-2,4-dimethyl-fluorone, 3-phenylcoumarone, ethyl cumarin-3-carboxylate, 3-acetylcoumarin, -chloro-3- (4-oxyphenyl) anthranyl and 3-nitroacridone; benzene derivatives also having a substituent other than an acyl group, such as xanthone, 2-benzoylxanthone, xanthene and fluorene; benzene derivatives and toluene derivatives having three or more different substituents such as 7-acetoxy-8-methoxy-3- (2-nitrophenyl) carbostyril; and aralkyl compounds such as 9-benzylacridine; diazo compounds and azo compounds, such as 1,1'-azonaphthalene and azoxyphenol. Then, the following may be included as a naphthalene derivative: alkyl, alkenyl and phenylnaphthalenes such as 2-methylnaphthalene, 1-ethyl-naphthalene, 2-ethyl-naphthalene and 1,2-dimethyl-naphthalene; dynaphthyl such as 1,1 '-dinaphthyl, 1,2' -dinaphthyl and 2,2'-dinaphthyl; naphthylarylmethanes such as 1-benzylnaphthalene, 2-benzylnaphthalene, 1- (Á, Á-dichlorobenzyl) naphthalene, diphenyl-Á-naphthyl-methane, diphenyl-β-naphthylmethane and di-α-naphthylmethane; naphthylarylethanes, such as 1,2-di-α-naphthanenet and 1,2-di-β-naphthatane, - hydronaphthalenes such as 1,2-dihydronaphthalenes, 1,4-dihydronaphthalene and 1,2,3,4-tetrahydronaphthalene, - nitronaphthalenes and derivatives thereof such as nitromethyl-naphthalene, nitroalkylnaphthalene, nitrophenyl-naphthalene, halo-nitronaphthalene, halo-dinitro-naphthalene, nitrosonaphthalene, diaminonaphthalene, triaminonaphthalene and tetraaminonaphthalene; halogenated naphthalenes such as 1-fluoro-naphthalene, 1-chloronaphthalene and l-chloro-3,4-dihydronaphthalene; naphthylhydroxylamines, naphthylpyrazines and naphthylurea such as naphthylhydroxylamine, ß-naphthylthiohydroxylamine, N-nitroso-α-naphthylhydroxylamine, α-naphthylhydrazine and 1,2-dibenzocarbazole; aralkyl naphthalene-based compounds such as dibenzoanthracene, acenaphthene, and nitromethylnaphthalene; naphthoaldehydes and derivatives thereof such as α-naphthoaldehyde and 2- (2,4-dinitrophenyl) -1- (α-naphthyl) -ethylene; acetonaphthenes and benzoylnaphtenes such as 1,2: 5,6-dibenzanthracene, 2'-methyl-2, 1'-dinaphthyl ketone, 2-methyl-1, 1'-dinaphthyl ketone and styryl-2-naphthyl ketone. As the polynuclear aromatic compounds can be included: anthracenes and derivatives thereof such as anthracene, 1,2-dihydroanthracene, 1-chloroanthracene, 1,4-dichloroanthracene, 1-nitroanthracene, 9,10-dinitroanthracene, 1-aminoanthracene, 2 -dimethyl-aminoanthracene, 2-anilinoanthracene, 9-methylamino-anthracene, 1,4-diaminoanthracene; phenanthrenes and derivatives thereof such as phenanthrene, 9,10-dihydrophenanthrene, 1,2,3,4-tetrahydrophenanthrene and 1-chlorophenanthrene; phenanthrenequinones such as phenanthrene-1,2-quinone and phenanthrene-1,4-quinone; and polynuclear aromatic compounds derived therefrom such as pentacene, hexacene, benzophenanthrene, benzo [a] anthracene, pyrene and coronene.

Quinones and derivatives thereof may include: naphthoquinones and derivatives thereof such as 1,2-naphthoquinone, 3-oxy-2, 2'-hydrophthyl-1,4'3 ', 4'-diquinone, 5, 6-benzoquinoxaline, 1,2-benzofenaxin, 2-benzoazo-l-naphthol, 4- (2,4-dioxyphenyl) -1,2-dioxynaphthalene, 4- (3,4,5-trioxyphenyl) -1, 2- dioxinaphthalene and 1,4-naphthol; and anthraquinones and derivatives thereof such as 1,2-anthraquinone, 2,3-anthraquinone, 1,4-anthraquinone, alizarin, quinizarin, chrysazine, histazarin, anthraflavin, isoantraflavine, anthragallol, glitter, oxyanthruraphine, oxychisazine, oxyflavopurpurine, quinazarine , alizarinpentacyanine and glitter. In addition, the aromatic non-benzene compounds may include, for example, azulene, cyclodecapentane, cyclootetradecaheptane, cyclooctadecanonene, cyclotetracosa-dodecane, heptalene, fulvalene, sesquiflulvalene, heptafluvalene and perinaphthene. The condensation products of aromatic compounds having a molecular weight of 500 or more can conveniently be condensation products of aromatic compounds preferably having a weight average molecular weight of from 500 to 70,000, preferably from 1,500 to 30,000.

Preferred aromatics condensation products include the following compounds, for example.

Condensation products of aldehyde compounds / aromatic hydroxyl compounds The condensation product of aldehyde compounds / aromatic hydroxyl compounds is a product of the condensation of an aldehyde compound and an aromatic hydroxyl compound. The use of said condensation products of aldehyde compound / aromatic hydroxyl compound in polymer scale preventive agents is disclosed, for example, in the Japanese Pre-Examined Patent Publication (Kokai) No. 57-192413, Japanese Patent Publication (kokoku) No. 6-62709, Japanese Pre-Examined Patent Publication (kokai) No. 57-164107 and O98 / 24820. The aldehyde compounds include for example, formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, arolein, crotonaldehyde, benzaldehyde, furfural, phenylacetaldehyde, 3-phenylpropionaldehyde and 2-phenylpropionaldehyde. From an industrial and economic point of view, formaldehyde and acetaldehyde are advantageous. Aromatic hydroxyl compounds include, for example, dihydroxybiphenyl compounds, naphthol compounds, phenol compounds, tannins and 2,3-dihydroxynaphthalene dimer compounds.

Examples of the dihydroxyphenyl compounds include 2,2'-dihydroxybiphenyl, 2,2'-dihydroxy-5,5'-dimethylbiphenyl, 2,2'-dihydroxy-4, 4 ', 5,5' -tetramethylbiphenyl, 2,2 ', -dihydroxy-5,5'-dichlorobiphenyl, 2,2'-dihydroxy-5,5'-dichlorohexylbiphenyl and 2,2'-dihydroxy-5, 5 '-di-tert-butylbiphenyl. In particular, from an industrial point of view, 2,2 '-dihydroxybiphenyl is preferred. Examples of the naphthol compounds include 1-naphthol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 6-hydroxy-2-naphthoic acid, 2-hydroxy-1-acid. naphthoic, 1-hydroxy-2-naphthoic acid and 1-hydroxy-8-naphthoic acid. Examples of the phenol compounds include phenol, cresol, pyrogallol, hydroxyhydroquinone, resorcin, catechol, hydroquinone, bisphenol A, hydroxybenzoic acid, dihydroxybenzoic acid, 2-hydroxy-5-methoxybenzoic acid and salicylic acid. Examples of tannins include tannic acid, galotanine China, Turkish galotanin, sumac tannin, quebrachotanina, and medlar tannin (shibuol). Dimeric 2,3-dihydroxynaphthalene compounds include for example 2, 3, 2 ', 3' -tetrahydroxybinaphthyl. The above condensation product of an aldehyde compound with an aromatic hydroxyl compound can be produced by reacting these reactive components in a suitable medium in the presence of a catalyst, usually at room temperature up to 200 ° C for 2 to 100 hours, preferably 30 hours. at 150 ° C for 3 to 30 hours. Each of the aromatic hydroxyl compounds and the aldehyde compound can be used individually or in combination of two or more types. The medium in which the above condensation reaction is carried out includes, for example, water; organic solvents such as alcohols, ketones and esters. Organic solvents include, for example, alcohols such as methanol, ethanol and propanol; ketones such as acetone and methylethyl ketone; and esters such as methyl acetate and ethyl acetate. The medium in which the above condensation reaction is carried out has a pH on the scale usually from 1 to 13, and pH adjusters can be used without any particular limitation. The catalyst used in the above condensation reaction includes for example acid catalysts such as sulfuric acid, hydrochloric acid, perchloric acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid; and basic catalysts such as NaOH, KOH and NH4OH. The ratio of the aldehyde to the aromatic hydroxyl compound used when the condensation reaction is carried out, depends on the types of the aldehyde compound, the aromatic hydroxyl compound, the solvent and the catalyst used, the reaction time, the reaction temperature , etc. Generally, it is preferred to use 0.1 to 10 moles of the aldehyde compound per mole of the aromatic hydroxyl compound.

Conversion products pyrogallol / acetone The condensation product of pyrogallol / acetone is a product of the condensation of pyrogallol with acetone, with the molar ratio of pyrogallol to acetone on the scale, usually from 1 / 0.1 to 1/10, and the melting point being usually from 100 to 500 ° C. The melting point increases with an increase in molecular weights. For example, melting points of 160 to 170 ° C correspond to molecular weights of 1.450 to 1.650; and melting points of -200 to 220 ° C, at molecular weights of 2,600 to 4,000. The use of said pyrogallol / acetone condensation products in polymer scale preventative agents is described, for example, in the Japanese Pre-Examined Patent Publication (Kokai) No. 4-328104. The pyrogallol / acetone condensation product can be produced by dissolving pyrogallol in acetone, and condensing them in the presence of a condensation catalyst. Pyrogallol is used in an amount usually from 1 to 100 parts by weight per 100 parts by weight of acetone. As the condensation catalyst, for example phosphorus oxychloride is used. The reaction can be carried out at room temperature up to 100 ° C.

Autocondensation products of polyhydric phenol and self-condensation products of polyhydric naphthol Polyhydric phenols are exemplified by catechol, resorcinol, chlororesorcinol, hydroquinone, phloroglucinol and pyrogallol; dihydroxytoluene and xylene; trihydroxy-toluene and trihydroxixylene; ethyl-di-, propyl-di-, butyl-di- or pentyl-di-hydroxybenzene; and trihydroxybenzene. The polyhydric naphthols are exemplified by naphthol derivatives such as 1,3-, 1,4-, 1,5- or 1,7-dihydroxynaphthalene. The use of such polyhydric phenol self-condensation products and self-condensation products of polyhydric naphthol in polymer scale preventive agents is described, for example, in the Japanese Pre-Examined Patent Publication (Kokai) No. 54-7487. The self-condensation product of polyhydric phenol or the self-condensation product of polyhydric naphthol can be produced by heating polyhydric phenol or polyhydric naphthol in an inert atmosphere, such as nitrogen, argon or the like, at a temperature ranging from 200 to 350 ° C for 4 hours. at 100 hours. In this reaction, several catalysts exemplified by zinc chloride, aluminum chloride and sodium hydroxide can be used.

Condensation products of aromatic amine compounds The condensation products of aromatic amine compounds include for example: (1) a self-condensation product of an aromatic amine compound; (2) a condensation product of an aromatic amine compound with a phenol compound; (3) a condensation product of an aromatic amine compound with a nitro aromatic compound; and (4) a basic product obtained by making basic a condensation product of an aromatic amine compound with a nitro aromatic compound using an alkali metal salt or an ammonium compound. The use of said condensation products of amine aromatics is described, for example, in Japanese Patent Publication (kokoku) Nos. 59-16561 and 60-30681. Aromatic amine compounds are exemplified by aniline, o-, m-, or p-phenylenediamine, o-, m-, or p-aminophenol, o-, m-, or p-chloroaniline, p-aminobenzene, 2, 4 diaminoazobenzene, p-aminoacetanilide, o-, m-, or p-methylaniline, N, N-dimethyl-p-phenylenediamine, 4-chloro-o-phenylenediamine, 4-methoxy-o-phenylenediamine, 2-amino-4- chlorophenol, 2,3-diaminotoluene, 2,4-diaminophenol, and diphenylamines such as 4-aminodiphenylamine, 2-aminodiphenylamine, 4,4'-diaminodiphenylamine, 4-amino-3'-methoxydiphenylamine and 4-amino-4'-hydroxydiphenylamine. The phenol compounds are specifically exemplified by phenol, hydroquinone, resorcinol, catechol, hydroxyhydroquinone, pyrogallol, o-, m-, or p-chlorophenol, o-, m-, or p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and 2,5-, 2,6-, or 3,5-dihydroxytoluene. Aromatic nitro compounds are exemplified by nitrobenzene, o-, m-, or p-hydroxynitrobenzene, o-, m-, or p-nitroanisole, o-, m-, or p-nitrofenetrolo, o-, m-, or p -chloronitrobenzene, o-, m-, or p-aminonitrobenzene, o-, m-, or p-nitrobenzoic acid, o-, m-, or p-nitrobenzenesulfonic acid, o-, m-, or p-nitroaniline, 2 -nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol and 4-amino-2-nitrophenol. To carry out the autocondensation reaction of an amine aromatic compound alone, the condensation reaction of an aromatic amine compound with a phenol compound and the condensation reaction of an amine aromatic compound with a nitro aromatic compound is used a mineral acid as a condensation catalyst. The mineral acids are exemplified by hydrochloric acid, nitric acid, hydrobromic acid, phosphoric acid and sulfuric acid. Preferred condensation catalysts are exemplified by permanganic acid and salts thereof such as permanganic acid and potassium permanganate; compounds related to chromium acids such as chromium trioxide, potassium dichromate and sodium chlorochromate; metal nitrate such as silver nitrate and lead nitrate; halogens such as iodine and bromine; peroxide such as hydrogen peroxide, sodium peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, peracetic acid, eumeno hydroperoxide, perbenzoic acid and p-menthane hydroperoxide; oxygenated acids or salts of oxygenated acids such as iodic acid, potassium iodate and sodium chlorate; metal salts such as ferrous chloride, ferric chloride, copper sulfate, cuprous chloride, uric chloride and lead acetate; ozone; and oxides such as copper oxide, mercury oxide, cerium oxide, manganese dioxide and osmic acid. It is also effective to use hydrogen peroxide and ferrous chloride in combination. The autocondensation reaction of an amine aromatic compound alone, the condensation reaction of an aromatic amine compound with a phenol compound and the condensation reaction of an aromatic amine compound with the condensation reaction of a nitro aromatic compound, can carried out in the presence of a condensation catalyst at a temperature of 100 to 350 ° C for 2 to 100 hours. The ratio between an aromatic amine compound and a phenol compound or a nitro aromatic compound, which are used in the condensation reaction of an aromatic amine compound with a phenol compound, and the condensation reaction of an aromatic amine compound with a nitro aromatic compound, it depends on the types of amine aromatics, the phenol compounds and nitro aromatics, and the catalysts used, the reaction time, the reaction temperature, etc. In general, it is preferable to use 0.1 to 10 moles of the phenol compound or the aromatic compound nitro per mole of the aromatic amino compound. To make basic a condensation product of an aromatic compound of amine with a nitro aromatic compound using an alkali metal salt or an ammonium compound, for example, 100 parts by weight of the condensation product of an aromatic compound of amine with a nitro aromatic compound, 10 to 20 parts by weight of an alkali or ammonium compound such as NaOH, KOH, Na2CO3, NH40H or (NH4) 2C03 are added thereto, and the mixture obtained is treated with a heat of 90 at 140 ° C. The alkali or ammonium compound can be used in an amount sufficient to neutralize the mineral acid used at the time of the condensation reaction.

Condensation products of quinone compounds The condensation products of the quinone compound include, for example, (A) a self-condensation product of a quinone compound, and (B) a condensation product of a quinone compound with at least one compound selected from the group consisting of a hydroxyl aromatic compound and an aromatic amine compound. The use of said condensation products of quinone compounds or self-condensation products of polyhydric naphthol in polymer scale preventive agents is described, for example, in the Japanese Pre-Examined Patent Publication (kokai) Nos. 5-112603 and 6- 56911 Quinone compounds include, for example, benzoquinones and derivatives thereof, such as o-, m-, or p-benzoquinone, tolu-p-quinone, o-xyl-p-quinone, thymquinone, 2-methoxybenzoquinone, gentisylquinone, acid polychoric and ubiquinone-n; naphthoquinones and derivatives thereof such as 6-methyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, alpha-naphthoquinone, juglone, lawsone, plimbagin, alkannin, echinochrome A, vitamin k] _, vitamin k2 , shikinina, & & ' -dimethyl acrylshikonin, β-hydroxyisovalerohikonin and teracrilshikonin; anthraquinone and derivatives thereof such as 3-hydroxy-2-methylanthraquinone, anthraquinone, 2-hydroxyanthraquinone, alizarin, xantopurpurine, rubiadine, munjistine, chrysopanic acid, carminic acid, kermesic acid and laccalic acid A; and phenanthrenoquinones such as phenethrenoquinone. Aromatic amine compounds are specifically exemplified by aniline, o-, m-, or p-chloroaniline, o-, m-, or p-methylaniline, N, N-dimethyl-p-phenylenediamine, 4-chloro-o-phenylenediamine , 4-methoxy-o-phenylenediamine, 2-amino-4-lorophenol, 2, 3-diaminotoluene, 4-amino-2-aminophenol, o-, m-, or p-aminophenol, o-, m-, or p-aminobenzoic acid, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, or 4,6-diaminobenzoic acid, 3- or 4-aminophthalic acid, 2-, 4-, or 5-aminoisophthalic acid, 4,6-diaminoisophthalic acid, 2,5- or 2,6-diaminoterephthalic acid, 3-, 4- or 5-aminosalicylic acid, 4-hydroxyanthranilic acid, or , m-, or p-aminobenzenesulfonic acid, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-diaminobenzenesulfonic acid, 2-amino-1-phenol acid 4-sulfonic acid and 6-amino-4-loro-l-phenol-2-sulfonic acid, alpha-naphthylamine, ß-naphthylamine, 1,5-diaminonaphthalene, 1-amino-5-hydroxynaphthalene, 1,8-diaminonaphthalene, 2,3-diminonaphthalene, 4-amino-1-naphthol, 1-amino-5-naphthol, 1,2-naphthyl acid endiamine-7-carboxylic acid, l-5-naphthylenediamine-2-carboxylic acid, 1,5-naphthylenediamine-4-arboxylic acid, 1,6-naphthylenediamine, -4-carboxylic acid, 1,8-naphthylenediamine-4-arboxylic acid , 1,2-naphthylenediamine-3-sulfonic acid, 1,2-naphthylenediamine-4-sulfonium acid, 1,2-naphthylenediamine-5-sulfonic acid, 1,2-naphthylenediamine-6-sulfonium acid, 1,2-acid Naphthylenediamine-7-sulphonic acid, 1,3-naphthylenediamine-5-sulfonic acid, 1,3-naphthylenediamine-6-sulfonic acid, 1,4-naphthylenediamine-2-sulfonic acid, 1,4-nasphthylenediamine-7-sulfonic acid, 1, 5-naphthylenediamine-2-sulfonic acid, 1,5-naphthylenediamine-4-sulfonic acid, 1,5-naphthylenediamine-7-sulfonic acid, 1,6-naphthylenediamine-2-sulfonic acid, 1,6-naphthylenediamine acid -4-sulphonic, 1,6-naphthylenediamine-4-sulfonic acid, 1,8-naphthylenediamine-3,6-disulfonic acid, 1,8-naphthylenediamine-4,5-disulfonic acid, A-amino-β-naphthalene-propionic acid , Á-amino-β-naphthalene-carboxylic acid lico, 2-naphthylamin-l-sulphonic acid, 8-naphthylamine-1-sulfonic acid, 5-naphthylamine-l-sulfonic acid, l-amino-2-naphthol-4-sulfonic acid, 2-amino-8-naphthol acid -6-sulfonic acid (acid Ó), 2-amino-5-naphthol-7-sulfonic acid (acid J) and l-amino-8-naphthol-3,6-disulfonic acid (acid H), and diphenylamines such as -aminodiphenylamine, 2-aminodiphenylamine, 4,4'-diaminodiphenylamine, 4-amino-3'-methoxydiphenylamine, 4-hydroxydiphenylamine, 4-amino-4'-hydroxy diphenylamine, 4-carboxydiphenylamine, 4-amino-4 '-carboxydiphenylamine , 4-sulfodiphenylamine and 4-amino-4 '-sulfo-diphenylamine. Aromatic hydroxyl compounds are exemplified by phenols and derivatives thereof such as phenyl, hydroquinone, resorcinol, catechol, hydroxyhydroquinone, pyrogallol, o-, m-, or p-chlorophenol, o-, m-, or p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, acid 2, 6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and 2,5-, 2,6- or 3,5-dihydroxytoluene. In addition, they are exemplified by naphthols and derivatives thereof such as Naphthol, β-naphthol, 1,3-, 1,4-, 1,5-, 2,3-, 2,6- or 2, 7- dihydroxynaphthalene, 1-hydroxy-2-naphthoic acid and 3-hydroxy-2-naphthoic acid. The self-condensation of a quinone compound or the condensation of a quinone compound with an aromatic hydroxyl compound and / or an aromatic amine compound is carried out in an organic solvent medium, optionally in the presence of a condensation catalyst. The organic solvent medium has a pH on the scale of 1 to 13, preferably 4 to 10, and pH adjusters can be used without any particular limitation. The pH adjusters used include acidic compounds for example phosphoric acid, sulfuric acid, phytic acid and acetic acid; and alkali compounds for example alkali metal compounds or ammonium compounds such as LiOH, KOH, NaOH, Na 2 CO 3, Na 2 SiO 3, Na HP 4 and NH 4 OH; and organic amine compounds such as ethylenediamine, monoethanolamine and triethanolamine. As the medium for the condensation reaction, organic solvents exemplified by alcohols, ketones and esters, or mixed solvents of water and organic solvents miscible with water are preferred. Usable organic solvents miscible in water include, for example, alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; and esters such as methyl acetate and ethyl acetate. Condensation catalyst can optionally be used which is exemplified by the azo catalysts such as A, Á'-azobisisobutylonitrile and Á, Á'-azobis-2,4-dimethylvaleronitrile; elemental or single-molecule halogens such as iodide, bromine and chlorine; peroxides such as hydrogen peroxide, sodium peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, peracetic acid, eumeno hydroperoxide, perbenzoic acid and p-menthane hydroperoxide; oxygen acids or oxygen acid salts such as iodic acid, periodic acid, potassium periodate and potassium perchlorate. Incidentally, since the quinone compound acts as a condensation catalyst, the condensation reaction occurs even in the absence of a condensation catalyst. The condensation reaction can be carried out generally at a temperature of room temperature at 200 ° C for 0.5 to 100 hours. When (a) a quinone compound and (b) an aromatic hydroxyl compound and / or an aromatic amine compound are condensed, the proportion of both reactive components used depends on the types of aromatic amine compounds, the quinone compounds and the aromatic hydroxyl compounds, the reaction temperature and the reaction time. It is preferred to use from 0.01 to 10.0 moles of component (b) per mole of component (a).

Sulfur Compounds of Hydroxyl Aromatic Compounds The sulfur compounds of the hydroxyl aromatic compounds refer to condensation products of aromatic hydroxyl compounds with sulfur chlorides such as sulfur monochloride and sulfur dichloride. The use of said sulfur compounds of hydroxyl aromatics in the polymer scale preventive agent is described for example in the Japanese Pre-Examined Patent Publication (kokai) Nos. 4-311702, 4-339801, 5-155905 and 6-9711. Aromatic hydroxyl compounds can include aromatic hydroxyl compounds of the naphthol compounds described above, phenol compounds and the like. To obtain sulfur compounds, several methods are available. For example, a method is available in which the above phenols and sulfur chlorides such as sulfur monochloride and sulfur dichloride are subjected to the condensation reaction. This reaction is carried out in an inert organic solvent for the sulfur chlorides, in which a polyhydric phenol has been dissolved. Said organic solvent may include for example aromatic hydrocarbons such as toluene, xylene and chlorobenzene, and ethylene dichloride, chloroform and ethyl acetate. The phenol and the sulfur chloride may be in a ratio such that the latter is from about 0.5 to 2 moles, preferably from about 0.9 to 1.2 moles, per mole of the former. The reaction can be carried out at a temperature from about 50 ° C to about 150 ° C. The hydrogen chloride formed as a by-product can be evaporated, or in a closed system, a hydrogen chloride scavenging agent such as triethyleneamine can be used. After finishing the reaction, in the case where the reaction product remains dissolved in the solvent, the solvent can be removed by evaporation to take the reaction product. In the case in which the reaction product remains deposited, a liquid solid separation operation such as filtration to take the reaction product can be carried out. As another method to obtain the sulfur compound, a method is available in which a polyhydric phenol and a small amount of alkaline hydroxide are heated and melted, sulfur powder is added to it little by little and then the temperature is high to about 150 ° C at about 200 ° C, where the reaction is carried out while releasing the hydrogen sulfide formed at the outside of the system, the reaction mixture is cooled and then dissolved in the solvent described below, followed by filtration to collect the insoluble matter, which is then neutralized with a dilute acid, and the aqueous phase is removed to obtain the compound in the form of a solution. - Heterocyclic compound having 5 or more conjugated D bonds: Heterocyclic compounds having 5 or more conjugated D bonds include, for example, oxygen-containing heterocyclic compounds, nitrogen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds, dicyclic compounds having one atom of hydrogen possessed in common by the two rings, and alkaloids. First, as the heterocyclic oxygen-containing compounds can be included: benzofuran, isobenzofuran, dibenzofuran and derivatives thereof such as furan- [2 ', 3' -7, 8] flavone, 9-phenylanthracene, o-oxymethyltriphenylcarbinol, , 3,3'-diphenylphthalide, rubrene, Á-sorinine and phenazone; pyran derivatives and pyrone derivatives such as 2-p-oxyphenyl-4,6-diphenylpyryl ferricchloride, baseanhydride, benzopyran and 6-phenylcoumarin; Chromenol derivatives and chromene derivatives such as 6-methyl-2,3-diphenylchromone, 6-methyl-2,3-diphenyl-4- (p-tolyl) -1,4-benzopyran-4-ol, chromanol, 7 -chromene, oxycodone, chromene, cyanizine chloride, festin, crisinidine, apigenidin, rotoflavinidin, lutosonidin, galanginidin, fisenidin and molinidin; flavone, flavonol and isoflavone derivatives such as flavonol, flavone, coumarin fukegetin, its derivatives, isocoumarin and its derivatives such as 7-oxy-3,4-benzocoumarin, dicumarol, angelicin, psoralen, bergapten, bergaptol, xantotoxin, xantotoxal, isopimpinelin , pimpinelin, oroselol, oroselone, peucedanin, oxipeucedanin, ostrrutol, medakenin, nodakenetin, seselin, xantiletin, xanthoxiletin; and xanthone and related compounds such as dixanthylene, 9-phenylxanthene, isoxanthone, 1,2,7,8-dibenzoxanthene, 3,9-diphenylxanthene, 9,9-diphenylxanthene, and the like.

Then, the nitrogen-containing heterocyclic compounds may include: indoles such as indole [3, 2-c] quinoline, indole [1,2-c] quinazoline, 2- (1-naphthyl) -3-triphenylmethylindole, 2- (2 -naphthyl) -3-triphenylmethylindol, 3, 3'-diindolyl and 3,2'-diindolyl; indole oxoderivatives such as 3- (4-ethoxy-1-naphthyl) oxyindole and indophene; carbazoles such as 1-phenyl-1,2,8-benzothianol, 2,2'-diaminodiphenyl, 1,1' -dicarbazole; porphyrins such as porphirazine, octamethyltetraazaporforin magnesium, azadipiromethine, diazacoproporphyrin, porphine and mesotetraphenylporphyrin; oxazoles such as phenanthrooxazole; thiazoles such as α-naphthhothiazole, β-naphthhothiazole, naphthol [1,2] thiazole, 2-methyl [1,2] thiazole, 2-phenylnaphtho [1,2] thiazole, 2-methylnaphtho [2, 1] -thiazole, 2-oxaphtho [2,1] thiazole, 2-aminonaphto- [1,2] thiazole and 2-mercaptonaphtho [1,2] -thiazole; oxadiazoles, such as naphtho [1,2] furazana; quinolone and related compounds such as quinoline, quinaldine, quinaldine N-oxide, ethylquinoline, 2-phenylquinoline, 3-methylquinoline, 4-phenylquinoline, 6-methylquinoline and 2,4-dimethylquinoline; isoquinoline and related compounds such as 1-methylisoquinoline, 1-phenylisoquinoline, 4-phenylisoquinoline, 1,1'-biisoquinoline and 5'-biisoquinoline; acridine and related compounds such as acridine, 1-methylacridine, 9-phenylacridine, 9- (3-pyridinyl) acridine, 2-acridinol, acridino-3,6-diol, 4-methoxyacridine, 9-phenoxyacridine, 1-nitroacridine, -aminoacridine, 1-aminoacridine, 9-phenylaminoacridine, 9-oxyacridine and 3,6-diamino-4,5-dimethylacridine; phenanthridines such as 3,4-benzoquinoline, 6-methylphenanthridine, 6-aminomethylphenanthridine and 6-pheny1fenanthridine; anthrazolines such as pyrido [2, 3-g] quinoline, 2,7-diphenyl [2, 3-g] quinoline, 2, 8-diphenyl-pyrido [3,2-g] -quinoline; phenanthroline and related compounds such as 1,7-phenatroline and 1, 10-phenatroline; pyridoindoles such as 1,9-pyridoindole, 2,9-pyridoindole and 4,9-pyridoindole; Naphthlyidine and related compounds such as 1,5-maftilidine, 1,7-naphthylidine, 1-8-naphthylidine, 3-amino-1, 5-naphthylidine, 2-amino-1, 5-naphthylidine and 2-oxy-1, 7-naphthylidine; oxazine and related compounds such as phenoxazinone and resazurin, thiazine and related compounds such as phenothiazine, nophophenothiazine, 4-amino-4? -anilinodiphenyl disulfide, 2-chloro-10- (3-dimethylamino-propyl) phenothiazine, - [1-methyl-3-piperidylmethyl) phenothrizine and 2-acetyl-10- (3-dimethylamopropyl) phenothrizine; pyridazine and related compounds such as cinnoline, 3-methylcinoline, 4-chlorocinoline, 3-bromocholine, 4-cinolinol, 4-aminocinoline, phthalazine, 4-ethyl-2-phenylphthalazinone and phthalazoline; pyrimidine and related compounds such as sulfadiazine, sulfisomidine, fteridine, 2,4-fterindiol, 2-amino-6-methyl-4-fteridinol, xanthopterin, quinazoline, 2,4-dichloroquinazoline and 2,3-diphenyl-4-quinazoline; pyrazine and related compounds such as quinoxaline and 2-methylquinoxaline, tri- and tetra-heterocyclic 6-membered compounds such as 1,2,4-benzotriazine and 1,2,4-benzotrizin-3-ol; In addition, heterocyclic sulfur-containing compounds may include: Fused thiophene compounds such as dihydronaphtho [2, 1-b] -trianaphtene, 1,3-diphenylisothianaphthenum and dibenzothiophene; 5-membered monocyclic compounds containing 2 heteroatoms such as 3,4-dihydronaphth-2, 1-trithione, triaflavono, thiacoumarin, thiazantene, triazantoidrol, thiazantrone, Milacil D, and bistiazantilene; 6-membered cyclic compounds having 2 or more heteroatoms such as trianthrene, 2,7-dimethylflyrene, 1-thiantrenyl lithium, 1-chlorothianthrene and phenoxathine. In addition, other useful compounds may include: Dicyclic compounds having a nitrogen atom possessed in common by the two rings, such as 2: 3-benzopyrrocholine, 1, 5, 8-trimethyl-2: 3-benzopirrocholine and 1-ethyl-5, 8-dimethyl-2: 3-benzopyrrocholine; and alkaloids such as casimiroin, 2-fentilquinoline, 4-oxy-2-fentilquinoline and 4-methoxy-2-fentylquinoline. Of the compounds with conjugated D-bond, it is preferred to use those which are condensation products of aromatic compounds and have a weight average molecular weight of 500 or more. Of the condensation products of the aromatic compounds, the condensation products of the aldehyde compound / aromatic hydroxyl compound and the condensation products of quinone compounds are particularly preferred. Having formed the first layer, it may preferably have a surface having a contact angle to water of 60 ° or more, and preferably of 70 to 130 °, and is even more preferable of 80 to 130 °, after having put in contact the surface with a solution of a mixture of water and a vinyl chloride monomer in a weight ratio of 1: 1, at 50 ° C for 1 hour. Accordingly, it is preferred to use a first coating liquid that can form said first layer. The selection of a compound with conjugated D bond capable of forming a first layer having a water contact angle of 60 ° or more can be easily carried out by means of a simple test. By making this layer have a water contact angle of 60 ° or more, it can be effective to form a first layer having a high adhesion to the surface of the inner wall, which is constituted by a metal such as stainless steel or glass , of the polymerization vessel and having some durability. If this contact angle is too small, the first layer may have such a weak adhesion to the surfaces of the inner wall and other surfaces that the resulting coating films tend to wash out with the water formed by the condensation of the vapor. In this way, any first uniform layer can not be formed with good adhesion. The first coating liquid for the formation of the first layer is prepared by dissolving the conjugated D-linking compound in an appropriate solvent. The solvent includes, for example, water; alcohol solvents such as methanol, ethanol, propanol, butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 2-methyl-2-butanol and -fentanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvent such as methyl formate, ethyl formate, methyl acetate, ethyl acetate and ethyl acetoacetate; ether solvents such as 4-methyldioxolane and ethylene glycol diethyl ether; furan; and non-protonic solvents such as dimethyl formamide, dimethyl sulfoxide and acetonitrile. The solvents can be used appropriately individually or as a combined solvent of two or more thereof. Among the above solvents, water and a combined solvent of water and an organic solvent miscible with water are preferred. Among the above organic solvents, organic solvents miscible in water include alcohol solvents such as methanol, ethanol and propanol; ketone solvents such as acetone and methyl ethyl ketone; and ester solvents such as methyl acetate and ethyl acetate. Particularly, it is preferred to use the alcohol solvents. In the case where a combined solvent of water and a water miscible organic solvent is used, the organic solvent is preferably contained in an amount such that there is no danger of ignition, evaporation and the like and there is no problem about the safety of its handling, for example by toxicity. Specifically, the amount is preferably 50% by weight or less, preferably 30% by weight or less. The pH of the first coating liquid is appropriately selected depending on the type of conjugate binding compound. For example, for pyroaloacetone condensation products, self-condensation products of polyhydric phenol and autocondensation products of polyhydric naphthol, a pH of 2.0 to 6.5 is preferred. For this the pH adjusters used to adjust the pH include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid and nitric acid. For the condensation products of aldehyde / hydroxyl aromatic compounds, the condensation products of an amine aromatic compound, and the condensation products of a quinone compound, a pH of 7.5 to 13.5 is preferred, and preferably a pH of 8.0 to 12.5. For that case, alkaline compounds used to adjust the pH include for example alkali metal compound or ammonium compound such as LiOH, NaOH, KOH, Na2CO3, Na2HP04 and NH4OH; and organic amine compounds such as ethylenediamine, monoethanolamine, diethanolamine and triethanolamine. The B-conjugated compound conjugated in the first coating liquid may preferably be in a concentration ranging from 1.0 to 25.0% by weight, preferably from 2.5 to 15.0% by weight, and even more preferred from 4 to 10% by weight. If they are at too low a concentration a difficulty may arise since the steam must be used in a large quantity to form the first layer in an effective amount. If they are in a very high concentration, the coating liquid can become unstable and cause a precipitate during storage in a storage tank, or the first layer obtained by coating on the surfaces of the inner wall and other surfaces can have a thickness of uneven coating and cause a cancellation of the incrustation prevention effect.

Preferably, all solutes are completely dissolved in a solvent to form the first coating liquid in a uniform solution. The first coating liquid may optionally contain a water-soluble polymeric compound, an inorganic colloid, etc., to a degree such that the performance of the uniform coating film formation and the adhesion of the first layer to the surface of the coating are not impaired. the inner wall, in addition to the conjugated B-binding compounds.

SECOND FILM LAYER The second layer is formed on the first layer thus formed. This second layer has a surface having a contact angle to water of less than 60 °, and preferably 10 to 55 °, after having contacted its surface with a solution of a mixture of water and a chloride monomer of vinyl in a 1: 1 weight ratio, at 50 ° C for 1 hour. When this contact angle to water is less than 60 °, the second layer exhibits a good adhesion effect to the first layer. Simultaneously, the monomers and polymers contained in the polymerization reaction mixture can be prevented from adhering to the surface of the inner wall of the polymerization vessel and other surfaces during the polymerization, making it possible to achieve the scale prevention effect. If, on the other hand, the contact angle to water is 60 ° or more, the monomers and polymers will tend to be absorbed onto the coating film, making it impossible to achieve a sufficient incrustation prevention effect. As a second coating liquid used to form said second layer having a water contact angle of less than 60 °, it is preferable to use a coating liquid containing at least one hydrophilic compound selected from the group consisting of a polymeric compound soluble in water, an inorganic colloid, a salt and an inorganic acid.

Water-soluble polymeric compound The water-soluble polymeric compound includes, for example, water-soluble polymeric compounds containing hydroxyl group, water-soluble amphoteric polymeric compounds, water-soluble anionic polymeric compounds, and water-soluble cation polymeric compounds. Water-soluble polymeric compounds containing hydroxyl group include for example starches such as amylose, amylopectin, dextrin and oxidized starch; viscous liquid materials of animal origin such as chitin, cellulose derivatives such as methyl cellulose, glycol cellulose, methyl ethyl cellulose, hydroxymethyl cellulose, and hydroxyethyl methyl cellulose; hemicellulose such as xylan, mannan, arabogalactan, galactane and araban; lingnins such as alcohol lignin, dioxane lignin, phenol lignin, hydrotropic lignin, mercaptolignin, alkaline lignin, thiolalkaline lignin, acid lignin, cuproxam lignin, and periodate lignin; and partially saponified polyvinyl alcohols and polyvinyl alcohols. Among these, amylopectin, dextrin, methylcellulose, glycolcellulose, mannan, galactan, alcohol lignin, dioxane lignin, alkaline lignin, and acid lignin are preferred. Water-soluble amphoteric polymeric compounds include, for example, glue, gelatin, casein, albumin, ribonucleic acids, deoxyribonucleic acids and chitosan. Water-soluble anionic polymeric compounds include, for example, anionic polymeric compounds having a carboxyl group or a subphonic acid group in their side chain, exemplified by sulfomethylated polyacrylamide compounds, polyacrylic acid, alginic acid, an acrylamide / vinylsulfonic acid copolymer, polymethacrylic acid and polystyrene sulfonic acid, carboxylmethystarch, peptic acid, peptic acid, protopeptinic acid, carrageenan, hyaluronic acid, chondroitin sulfuric acid, heparin, keratosulfuric acid, thioglycolic acid, lignin sulphonic acid, styrene-maleic anhydride copolymers, copolymers of acid and caboxymethylcellulose. Water-soluble cationic polymeric compounds include cationic polymer electrolytes having nitrogen atoms on the side chains, nitrogen atoms on the side chains, nitrogen atoms having positive charges, exemplified by polyethyleneamine, polyvinylamine, polyacrylamide, an N-copolymer. -vinyl-2-pyrrolidone acrylamide, a cyclized polymer of dimethyldiamylammonium chloride, a cyclized polymer of dimethyldiethylammonium bromide, a cylindrized polymer of diallylamine hydrochloride, a cyclized copolymer of dimethyldiallylammonium chloride with sulfur dioxide, polyvinyl pyridine, polyvinylpyrrolidone, polyvinylcarbazole, polyvinyl imidazoline, polydimethylaminoethyl acrylate, polydiethylaminoethyl acrylate, polydiethylaminoethyl methacrylate, and derivatives or modified products of any of these polymeric compounds, exemplified by partially entangled products, copolymers, copolymers, grafting, and these polymeric compounds in which a functional group such as -OH, -NH, -COOH or -S02H has been introduced. Of the polymeric water soluble compounds exemplified above, methylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, polyvinyl alcohol, partially saponified polyvinyl alcohol, glue, casein, gelatin, chitosan, polyacrylic acid, alginic acid, polymethacrylic acid, peptic acid, carrageenan, acid are preferred. hyaluronic, carboxymethylcellulose, polyvinyl pyrrolidone and a styrene-maleic anhydride copolymer.

Inorganic Colloid Inorganic colloids include, for example, oxides or metal hydroxide colloids selected from aluminum, thorium, titanium, zirconium, antimony, tin, iron, etc .; colloids of tungstic acid, vanadium pentoxide, selenium, sulfur, silica, gold or silver; and sun of silver iodide. Among them, the colloids of oxides or hydroxides of metals selected from aluminum, titanium, zirconium, tin and iron, and colloidal silica are preferred. These inorganic colloids may be those obtained by any production process over which there are no particular limitations. For example, particulate colloids produced by a dispersion process using water as a dispersion medium or an agglomeration process are available. The colloidal particles preferably have a size of 1 to 500 μm.

Inorganic salt Inorganic salts include, for example, alkali metal silicates, inorganic salts of alkaline earth metals. The alkali metal silicate includes for example metasilicate (M2Si? 3), orthosilicates (M4SÍO4), disilicates (M2Si? 3), trisilicates (M3SÍ3O7) and sesquisilicatos (M4SÍ3O10). wherein in these formulas, M represents an alkali metal such as lithium, sodium or potassium, of alkali metals; and liquid glass. The inorganic salts of alkaline ferrous metals include for example silicates, carbonates, phosphates, sulfates, nitrates, borates, acetates, hydroxides, oxides or alkaline earth metal alloys such as magnesium, calcium and various. Of these alkaline earth metal compounds, magnesium carbonate, calcium carbonate, magnesium phosphate, calcium phosphate, calcium pyrophosphate, calcium diacid pyrophosphate, barium phosphate, calcium sulfate, calcium borate, hydroxide are particularly preferred. of magnesium, calcium hydroxide, barium hydroxide, magnesium chloride and calcium chloride.

Acid The acid may include inorganic acids such as phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphomolybdic acid, silicomolybenadic acid, phosphotungstic acid, and silicotungstic acid, molybdic acid, and tungstic acid; and organic acids such as terephthalic acid, 1,2-dodecanedicarboxylic acid, 1-dodecanedisulfonic acid, benzoic acid, lauric acid, sulfonyl acid, p-styrenesulfonic acid, propionic acid, salicylic acid, copper phthalocyanine tetrasulfonic acid, urocanic acid, L-ascorbic acid, D-isoascorbic acid, chlorogenic acid, caffeic acid, p-toluenesulfonic acid, sorbic acid, β-naphthoquinone, 4-sulfonic acid, phytic acid and tannic acid. Of the above hydrophilic compounds, water-soluble polymeric compounds, inorganic colloids and inorganic salts are preferred, and water-soluble polymeric compounds are particularly preferred. The second coating liquid for the second layer is prepared by dissolving at least one of the compounds selected from the above hydrophilic compounds in a suitable solvent. As a solvent, water or a combined solvent of water and a hydrophilic organic solvent having an affinity for water can be used. Of the above solvents, the hydrophilic organic solvent may include alcohol type solvents such as methanol, ethanol, and propanol; ketone type solvents such as acetone and methyl ethyl ketone; and ester type solvents such as methyl acetate, and ethyl acetate. In addition to the above solvents, it is preferable to use alcohol-type solvents. In the case where the combined solvent of water and the hydrophilic organic solvent are used, the hydrophilic organic solvent may preferably be used in such a way that there is a non-hazardous combustion or explosion content and there is no problem with the safety in handling such as toxisity. Specifically indicated, the hydrophilic organic solvent may preferably be at a content of 50% by weight or less, and preferably 30% by weight or less.

Preferably, all solvents are completely dissolved and the colloidal particles are completely dispersed uniformly in a solvent to form the second coating liquid in a uniform solution. A pH adjuster such as NaOH or ethylenediamine may also be optionally used. The hydrophilic compound in the second coating liquid may preferably be in a consentration ranging from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight.

Steam vehicle According to the process of the present invention, both the first layer and the second layer are formed by coating the respective coating liquids by means of steam as a vehicle. The steam used may be usually available steam or superheated steam, and preferably it may be steam having a pressure of 2 to 35 kgf / cm.G, and preferably one having a pressure of 2.8 to 20 kgf / cm.sup.2 G. preferably having a temperature of 120 to 260 ° C, and preferably 130 to 200 ° C. The pressure and steam temperature described above are the values measured before mixing the vapor with a coating liquid, for example, inside the steam supply line 16, as shown in Figure 1 described below.

Formation of the coating film The coating film comprising the first layer and the second layer will be described with reference to FIG. 1, which illustrates the arrangement in a polymerization apparatus. Step 1. - Preheating the surface of the inner wall and other surfaces of the polymerization vessel by steam. Hot water or its like is passed through a fixed jacket 2 to a polymerization vessel 1 to preheat the surface of the inner wall of the polymerization vessel at a temperature of 50 ° C or more (preferably 50 to 95 ° C. ). At the top of this polymerization vessel, a coating ring 4 is provided which is formed of a ring-shaped tube and has ascending nozzles 3b and descending nozzles 3a. To the cladding ring 4, a line 5 is connected through which the steam and the coating liquid are fed from the outside of the polymerization vessel 1. To line 5 are connected a steam feed line 6, the first coating liquid supply line 7 and the second coating liquid supply line 8 through the respective valves. If necessary, the steam (usual steam or superheated steam) can be blown into the container from the coating nozzles 3a and 3b of this coating ring 4 to preheat also deflectors (not shown) and stirring blades (not shown). In this apparatus, steam is fed to the coating ring 4 from a steam feeder 9 via a flow meter 10 through lines 6 and 5.

Step 2. - First Stage Coating The steam is fed to the coating ring 4, and the first coating liquid maintained in a first coating liquid tank 11 is fed to the coating ring 4 through lines 7 and 5 by means of a pump 12 or a suction valve (not shown). P denotes a pressure gauge. The first coating liquid is carried by the vapor and is, in the fog state, applied to, and coated on, the surface of the inner wall of the polymerization vessel and the surfaces with which the polymers come into contact during the polymerization , such as the surfaces of the deflector and the surfaces of the stirring blade.

Simultaneously with this coating, the first coating liquid coated on these surfaces is dried (simultaneous drying), so that the first layer is formed. Consequently, it is unnecessary to perform any particular operation to achieve drying.

The vapor (G) and the coating liquid (L) may preferably be in a mixing ratio (L / G) of 0.01 to 1.0, and more preferably 0.03 to 0.2, as the ratio of flow velocity to the weight basis .

Step 3. - Second stage coating Subsequently, in the state in which the vapor remains flowing, the second coating liquid maintained in a second coating liquid tank 13 is fed to the coating ring 4, in the same way through lines 8 and 5 by means of a pump 14, and is coated to form the second layer (not shown). As in the case of the first stage coating, the second coating liquid coated on the first layer is dried simultaneously with the coating (simultaneous drying), so that the second layer is formed, making it unnecessary to perform any drying operation. in particular. Also in this second stage coating, the vapor (G) and the coating liquid (L) may preferably be in a mixing ratio (L / G) of 0.01 to 1. 0, more preferably from 0.03 to 0.2, in terms of flow rate ratio based on weight.

Step 4. - Washing with water After the steam supply and the coating liquid are interrupted, the interior of the polymerization vessel is washed with cleaning water kept in a water tank 15. The cleaning water is fed into the tank. polymerization vessel 1 from nozzles 18 through a line 17 by means of a pump 16. However, washing with water is unnecessary if the coating liquid does not thereby affect the quality of the product. The first layer thus formed may preferably have a dry coating weight of 0.0005 to 3 g / m, and more preferably of 0.0005 to 1 g / m. The second layer may preferably have a dry coating weight of 0.0005 to 2 g / m2, and more preferably of 0.0005 to 1 g / m2. The first and second layers may preferably have a total dry coating weight of from about 0.001 to 5 g / m2, and more preferably from 0.001 to 2 g / m.

Polymerization The process of the present invention is applied to the polymerization of a monomer having an ethylenically unsaturated double bond. Examples of the monomer include vinyl halides, such as vinyl chloride; vinyl esters, such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid and its esters or salts; maleic acid, fumaric acid and its esters or anhydrides; diene monomers such as butadiene, chloroprene and isoprene; styrene; acrylonitrile; vinylidene halides; and vinyl ether.

Particularly suitable examples for practicing the process of the present invention, include the production of vinyl halide polymers, such as vinyl chloride, vinylinide halides, or a monomer mixture formed mainly thereof by polymerization of suspension or polymerization of emulsion in an aqueous medium. The coating film formed by the process of the present invention has a high durability even for monomers, such as allymethylstyrene, acrylic acid esters, acrylonitrile and vinyl acetate, which have a high solvency capacity for conventional coating films, so that the process can be conveniently carried out even for the production of latexes and polymer beads formed of polystyrene, polymethacrylate, polyacrylonitrile, etc .; the production of synthetic rubbers such as SBR, NBR, CR, IR, IIR, etc. (these synthetic rubbers are generally produced by emulsion polymerization); and the production of ABS resin. In the polymerization of one or more of these monomers, the objective of preventing fouling can be effectively achieved regardless of the types of polymerization, such as suspension polymerization, emulsion polymerization, overall polymerization and solution polymerization, even in the presence of any additive, such as emulsifiers, stabilizers, lubricants, plasticizers, pH adjusters and chain transfer agents. For example, in the case of suspension polymerization or emulsion polymerization, of a vinyl monomer, several additives are optionally added, if required. The additives include, for example, suspending agents such as partially saponified polyvinyl alcohol and methylcellulose; anionic emulsifiers such as sodium lauryl sulfate; nonionic emulsifiers such as sorbitan monolaurate and polyoxyethylene alkyl ether; stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, and dioctyltin mercaptide; chain transfer agents such as trichlorethylene and mercaptans; and pH adjusters. In accordance with the present process, the deposition of scale is effectively prevented in the presence of any of the above additives. The remarkable preventive polymer deposition deposition effect of the invention is exhibited without being affected by the type of polymerization catalysts, even when any catalyst is used. Specifically, the catalysts include, for example, t-butyl peroxydecanoate, bis (2-ethylhexyl) peroxydicarbonate, 3,5,5-trimethylhexanoyl peroxide, alpha-cumyl peroxydecanoate, eumenohydroperoxide, cyclohexanone peroxide, peroxypivarate t-butyl, bis (2-ethoxyethyl) peroxydicarbonate, benzoyl peroxide, diisopropylbenzene hydroperoxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, alpha, alphap-azobisisobutylnitrile, alpha, alpha] - azobis -2, 4-dimethylvalero-nitrile, di-2-ethylhexyl diperoxyisophthalate, potassium persulfate and ammonium persulfate. Other conditions for polymerization may be those that are conventionally used, and there are no limitations, unless the effects of the present invention are affected. In the sequential, considering the cases of suspension polymerization, solution polymerization and overall polymerization as examples, the typical polymerization conditions will be described. First, in the suspension polymerization, water and a dispersant are charged to a polymerization vessel. Subsequently, the polymerization vessel is evacuated to reduce the initial pressure to a value of 0.01 to 760 mm Hg (0.01 to 101 kPa), and a monomer or monomers are then charged, after which the internal pressure usually takes a value from 0.5 to 30 kgf / cm G (150 to 3,040 kPa). Then, the polymerization is carried out at a reaction temperature of 30 to 150 ° C. During the polymerization, one or more materials selected from water, a dispersant and a polymerization initiator are optionally added. The reaction temperature during the polymerization is different, depending on the type of monomer that will be polymerized. For example, in the case of polymerization of vinyl chloride, the polymerization is carried out at 30 to 80 ° C, whereas in the case of polymerization of styrene, the polymerization is carried out at 50 to 150 ° C. . The polymerization can be estimated to end when the pressure inside the polymerization vessel has decreased to a value of 0 to 7 kgf / cm 'G (100 to 790 kPa), or when substantially no difference between the inlet temperature has been observed. and the outlet temperature of the cooling water flowing in and out of a circumferentially provided polymerization vessel liner (ie, when the release of heat due to the polymerization reaction has decreased). The amounts of water, dispersant and polymerization initiator are generally from 20 to 500 parts by weight, from 0.01 to 30 parts by weight, and from 0.01 to 5 parts by weight, respectively, per 100 parts by weight of the monomer. In the solution polymerization, an organic solvent, such as toluene, xylene or pyridine, is used as the polymerization medium, instead of water. If necessary, a dispersant can be used. The other conditions for polymerization are generally the same as those described for suspension polymerization. In the overall polymerization, after a polymerization vessel is evacuated to a pressure of about 0.01 to 760 mm Hg (0.001 to 101 kPa), a monomer and a polymerization initiator are charged to the polymerization vessel, and then the Polymerization is carried out at a reaction temperature of -10 to 250 ° C. For example, the reaction temperature is from 30 to 80 ° C for the polymerization of vinyl chloride, and it is from 50 to 150 ° C for the polymerization of styrene.

EXAMPLES The present invention will now be described in more detail below by examples. In the sequential, "parts", refers to "parts in weight". In the tables, "auxiliary agent" refers to "preventive auxiliary agent of polymer inlay".

Production of condensation products In the following production examples, the average molecular weight-weight of each condensation product obtained was measured in the following manner.

Measurement of weight-average molecular weight The average molecular weight-weight in terms of polystyrene was measured by gel permeation chromatography (GPC) under the following measurement conditions. Columns: Shelter Column: Trade name: slim-pack GPC-800DP, manufactured by Shimadzu Corporation. Analytical Columns: Trade name: slim-pack GPC-803D, 802D, manufactured by Shimadzu Corporation. Mobile phase: LiBr at 10 M / DMF Flow rate: 1.0 ml / min Detector: Rl Temperature: 60 ° C.

EXAMPLE OF PRODUCTION 1 Production of the condensation product No 1; In a pressure resistant reaction vessel, 30,000 moles (960 kg) of methanol, 100 moles (15.8 kg) of 1,8-diaminonaphthalene, 50 moles (5.4 kg) of p-benzsquinone and 250 moles (31.5 kg) were charged. ) of pyrogallol, and the temperature was raised to 70 ° C with stirring. After the reaction was carried out at 70 ° C for 10 hours, the reaction mixture was cooled to a methanol solution of a condensation product (condensation product No 1). The condensation product No 1 had an average molecular weight-weight of 3,500.

EXAMPLE OF PRODUCTION 2 Production of condensation product No 2: In relation to the production example 3 described in the Japanese patent publication (kokoku) No. 6-62709, an inlay deposition preventive agent was produced. In a pressure resistant reaction vessel, 30 moles (5.59 kg) of 2,2'-dihydroxybiphenyl, 30 moles (0.948 kg) of paraformaldehyde with a purity of 95%, 0.19 kg of paratoluenesulfonic acid, and 10 1 were charged. of ethylene glycol dimethyl ether, and the temperature was raised to 130 ° C with stirring. After the reaction was carried out at 130 ° C for 17 hours, the reaction mixture was cooled to 50 ° C, and then placed in 50 liters of water. The separated resin by placing said mixture in water was filtered, and then washed with water, followed by drying to obtain 5.1 kg of a condensation resin of 2,2'-dihydroxybiphenyl-formaldehyde (condensation product No 2). The condensation product No 2 had an average molecular weight-weight of 5,400.

EXAMPLE OF PRODUCTION 3 Production of the condensation product No 3 In relation to the production example 1 described in the Japanese pre-inspection patent publication (kokai No. 57-164107, a polymer scale deposition preventive agent was produced.) In a pressure resistant reaction vessel, 250 moles were charged. (36.0 kg) of 1-naphol and 180 liters of aqueous NaOH solution to IN (containing 180 moles or 7.2 kg of NaOH), and the temperature was raised to 50 ° C with stirring, then to the reaction mixture, formaldehyde (19.75 liters of aqueous solution at 38% w / v, 250 moles) was added dropwise over a period of 1.5 hours During the addition, the internal temperature of the reaction vessel was controlled so that it did not exceed 80 ° C. Then, the reaction mixture was cooled to 60 ° C for a period of 3 hours, stirring was maintained, then the temperature of the reaction mixture was raised to 98 ° C to carry out the reaction at that temperature for 1.5 hours. hours later, the reaction mixture was cooled to an alkaline solution of a condensation product (condensation product No 3). The condensation product No 3 had an average molecular weight-weight of 2,400.

EXAMPLE OF PRODUCTION 4 Production of condensation product No 4: In relation to the synthesis of coating compound 2 described in the Japanese pre-inspection patent publication (kokai) No. 57-192413, an incrustation deposition preventive agent was produced. In a pressure resistant reaction vessel, 100 moles (12.6 kg) of pyrogallol and 100 liters of water were charged, and the pyrogallol was dissolved in water. Then, to the obtained solution, 200 moles (21.2 kg) of benzaldehyde and 300 moles (29.4 kg) of phosphoric acid were added, and the mixture thereof was reacted at 95 ° C for 10 hours. As a result, a reddish brown product insoluble in water was obtained. This water-insoluble product was washed with ether, followed by extraction with methanol to extract a soluble material in methanol from the insoluble product in water. Then, the methanol was removed from the extract by drying to obtain the condensation product No 4 (pyrogallol-benzaldehyde condensate) as a residue, which had an average molecular weight-weight of 4,500.

EXAMPLE OF PRODUCTION 5 Production of condensation product No 5 In relation to the production example I described in the Japanese patent publication (kokoku) No. 59-16561), an inlay deposition preventive agent was produced. In a pressure resistant reaction vessel, 100 moles (10.8 kg) of m-phenylenediamine, 200 moles (22.0 kg) of resorcinol and 1.04 kg of 35% hydrochloric acid (10 moles as HCl) were charged as catalyst, and the temperature rose to 305 ° C. Immediately after the mixture in the reaction vessel reached 305 ° C, it was cooled. The water vapor produced in the course of the increase in temperature and reaction was removed, and the internal pressure was maintained at 150 kPa or less. After cooling, the resulting m-phenylenediamine / resorcinol condensate was pulverized, followed by water washing, filtration and drying, until obtaining the condensation product No 5, which had an average molecular weight-weight of 4000.

EXAMPLE OF PRODUCTION 6 Production of condensation product No 6 In relation to the production example VI described in the Japanese patent publication (kokoku) No. 59-16561, an inlay deposition preventive agent was produced. In a pressure resistant reaction vessel, 100 moles (10.9 kg) of p-aminophenol and 0.99 kg of 30% hydrochloric acid (9.5 moles as HCl) were charged, and the temperature was raised to 169 ° C. Immediately after the reaction mixture reached 169 ° C, 18 liters of xylene was added slowly. The xylene was added so that the water formed during the condensation reaction was removed as an azeotropic mixture. Then, the temperature of the reaction mixture was raised to 222 ° C, and the reaction was carried out at the same temperature for 3 hours. The mixed xylene-steam of water produced during the reaction was removed, and the internal pressure was maintained at 150 kPa or less. After the reaction was carried out for 3 hours, the reaction mixture was cooled. The reaction product (condensation product No 6) obtained was solid. Then, the reaction product was pulverized into fine particles, and then washed with water, followed by filtration and drying to obtain the condensation product No 6, which had an average molecular weight-weight of 2,500.

EXAMPLE OF PRODUCTION 7 Production of condensation product No. 7; In relation to the production example 1 described in the Japanese pre-inspection patent publication (kokai) No. 54-7487, an inlay deposition preventive agent was produced. In a reaction vessel, 200 moles (22.0 kg of resorcinol) were charged, and then heated under a nitrogen atmosphere. The temperature of the resorcinol was raised to 300 ° C, and the reaction was carried out at the same temperature for 8 hours, followed by cooling. The self-condensed solid resorcinol thus obtained was pulverized to obtain the condensation product No 7, which had an average molecular weight-weight of 1,700.

EXAMPLE OF PRODUCTION 8 Production of the condensation product No 8: (1) Synthesis of a 2,3-dihydroxynaphthalene dimer compound: In a flask having an internal capacity of 3 liters provided with a reflux condenser, 1,300 ml of methanol was charged and then 144 g (0.9 mol) was dissolved of 2,3-dihydroxynaphthalene. After dissolution, the temperature was raised to 65 ° C, and 243 g (0.9 moles) of hydrated ferric chloride (FeCl 3 6H 0) dissolved in 450 ml of methanol were added dropwise to the solution obtained under reflux for 30 minutes. minutes After the addition, the reaction was continued under reflux for 5 hours. Subsequently, the reaction solution was transferred to 4.5 liters of dilute hydrochloric acid, and then the resulting mixture was stirred for 12 hours, to produce a 2,3-dihydroxynaphthalene dimer compound. The reaction solution thus obtained was filtered to remove the solvents, and then the residual material was washed with 2 liters of pure water for 2 hours. The solution was filtered again to remove the hydrated ferric chloride (FeCl3 6H20). The 2,3-dihydroxynaphthalene dimer compound obtained was dried in a dryer at 40 ° C. (2) Into a 3 liter flask fitted with a reflux condenser, one liter of pure water was charged, and then 5 g of sodium hydroxide and 50 g of the 2,3-dihydroxynaphthalene dimer compound obtained above were charged. Subsequently, after the temperature was raised to 70 ° C, 12.75 g of an aqueous 37% formaldehyde solution dissolved in 237.3 g of distilled water was added dropwise over 30 minutes. After the addition, the reaction was continued at the same temperature for 5 hours, and then the temperature was raised to 95 ° C, and the reaction was continued for another 2 hours, thus obtaining the condensation product No 8. By the way , all reactions were carried out in N2 atmospheres. After concluding the reactions, the condensation product No 8 was cooled to 25 ° C, and then preserved under an N 2 atmosphere. The average molecular weight-weight was 22,000.

EXAMPLE OF PRODUCTION 9 Production of the condensation product No 9; In a reaction vessel having an internal capacity of 2 liters provided with a reflux condenser, a mixed solvent of methanol (450 g) was charged with water (450 g), and subsequently 100 g of alpha-naphthoquinone and 10 g of water were charged. g of sodium hydroxide. Then, the internal temperature of the reaction vessel was raised to 50 ° C, and the mixture therein was reacted at 50 ° C for 24 hours, followed by cooling to room temperature. Thus, a solution of the condensation product No. 9 was obtained. The condensation product No. 9 had an average molecular weight-weight of 3,000.

EXAMPLE OF PRODUCTION 10 Production of condensation product No. 10; In an internal volume reaction vessel of 20 1 having a reflux condenser, 1.5 kg of l-naphthol and 7.5 l of toluene were placed, and the obtained mixture was heated with stirring until the toluene was refluxed. Under reflux at this temperature, 930 ml of sulfur monochloride was added dropwise over a period of 6 hours, and then the mixture obtained was kept for 1 hour at that temperature. After the reaction mixture was cooled, 5 1 of hexane was added with stirring to cause the reaction product to precipitate. Then, the reaction product was filtered, and then dried to obtain the condensation product No. 10. The condensation product No. 10 had an average molecular weight-weight of 1,200.

EXAMPLE OF PRODUCTION 11 Production of condensation product No. 11: In a reaction vessel of internal volume of 20 1 having a reflux condenser, 6.7 1 of water, 1,786 g (9.5 moles) of 6-hydroxy-2-naphthoic acid, 55 g (0.5 moles) of resorcinol were placed and 620 g (15.5 moles) of NaOH, and then the mixture obtained was heated to 50 ° C with stirring. By the time it reached 50 ° C, an aqueous solution of formaldehyde (formaldehyde: 10 moles) at 30% w / v was added dropwise over a period of 1 hour. During the addition, the internal temperature of this reaction vessel was controlled so that it was not higher than 55 ° C. Then, the reaction mixture thus obtained was heated to 85 ° C, and allowed to react at this same temperature for 3 hours. Then, the obtained reaction mixture was cooled to an alkaline solution of a condensation product (condensation product No. 11). The condensation product No. 11 had an average molecular weight-weight of 2,200.

Preparation of the first coating liquid Preparation of the first coating liquids Nos. 101 to 126: Using a conjugate B-binding compound, pH adjuster and solvent shown in Table 1, first coating liquids forming the first layer were prepared to satisfy the conditions shown in Table 1 [compound of conjugated B-bond (A), auxiliary agent (B), pH adjuster, weight ratio of (A) / (B), total concentration of (A) + (B), solvent composition, and pH] . In the table, coating liquid No. 102 is a comparative coating liquid containing a polymer scale preventative agent at a low concentration, to be used as a spray coating. As in the case of the coating liquids using the water-soluble polymeric compound, the water-soluble polymeric compound (D) was so slightly soluble at room temperature that the solvent was heated to about 70 ° C to dissolve the compound.

Preparation of coating liquids Nos. 127 to 131: The following compounds I to V were used as conjugated B-bond compound.

I: phenanthrene-1,2-quinone II: flavonol III: phenothiazine IV: 1,8-diaminonaphthalene V: anthraquinonoacridone.

Using a compound of the above, pH and solvent adjuster shown in Table 1, first coating liquids were prepared to meet the conditions shown in Table 2 [B-conjugate-conjugate compound (A), auxiliary agent (B), adjuster of pH, weight ratio of (A) / (B), total concentration of (A) + (B), solvent composition, and pH]. In the following table, the condensation product is simply called "CP". For example, "CP 9" means "condensation product No. 9".

TABLE 1 TABLE 2 Preparation of the second coating liquid Preparation of the second coating liquids Nos. 201 to 218: Using an auxiliary agent (B), pH adjuster and solvent shown in Tables 3 and 4, coating liquids containing the auxiliary agent (second coating liquids) were prepared to satisfy the conditions shown in Tables 3 and 4 [Agents] auxiliaries (B), weight ratio of (l) /. { (2), (3) or (4)} , total concentration of (B), solvent, pH adjuster, and pH]. In the table, the coating liquid No. 202 is a comparative coating liquid containing a polymer scale preventative agent at a relatively low concentration, to be used as a spray coating.

TABLE 3 TABLE 4 EXAMPLE 1 Figure 2 schematically illustrates the arrangement of a polymerization apparatus. In relation to a polymerization apparatus, the same elements as in Figure 1 are denoted by the same numbers. The following experiments were carried out using a polymerization apparatus shown in Figure 2. In Figure 2, a polymerization vessel 1 of internal volume of 2 m made of SUS 316L stainless steel, is equipped with a stirrer 21 having blades of stirring 20 (the agitation motor is not shown), a heating-cooling jacket 2, an inspection opening 22, a baffle 23 and other accessories (not shown), usually providing polymerization vessels for polymerizing vinyl chloride. A line 24 connected to the top of the polymerization vessel 1 is a line for loading materials. Line 24 is connected to branch lines such as a vinyl chloride monomer (VCM) charging line 24a, a catalyst solution charging line 24b, a suspension agent charging line 24c, and a line pure water load 24d as shown in figure 2. These load lines 24 and 24a-24d are provided with valves VI, V2, V3, V4 and V5 in the positions shown in the drawing. A line 25 also connected to the top of the polymerization vessel 1 is provided for evacuating the interior of the polymerization vessel 1 and for recovering monomers, and is conducted to a gas support 27 via a line 26 branched from line 25. A monomer recovery line 28 is brought out of the gas holder 27, and a line 29 carried outside the gas holder 27 is connected to line 25 so that it can be used in the pressure equalization described below. These lines 25, 26, 28 and 29 are provided with valves V6, V7, V8, V9, VIO, VIL, V12 and V13. Line 26 branches into a line 26a provided with a vacuum pump 30, so that the monomers can be recovered, and a line 26b without any pump, and then the branched lines are joined together to form a single line which is connected to the gas support 27. To the top of the polymerization vessel, a line 31 is also connected to flush the interior of the polymerization vessel with water. Line 31 is provided with valves 14 in the position shown in the drawing, and has a nozzle 32 at the end inserted into the container. To the top of the polymerization vessel 1, a first coating liquid supply line 34 and a second coating liquid supply line 35 are connected to a coating liquid supply line 33 through valves, as shown in FIG. shows in the drawing. In addition, to line 33 a steam feed line 36 is connected by a valve. Line 33 is provided at its end located inside the container with a coating ring 4 to which coating nozzles 3a are fixed3b. These lines are provided with valves V15, V16, V17 and V18 in the positions shown in the drawing. The steam feed line 36 is provided with a valve 19 in the position shown in the drawing. At the bottom of the polymerization vessel 1, a line 37 is connected, which branches into a line 38a through which the monomer suspension is led to a descending blow tank, and a line 38b through the which coating liquids or washing water are discharged. The lines 38, 38a and 38b are provided with valves V20, V21 and V22 in the positions shown in the drawing. The coating liquors used in each experiment are shown by numbers in Table 5. The coating liquids were precoated onto the surface of the inner wall of the polymerization vessel and other surfaces in the manner as described below, optionally followed by dried to form a coating film. In the polymerization vessel, the vinyl chloride monomers are polymerized in the manner as described below. (1) Coating and drying: The coating film is formed on the surface of the inner wall and other surfaces of the polymerization vessel of the polymerization apparatus shown in Figure 2, by a method of a), b), c) od ) , as it's shown in the following. Methods a), b) and c) are methods of comparative examples. In the initial stage of each method, all the valves close. a) Spray coating and drying of a stage: Hot water is passed through the jacket 2 to keep the surface of the inner wall 1 of the polymerization vessel warm up to a temperature of 70 ° C (preheating time with the jacket) : 10 minutes) . Valves V17, V16, V15, V20 and V22 are opened, and the first coating liquid containing a polymer scale preventative is coated at a flow rate of 5 1 / min for 1.5 minutes. The valves V17, V16, V15, V20 and V22 are closed, and then the valves V6, V8, V13 and V9 are opened, where the vacuum pump 30 is operated to evacuate the interior to -700 mm Hg, and the Wet coating is dried (dried, if necessary, drying time: 25 minutes) to form a coating film. Then, the vacuum pump is stopped, and valves V8, V13 and V9 are closed. Then, the valves V7 and VIO are opened to make the internal pressure of the polymerization vessel 1 equal to the internal pressure of the gas support 27. Then, the valves V6, V7 and VIO are closed. The supply of hot water to the jacket 2 is interrupted. b) Spray coating and two-stage drying: Hot water is passed through the jacket 2 to keep the surface of the inner wall 1 of the polymerization vessel warm up to a temperature of 70 ° C (pre-heating time with the jacket : 10 minutes) . The valves V17, V16, V15, V20 and V22 are opened, and the coating liquid containing a polymer scale preventive agent (for lower coating) is coated at a flow rate of 5 1 / min for 1.5 minutes. The valves V17, V16, V15, V20 and V22 are closed, and then the valves V6, V8, V13 and V9 are opened, where the vacuum pump 30 is operated to evacuate the interior to -700 mm Hg, and the Wet coating is dried (dried, if necessary, drying time: 25 minutes) to form a first coat. Then, the vacuum pump is stopped, and valves V8, V13 and V9 are closed. Then, the valves V7 and VIO are opened to make the internal pressure of the polymerization vessel 1 equal to the internal pressure of the gas support 27. Then, the valves V6, V7 and VIO are closed. Then, the valves V18, V16, V15, V20 and V22 are opened, and the coating liquid containing a polymer scale preventative auxiliary agent (for topcoat) is coated on the first layer above at a flow rate of 5. 1 / min for 1.5 minutes. The valves V18, V16, V15, V20 and V22 are closed, and then valves V6, V8, V13 and V9 are opened, where the vacuum pump 30 is driven to evacuate the interior to -700 mm Hg, and the Wet coating is dried (dried, if necessary, drying time: 25 minutes) to form a second layer. Then, the vacuum pump is stopped, and valves V8, V13 and V9 are closed. Then, the valves V7 and VIO are opened to make the internal pressure of the polymerization vessel 1 equal to the internal pressure of the gas support 27. Then, the valves V6, V7 and VIO are closed. The supply of hot water to the jacket 2 is interrupted. c) One-stage steam coating (simultaneous drying): Hot water is passed through the jacket 2 to keep the internal surface of the polymerization vessel 1 warm up to a temperature of 70 ° C (pre-heating time with the jacket: 10 minutes) . Valves V19, V22, V20, V15 and V16 are opened, and 4 kgf / cm2 G (143 ° C) of steam are blown into the polymerization vessel 1 at a flow rate of 240 kg / hr for 3 minutes. After the interior of the container is preheated, the valve V17 is opened, and the coating liquid containing a polymer scale preventive agent is coated at a flow rate of 0.2 1 / min for 2 minutes, while the liquid is used. steam as a vehicle. Then, the valves V19, V22, V20, V15, V16 and V17 are closed. The supply of hot water to the jacket 2 is interrupted. d) Two-stage steam coating (simultaneous drying): (1) Coating and drying Hot water is passed through jacket 2 to keep the internal surface of polymerization vessel 1 warm up to a temperature of 70 ° C (time of preheating with the shirt: 10 minutes). The valves V19, V22, V20, V15 and V16 are opened, and 4 kgf / cm2 G (143 ° C) of steam are blown into the polymerization vessel 1 at a flow rate of 240 kg / hr for 3 minutes. After the interior of the container is preheated, valve V17 is opened, and the first coating liquid containing a polymer scale preventive agent (for bottom coating) is coated and dried simultaneously at a flow rate of 0.2 1 / min for 2 minutes, while steam is used as a vehicle to form a first layer. Then, valve 17 closes. Then the valve 18 is opened and, on the first layer, the coating liquid containing an auxiliary agent (for topcoat) is coated and dried simultaneously at a flow rate of 0.2 1 / min for 1 minute while the steam is used as a vehicle, to form a second layer on the first layer.

Then, the valves V19, V22, V20, V15, V16 and V18 are closed. The supply of hot water to the jacket 2 is interrupted. (2) Second water wash, inside the container: Valves V14, V20, V22, V6, V7 and VIO open to flush the interior of the polymerization vessel with water, and the wash water is discharged into a tank of water. waste water. Valves V14, V20 and V22 are closed. The washing time with water is four minutes when method a) or b) is used, and it is one minute when method c) or d) is used. (3) Charge .- Valves VI, V2 and V3 are opened, and 1 200 parts by weight of pure water, 0.022 parts by weight of partially saponified polyvinyl alcohol and 0.028 parts by weight of hydroxymethylcellulose are charged to the polymerization vessel. The valves VI, V2, V3, V6, V7 and VIO are closed. Afterwards, valves VI and V5 are opened, and loaded 100 parts by weight of vinyl chloride monomer (VCM). Then, valve V5 closes. Then, with the charged materials being agitated, valve V4 opens, and 0.03 parts by weight of t-butyl peroxine-decanate are loaded. Then valves VI and V4 close. (4) Polymerization: Hot water is passed through the jacket 2 to raise the temperature while stirring the charged materials. By the time the internal temperature has reached 52 ° C, cooling water is passed through the jacket 2 to maintain the internal temperature at 52 ° C, where the polymerization is carried out. By the time the internal pressure has dropped to 5 kg / cm, the polymerization ends. (5) Gas discharge: The valves V6, V8, V12 and V9 are kept open, and gas is discharged to the gas support 27 until the internal pressure returns to substantially atmospheric pressure.

Then, valves V12, V8 and V9 are closed. Then the valves VII and VIO are opened, and the monomers recovered in the gas holder 27 are sent to the recovery step of VMC.

Afterwards, the valves VII and VIO are closed. (6) Pressure equalization: The valves V7 and VIO are opened, and the internal pressure of the polymerization vessel 1 and the internal pressure of the gas support 27 (pressure equalization) are equal. (7) Extraction of the suspension: The valves V20 and V21 are opened, and the polymerization suspension is removed from the container to the down-blow tank (not shown). The polymerization suspension taken to the down-blow tank is then dehydrated and dried to a vinyl polymer product. (8) First wash inside the container: Valve V14 opens. The interior of the polymerization vessel is washed with water, and the washing water is sent to the down-blow tank. After, the V14 valves, V20, V21, V6, V7 and VIO are closed. During this washing of the interior of the vessel, hot water is passed through the jacket 2 to maintain the temperature of the wall surface of the polymerization vessel at 70 ° C. The operation from (1) coating and drying to (8) the first wash after the end of the polymerization, is established as batch 1 formation. The similar operation is repeated by the batching number, as shown in the box 6 < Evaluation > Time Required to Form Coating Films The time that is required for the formation of coating films in the examples and comparative examples is shown in Table 5.

Measurement of the amount of incrustation of polymer deposited In each experiment, after the final batch formation was completed, the accumulation of polymer scale in the liquid phase portion in the polymerization vessel was determined in the following manner, and the accumulation of polymer scale on the surfaces of stirring blades and baffles and in the vicinity of the boundary between the gas phase portion and the liquid phase portion. The incrustation deposited in an area of 10 cm x 10 cm on a surface to be measured, was detached by scraping with a spatula, completely as can be confirmed with the naked eye, and then the incrustation detached by scraping was weighed on a scale. The measured value was multiplied by 100 to obtain the amount of the polymer scale deposited per area of 1 m2. The results are given in table 7.

Measurement of fish eyes The fish eyes produced when a polymer product obtained in the final batch formation in each experiment is formed into a leaf, were measured by the following method. The results are given in Table 8. 100 parts by weight of a polymer obtained, 50 parts by weight of dioctyl phthalate (DOP), 1 part by weight of dibutyltin dilaurate, 1 part by weight of cetyl alcohol, 0.25 were mixed. parts by weight of titanium oxide and 0.05 parts by weight of carbon black. The resulting mixture was kneaded at 150 ° C for 7 minutes with 15.24 cm rolls, and then formed into a 0.2 mm thick sheet. The leaf obtained was examined for the number of fish eyes per 100 cm by light transmission.

Measurement of the luminosity index (L value) The measurement of the luminosity index (L value) of a sheet formed from a polymer obtained in each experiment was carried out in accordance with the following method. The results are given in Table 8. 100 parts by weight of a polymer obtained, 1 part by weight of a tin laurate stabilizing agent (TS-101, product of Akisima Chemical Co.) and 0.5 parts by weight of an organic cadmium complex stabilizing agent (C-100J, product of Katsuta Kako Co.), and 50 parts by weight of dioctyl phthalate as a plasticizer at 160 ° C for 5 minutes in a twin roll mill, and then formed on a thick Imm sheet. Subsequently, this sheet was placed in a molding structure measuring 4 x 4 x 1.5 cm, heated to 160 ° C under a pressure of 65 to 70 kgf / m to prepare a test specimen. This test specimen was measured for brightness index L in the following manner. First, the stimulus Y value of the XYZ color system is determined by photoelectric tristimulus colorimetry using the standard C light photoelectric colorimeter (color difference meter Model Z-1001DP, product of Nippon Denshoku Kogyo KK), in accordance with JIS Z 8722. As a geometric condition of lighting and light reception, the condition d defined in section 4.3.1 of JIS Z 8722 is adopted. Then, from the stimulus value Y obtained, the L value is calculated based on in the Hunter color difference equation: L = 10Y1 / 2 described in JIS Z 8730 (1980). The higher the value of L, the greater the whiteness that is evaluated, namely, the poorer the initial discoloration that is evaluated.

Examination of the colored particles: A mixture of 100 parts by weight of the polymer obtained in each experiment after the final batch formation was completed, 2 parts by weight of a TVS N-2000E stabilizer (available from Nitto Kasei Co., Ltd .), and 20 parts by weight of a dioctyl phthalate plasticizer, was fully kneaded and then placed in a casting structure of 160 mm x 130 mm x 3 mm, and subsequently molded under pressure at a temperature of 175 ° C. and at a pressure of 35 kg / cm2 to obtain a sample for examination. The samples thus obtained were examined visually based on the number of colored particles. The results are shown in table 8.

Measurement of the contact angles with respect to water after immersion in vinyl chloride monomer: Contact angles were also determined in the following manner with respect to the water of the surface of the first layer obtained after the first coating liquid was coated , and the surface of the second layer obtained after the second coating liquid was coated. a-1) Sample preparation for one-stage spray coating: Six 20 mm x 20 mm x 1 mm thick test pieces made of stainless steel (SUS 316L), are adhered at equal intervals along the circumference in the vicinity of a gas-liquid boundary surface of the inner wall of the polymerization vessel. Then, in accordance with the coating process (a) described above, a coating film is formed by a one-stage spray coating. Then, the test pieces are extracted from the polymerization vessel. These are designated as one-stage spray coating film test pieces. a-2) Preparation of samples for two-stage spray coating: i) Preparation of samples for first layer in two-stage spray coating: Test pieces are adhered in six positions on the surface of the inner wall of the polymerization vessel , in the same way as in a-1). Then, the coating process b) is followed, but only a first layer is formed in the polymerization vessel. Then, the test pieces are extracted from the polymerization vessel. These are designated as two-stage spray coating first layer test pieces. ii) Preparation of samples for second coating film coated in two-stage spray coating: Test pieces are adhered in six positions on the surface of the inner wall of the polymerization vessel, in the same manner as in a-1). Then, in accordance with coating process b), a first layer is formed in the polymerization vessel, and a second layer is further formed in said vessel. Then, the test pieces are extracted from the polymerization vessel. These are designated as two-stage spray coating film test pieces. a-3) Preparation of samples for one-stage vapor coating: Test pieces are adhered in six positions on the surface of the inner wall of the polymerization vessel, in the same manner as in a-1). Then, in accordance with the coating process c), a coating film is formed in the polymerization vessel. Then, the test pieces are extracted from said container. These are designated as one-stage vapor coating film test pieces. a-4) Preparation of samples for two-stage steam coating: i) Preparation of samples for first layer in two-stage steam coating: Test pieces are adhered in six positions on the surface of the inner wall of the polymerization vessel , in the same way as in a-1). Then, the coating process d) is followed, but only a first layer is formed in the polymerization vessel. Then, the test pieces are extracted from said container. These are designated as two-stage vapor coating layer test pieces. ii) Preparation of samples for second coating film coated in two-stage steam coating: Test pieces are adhered in six positions on the surface of the inner wall of the polymerization vessel, in the same manner as in a-1). Then, in accordance with the coating process d), a first layer is formed, and a second layer is further formed in the polymerization vessel. Then, the test pieces are extracted from said container. These are designated as two-stage vapor coating film test pieces.

Immersion of test pieces coated in vinyl chloride monomer: A pressure resistant 2 liter container is used, which has a stirrer and on the surface of the inner wall of which slots are provided to which the test pieces. The test pieces on which the coating films have been formed in the manner as described above, are adapted to the grooves of the pressure-resistant container to fix them to the surface of the inner wall of the container, in such a manner that its coated surfaces look inward (so that they appear on the surface of the inner wall). In the pressure-resistant container, to which surface of the inner wall the test pieces have been fixed in this way, 600 g of water and 600 g of vinyl chloride monomer are charged, and thus the test pieces are submerged in these contexts. Then, the contents of the pressure-resistant container are heated to 50 ° C with stirring, and stirring is continued for 1 hour at the temperature maintained at 50 ° C. Afterwards, the contents are cooled to room temperature. Simultaneously, the recovery of the vinyl chloride monomer present in the pressure resistant vessels is initiated. After the recovery of the vinyl chloride monomer is complete, water is withdrawn from the interior of the pressure resistant container. Then, the test pieces are separated from the surface of the inner wall of said container, and then dried in a vacuum dryer at a drying temperature of 50 ± 1 ° C for a drying time of 2 hours. After the test pieces have been dried, they are taken to a desiccator, and left there at 20 ° C for 24 hours. Thus, test pieces were obtained to measure the contact angles with respect to water.

Measurement of the contact angles with respect to the water The contact angles were measured with respect to water in the test pieces thus obtained, in air at a site at 20 ° C by the drip method, using a contact angle meter (Model CA-A, manufactured by Kyowa Kaimen Kagaku KK). The contact angles were measured at five points for each test piece, and an average value of the measurements was determined on six test pieces, which was considered as the contact angles with respect to the water of the coating films obtained in the test. experiment.

TABLE 5 TABLE 5 (CONTINUED) TABLE 6 TABLE 6 (CONTINUED) Comparative examples, TABLE 7 TABLE 7 (CONTINUED) TABLE 7 (CONTINUED) Comparative examples, TABLE 8 Accumulation of the incrustation and quality of the product TABLE 8 (CONTINUED) Comparative examples EXAMPLE 2 In experiments Nos. 201 to 207, the polymerization was repeated until the formation of batch 250, under the same conditions as experiments Nos. 101, 103 *, 105 *, 107, 111, 113 and 128, respectively. Here, a series of the operation of (1) coating and drying to the first (8) wash after the end of the polymerization was established as batch formation. The similar operation was repeated until the formation of batch 250. Then, the amount of scale, fish eyes, brightness index and the number of colored particles were measured in the same way as in example 1. The results are as shown in table 9.

TABLE 9 TABLE 9 (CONTINUED) *: Comparative examples.

Claims (19)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for producing a polymer by polymerizing in a polymerization vessel a monomer having an ethylenic double bond, characterized in that said polymerization vessel has a film of preventive coating of polymer inlay on the surfaces of its inner wall and other surfaces with the which the monomer comes in contact during the polymerization; said coating film comprising a first layer formed on said inner wall surfaces and other surfaces, and a second layer formed on the first layer; said first layer being formed by coating a first a coating liquid containing a compound containing a conjugated bond B selected from the group consisting of an aromatic compound having 5 or more conjugated B bonds and a heterocyclic compound having 5 or more B bonds conjugated by means of steam as a vehicle, and said second layer being formed by coating a second coating liquid on the first layer by means of steam as a vehicle; and said second layer having a surface having a contact angle with respect to water of less than 60 ° after its surface has been brought into contact with a solution of mixing water and a vinyl chloride monomer in a weight ratio of 1: 1 at 50 ° C for 1 hour.

2. - The method according to claim 1, further characterized in that said contact angle with respect to water varies from 10 to 55 °.

3. The method according to claim 1, further characterized in that the first layer that has been formed has a surface that has a contact angle with respect to water of 60 ° or more after the surface has been put in contact with a solution of a mixture of water and a vinyl chloride monomer in a weight ratio of 1: 1 at 50 ° C for 1 hour.

4. The method according to claim 1, further characterized in that said compound containing a conjugated B-bond contained in the first coating liquid is a condensation product of aromatic compound having an average molecular weight-weight of 500 or more. .

5. The process according to claim 4, further characterized in that said condensation product of aromatic compound has an average molecular weight-weight of 500 to 70,000.

6. The process according to claim 4, further characterized in that said condensation product of aromatic compound is selected from the group consisting of condensation products of aldehyde compound / aromatic hydroxyl compound, condensation products of pyrogallol / acetone, self-condensing products of polyhydric phenol, self-condensing products of polyhydric naphthol, condensation products of aromatic amine compound, condensation products of quinone compound, and sulfur compounds of aromatic hydroxyl compounds.

7. The process according to claim 4, further characterized in that said condensation product of aromatic compound is a condensation product of aldehyde compound / aromatic hydroxyl compound or a condensation product of quinone compound.

8. The process according to claim 1, further characterized in that said first coating liquid is a solution containing a compound selected from the group consisting of pyrogallol / acetone condensation products, self-condensation products of polyhydric phenol, and self-condensing products of polyhydric naphthol in water or a mixed solvent of water with a hydrophilic organic solvent miscible with water, and having a pH of 2.0 to 6.5.

9. - The method according to claim 1, further characterized in that said first coating liquid is a solution containing a compound selected from the group consisting of condensation products of aldehyde compound / aromatic hydroxyl compound, condensation products of an aromatic amine compound, and condensation products of a quinone compound in water or a mixed solvent of water with a hydrophilic organic solvent miscible with water, and having a pH of 7.5 to 13.5.

10. - The method according to claim 1, further characterized in that said first coating liquid contains the compound containing the conjugated bond B at a concentration ranging from 1.0 to 25.0% by weight.

11. The process according to claim 1, further characterized in that said second coating liquid contains a hydrophilic compound selected from the group consisting of water-soluble polymeric compounds, inorganic colloids, salts and inorganic acids, the second resulting layer thus containing the same .

12. - The process according to claim 1, further characterized in that said second coating liquid contains a water-soluble polymeric compound selected from the group consisting of polymeric compounds containing water-soluble hydroxyl group, water-soluble amphoteric polymeric compounds, water-soluble anionic polymer compounds and compounds water-soluble cationic polymer, the second resulting layer thus containing the same.

13. - The method according to claim 1, further characterized in that said second coating liquid contains a compound selected from the group consisting of alkali metal silicates and inorganic alkaline earth metal salts, the second resulting layer thus containing the same.

14. The process according to claim 1, further characterized in that said second coating liquid contains methylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, polyvinyl alcohol, partially saponified polyvinyl alcohol, glue, casein, gelatin, chitosan, polyacrylic acid, alginic acid, acid polymethacrylic, pectic acid, carrageenan, hyaluronic acid, carboxymethylcellulose, polyvinylpyrrolidone or a styrene-maleic anhydride copolymer; or a colloid of oxides or hydroxides of metals selected from aluminum, titanium, zirconium, tin and iron, or colloidal silica; or magnesium carbonate, calcium carbonate, magnesium phosphate, calcium phosphate, calcium pyrophosphate, calcium acid pyrophosphate, barium phosphate, calcium sulfate, calcium borate, magnesium hydroxide, calcium hydroxide, barium hydroxide , magnesium chloride or calcium chloride; or a combination of 2 or more thereof, the second resulting layer thus containing the same.

15. The process according to claim 8, further characterized in that the second coating liquid contains said hydrophilic compound in a concentration ranging from 0.01 to 20% by weight in water or a mixed solvent of water with a hydrophilic solvent miscible with water.

16. The process according to claim 1, further characterized in that said steam used in the application of said first coating liquid, and said steam used in the application of said second coating liquid, have a temperature of 120 to 260 °. C and a pressure of 2 to 35 kgf / cm2 G.

17. The process according to claim 16, further characterized in that said vapors have a temperature of 130 to 200 ° C and a pressure of 2.8 to 20 kgf / cm2 G

18. The method according to claim 1, further characterized in that in both applications of said first coating liquid and said second coating liquid, the coating liquid (L) and the vapor (G) are mixed in a ratio (L / G) from 0.01 to 1.0 in terms of flow rate ratio based on weight.

19. - The method according to claim 18, further characterized in that said L / G ratio is in the range of 0.03 to 0.2. SUMMARY OF THE INVENTION An improved process for producing a polymer is provided by polymerizing a monomer having an ethylenic double bond in a polymerization vessel having a polymer scale preventative coating film on the surfaces of its inner wall, etc .; the coating film is formed by coating a first coating liquid containing a compound selected from the group consisting of an aromatic compound having 5 or more conjugated B-bonds and a heterocyclic compound having 5 or more conjugated B-bonds, and then coating a second coating liquid on the first layer; the first and second coating liquids are applied by means of steam as a vehicle; the second layer has a surface having a contact angle with respect to water of less than 60 ° after its surface has been brought into contact with a solution of mixing water and a vinyl chloride monomer at a weight ratio of 1 : 1, at 50 ° C for 1 hour; this process can shorten the time to form the coating film to improve productivity, and can also improve the preventive effect of polymer scale adhesion, it can cause the colored particles to mix less in the polymer products obtained by this process, it can reduce fish eyes and the initial discoloration of the products formed, and can improve the quality of polymer products and their formed and molded products. EA / MG / xal * asg * amm * mvh * mmr * ram * aom. P98-1643.