JPH02138302A - Method for preventing polymer scale adhesion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for preventing polymer adhesion to the inner wall surface of a polymerization vessel during the polymerization of a monomer having an ethylenic double bond.

[Conventional technology]

BACKGROUND ART In a method of producing a polymer by polymerizing monomers in a polymerization vessel, there is a known problem that the polymer adheres as scale to the inner wall surface of the polymerization vessel. If polymer scale adheres to the inner wall surface of the polymerization vessel, the yield of the polymer, the cooling capacity of the polymerization vessel will decrease, and the quality of the product polymer will deteriorate due to the adhered polymer scale peeling off and contaminating the product. Furthermore, there are disadvantages such as a great deal of effort and time being required to remove the polymer scale.

Conventionally, as a method for preventing polymer scale from adhering to the inner wall surface of a polymerization vessel, for example, a method of applying polar compounds, dyes, pigments, etc. to the inner wall surface (Japanese Patent Publication Nos. 45-30343 and 45-30835) has been used. , a method of applying an aromatic amine compound (JP-A-51-50887), a method of applying a reaction product of a phenolic compound and an aromatic aldehyde (JP-A-55-54317), and the like have been proposed.

These are effective in preventing the adhesion of polymers in the polymerization of halogenated vinyl monomers such as vinyl chloride or monomer mixtures mainly composed of such monomers and containing small amounts of monomers copolymerizable therewith.

[Problem to be solved by the invention]

However, when the monomers subjected to polymerization are monomers having other ethylenic double bonds such as styrene, α-methylstyrene, acrylic esters, acrylonitrile, etc., these monomers are Because it has an extremely high dissolving ability for the coating film formed by the anti-adhesion method, part or all of the coating film is dissolved and lost, and as a result, it effectively prevents the polymer from adhering to the inner wall surface of the polymerization vessel. cannot be prevented.

Therefore, the present invention aims to provide a method that can effectively prevent polymer adhesion in the polymerization of not only halogenated vinyl monomers but also monomers having a wide range of ethylenic double bonds. be.

[Means to solve the problem]

The present inventors have discovered that the above object can be achieved by applying two groups of specific compounds in two stages to the inner wall surface of a polymerization vessel.

That is, the present invention solves the above-mentioned problems by providing a method for preventing the deposition of polymer scale during the polymerization of monomers having ethylenic double bonds in a polymerization vessel, the method comprising: 1. A method for preventing the adhesion of a polymer in the polymerization of a monomer having a double bond, the method comprising: first applying (a) A coating solution containing a cationic dye (hereinafter referred to as coating solution (a)) is applied, and then the resulting coating film is coated with (b) an anionic polymer compound, an amphoteric polymer compound, and a hydroxyl group-containing organic compound. Coating liquid (hereinafter referred to as coating liquid [
The present invention provides a method for preventing the adhesion of polymers, which comprises carrying out the polymerization in a polymerization vessel coated with a polymer.

Examples of the cationic dye contained in the coating liquid (a) used in the present invention include C,1, Paysic Red 2,
C,1, azine dye such as Paysic Blue 16, C,1, Paysic Black 2, C,1, Solvent Black 5,7, C,1, acridine dye such as Paysic Orange 14°15, C,1 , Paysic Blue 1.5,
7,26,C,1,Pasic Violet 3.14
Triphenylmethane dyes such as C,I.

Thiazine dyes such as Paysic Blue 9.24.25 ic, l Paysic Yellow 1, C,1, Paysic Green 5, C,1, Paysic Red 12, C,I.

Methine dyes such as Basic Yellow 11, C,1 Basic Yellow 2, C,1, Solvent Violet 8
Diphenyl and triphenylmethane dyes such as C,1, Solvent Blue 2.73; oxazine dyes such as C,1, Solvent Blue 6.12; C,1, Solvent Yellow 2.6.14,15°16. 19, 21, 5
6iC, I, Solvent Red 1.8, 23, 24, 2
5, 27, 100, 109, 121 ic, 1. Azo dyes such as Solvent Brown 3,520, 37 ic, L Solvent Black 3,22°23; C, 1, Paysic Orange 2iC, 1, Paysic Brown 1;
Xanthine dyes such as C,I, Paysic Violet 10, C,1, Paysic Red 1, phthalocyanine dyes such as C,1, Solvent Blue 55, C,! , Solvent Blue L 1. 12. 36, C, 1, Solvent Violet 1, 13. l 4 ;C,1
, Deathverse Violet, C,1, Solvent Green 3, and other anthraquinone dyes.

Among the above-mentioned cationic dyes, C,1 and Solvent Black 5,7 are preferred.

The coating liquid (b) needs to contain at least one selected from the group consisting of anionic polymer compounds, amphoteric polymer compounds, and hydroxyl group-containing organic compounds.

Examples of the anionic polymer compound that can be used in the present invention include sulfomethylated polyacrylamide; polyacrylic acid; alginic acid, acrylamide-vinylsulfonic acid copolymer, polymethacrylic acid, polystyrene sulfonic acid, etc., or alkali metal salts thereof. or ammonium salts; and those having a carboxyl group or sulfonic acid group in the side chain such as carboxymethylcellulose;
and anionic polymer compounds such as alkali metal salts thereof.

Among the above-mentioned anionic polymer compounds, polyacrylic acid, carboxymethylcellulose carboxylic acid sodium salt, or sulfonic acid sodium salt are preferred.

Examples of amphoteric polymer compounds include glue, gelatin, casein, albumin, and the like.

Among these, gelatin is preferred.

In addition, as organic compounds containing hydroxyl groups,
For example, phenol and its derivatives, naphthalene and its derivatives, anthracene and its derivatives, phenanthrene and its derivatives, oxynaphthoquinones and related compounds, anthraquinone and its derivatives, heterocyclic compounds containing hydroxyl groups, tartaric acid, lactic acid, apple Examples include aliphatic oxyacids such as acids, aliphatic alcohols such as glycerin, and the like.

Phenol derivatives include catechol, resorcinol,
Phloroglucin, gallein, phloroglucide, fluoroacetanilide, hydroquinone, bisphenol A, butylhydroxyanisole, p-tert-butylcatechol, P-hydroxyanisole, 2,5-diter
t-Butylhydroquinone, pyrogallol, pyrogallol-1-methyl ether, pyrogallol-2-methyl ether, pyrogallol-1,3-dimethyl ether, p
-hydroxydiphenyl, octadecyl-3-(3,5
-G-tert 7'thyl-4-hydroxyphenyl)propionate, dibutylhydroxytoluene, phenol-2-sulfonic acid, phenol-3-sulfonic acid, phenol-4-sulfonic acid, phenol-2,4-
Disulfonic acid, phenol-2,5-disulfonic acid, phenol-2,4,6-)disulfonic acid, resorcinol-
4-sulfonic acid, 2-aminophenol-4-sulfonic acid, 4-oxydiphenylamine, p-oxypropiophenone, 2.3-dioxyacetophenone, 2.4-
Dioxyacetophenone, 2-oxy-4-methoxyacetophenone, 2.5-dioxyacetophenone, 2.
6-dioxyacetophenone, 3.4-dioxyacetophenone, 4-oxy-3-methoxyacetophenone,
3.5-dioxyacetophenone, dioxypropiophenone, dioxymethylacetophenone, 2,3.4=
Trioxyacetophenone, 2.4.5-trioxyacetophenone, 2.4.6-) dioxyacetophenone, 3.4.5-) dioxyacetophenone, 2.6
-Syoxy-4-methylbenzoic acid, 0-oxybenzoic acid, m-oxybenzoic acid, p-oxybenzoic acid, 2.3-
Dioxybenzoic acid, 3,5-dioxybenzoic acid, 2,4
-dioxybenzoic acid, 2,5-dioxybenzoic acid, 3,
4-methylenedioxybenzoic acid, 3,4.5-trioxybenzoic acid (gallic acid), 2.3.4- ) dioxybenzoic acid, 2,4.6-1-dioxybenzoic acid, 2.4
．． 5-) Dioxybenzoic acid, 3oxy-2-methylbenzoic acid, 4,6-cyoxy-2-methylbenzoic acid, gallotannin, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 3-oxyphthalic acid, 4 −
Oxyphthalic anhydride, 3,6-dioxyphthalic acid, 5
-oxy-3-methylphthalic acid, 3,4-dioxyphthalic acid, 4,5-dioxyphthalic acid, 3,4.5-1-dioxyphthalic acid, 2-oxyisophthalic acid, 4-oxyisophthalic acid, 5-oxyisophthalic acid , 4゜6-dioxyisophthalic acid, 4.5-dioxyisophthalic acid, 2
, 4.6-) Dioxyisophthalic acid, 4゜5.6-1
Lioxyisophthalic acid, oxyterephthalic acid, 2.5-
Dioxyterephthalic acid, 2,3-dioxyterephthalic acid, 3,5-dioxyterephthalic acid, 3-oxy-4-sulfobenzoic acid, 4-oxy-3-sulfobenzoic acid, 3-
Aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 2-oxydiphenylmethane, 4-oxydiphenylmethane, 2.4-dioxydiphenylmethane,
2.4'-dioxydiphenylmethane, 4.4'-dioxydiphenylmethane, 2-oxytoluene-4-sulfonic acid, 2-oxytoluene-5-sulfonic acid, 4-oxytoluene-6-sulfonic acid, 4- Oxytoluene-
2-sulfonic acid, 4-oxytoluene-3-sulfonic acid, 3-oxytoluene-4-sulfonic acid, 3-oxytoluene-6-sulfonic acid, pyrocatechin-4-sulfonic acid, 1-oxy-2-methoxy Benzene-4-sulfonic acid, resorcin-4,6-disulfonic acid, 1.2.3-
Trioxybenzene-4-sulfonic acid, 1,3.4trioxybenzene-5-sulfonic acid, 112-dioxybenzene-3,5-disulfonic acid, hydroquinonesulfonic acid, hydroquinone-2,5-disulfonic acid, N -Phenylhydroxylamine, N-nitrosophenylhydroxylamine, N-benzenesulfonyl-N-phenylhydroxylamine, tolylhydroxylamine, N-formyl-N-phenylhydroxylamine, 2-amino-2oxytoluene, 4-amino-2 -oxytoluene, 5-amino-2-oxytoluene, 2-amino-3-
Oxytoluene, 4-amino-3-oxytoluene, 6
-Amino-3-oxytoluene, 2-amino-4-oxytoluene, 3-amino-4-oxytoluene, 3-aminocatechol, 4-aminocatechol, 2-aminohydroquinone, 0-oxyaminobenzoic acid, m-oxy Aminobenzoic acid, p-oxyaminobenzoic acid, 2-oxyaminoterephthalic acid, 5-oxyaminoterephthalic acid, 3
-aminoguaiacol, 6-aminoguaiacol, 4-
Aminoguaiacol, 5-aminoguaiacol, 3-aminoveratrol, 4-aminoveratrol, 2-amylsorcin, 4-amylsorcin, 5-amylsorcin, 2,4-diaminophenol, 2.5-diaminophenol, 435-diaminophenol , 3,4-diaminophenol, 2,6-diaminoanisole, 3.5-
Diaminophenol, 2,4-diaminoanisole, 4
．． Examples include 6-diamylsorcin, phenylhydroxylamine-3-sulfonic acid, 4-oxyaminotoluene-2-sulfonic acid, P-oxyphenylhydrazine, 2,5-dioxynyl-benzoquinone, and tetraoxybenzoquinone.

Examples of naphthalene derivatives include α-naphthol, β
-Naphthol, 1.2-dioxynaphthalene, 1.3-
Dioxynaphthalene, 1,4-dioxynaphthalene, 1
．． 5-Dioxynaphthalene, 1.6=Dioxynaphthalene, 1.7-Dioxynaphthalene, 1.8-Dioxynaphthalene, 2.3-Dioxynaphthalene, 2.6-Dioxynaphthalene, 2,7- Dioxynaphthalene, 1,2
．． 3-trioxynaphthalene, 1.2.4-1-dioxynaphthalene, 1,4.5-trioxynaphthalene, 1
, 2,3.4-tetraoxynaphthalene, 1,4.5.
8-tetraoxynaphthalene, 1,2°3.4,5.8
-hexaoxynaphthalene, 1,2,3.4,5°10
-hexahydroxynaphthalene, 1,2,3,4.9.
10-hexahydroxynaphthalene, 1,2.4-aminonaphtholsulfonic acid, 3,4-dihydroxynaphthalene-1,2-dicarboxylic acid, 4-mercapto-1-naphthol, 1-naphthol-4-sulfonic acid, 2- naphthol-1-sulfonic acid, 2-naphthol-8-sulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-
6,8-disulfonic acid, 2-naphthol-3,6-disulfonic acid, 2-naphthol-3,6,8-trisulfonic acid, 2-naphthol-1,3,6-trisulfonic acid; 2-
Oxy-1-naphthaldehyde, 4-oxy-1-naphthaldehyde, 5-oxy-1-naphthaldehyde, 1-
Oxy-2-naphthaldehyde, 3-oxy-2-naphthaldehyde, 4-oxy-2-naphthaldehyde, 6
-oxy-2-naphthaldehyde, 2,3-dioxy-
1-naphthaldehyde, 2゜4-dioxy-1-naphthaldehyde, 2.5-dioxy-1-naphthaldehyde, 2.6-dioxy-1-naphthaldehyde, 2,7-cyoxy-1-naphthaldehyde, 2.8 -dioxy-1
-naphthaldehyde, 3,4-dioxy-1-naphthaldehyde, 4,5-dioxy-1-naphthaldehyde,
4,6-dioxy-1-naphthaldehyde, 4,7-dioxy-1-naphthaldehyde, 4,8-dioxy-1-
Naphthaldehyde, 1,4-dioxy-2-naphthaldehyde, 1,5-dioxy-2-naphthaldehyde; 2
-oxy-1-naphthoic acid, 3-oxy-1-naphthoic acid, 4-oxy-1-naphthoic acid, 5-oxy-1-naphthoic acid, 7-oxy-1-naphthoic acid, 1-oxy-
2-naphthoic acid, 3-oxy-2-naphthoic acid, 3-oxy-2-naphthoic acid anilide, 1-acetyl-2-oxynaphthalene, 1-acetyl-4-oxynaphthalene, 2-acetyl-1-oxynaphthalene , 2-acetyl-4-oxynaphthalene, 2-acetyl-6-oxynaphthalene, l-oxy-2-propionylnaphthalene,
Examples include 1-benzoyl-2-oxynaphthalene and 1-benzoyl-4-oxynaphthalene.

Examples of anthracene derivatives include ■-oxyanthracene, 2-oxyanthracene, 9-oxyanthracene, 1,2-dioxyanthracene, 1,4-dioxyanthracene, 1,5-dioxyanthracene, 1
．． 8-dioxyanthracene, 2.3-dioxyanthracene, 2,6-dioxyanthracene, 2.7-dioxyanthracene, 1.9-dioxyanthracene, 9
．． Examples include 10-dioxyanthracene and 10-benzoylanthranol.

Examples of phenanthrene derivatives include l-oxyphenanthrene, 2-oxyphenanthrene, 3-oxyphenanthrene, 4-oxyphenanthrene, 7-oxyphenanthrene, 9-oxyphenanthrene, IO-chloro-9-phenanthrol, 10-bromo- 9-phenanthrol, 9-nitro-3-phenanthrol, 4
-amino-1-phenanthrol, 1-amino-2-phenanthrol, 4-amino-3-phenanthrol,
10-Amino-9-phenanthrol, 10-benzenezo-9-phenanthrol, 1,2-dioxyphenanthrene, 1.4-dioxyphenanthrene, 1.6-
Dioxyphenanthrene, 1,7-dioxyphenanthrene, 2,3-dioxyphenanthrene, 2,5-dioxyphenanthrene, 2,6-dioxyphenanthrene, 2,7-dioxyphenanthrene, 3,4-dioxy Phenanthrene, 3,6-dioxyphenanthrene, 3
．． 10-Dioxyphenanthrene.

9.10-Dioxyphenanthrene, 2.3.5.6-
Titraoxyphenanthrene, 2-oxyphenanthrene-1,4-quinone, 3-oxyphenanthrene-1,
4-quinone, 1-oxyphenanthrene-910-quinone, 2-oxyphenanthrene-9,10-quinone, 3
-oxyphenanthrenequinone, 4-oxyphenanthrenequinone, 2-oxyretinquinone (2-hydro
xyretenequinone), 3-oxyretinquinone, 6-oxyretinquinone, 2-oxy-3,
4-dinitrophenanthrenequinone, 4-oxy-2,
3-dinitrophenanthrenequinone, 4-amino-1-
Oxyphenanthrenequinone, 2-amino-3-oxyphenanthrenequinone, 1-nitroso-1-naphthol, 2-nitroso-1-naphthol, 4-nitroso-1-
Examples include naphthol.

Examples of oxynaphthoquinones and related compounds include 3-oxy-1,2-naphthoquinone, 4oxy-1,
2-naphthoquinone, 5-oxy-1゜2-naphthoquinone, 6-oxy-1,4-naphthoquinone, 6-oxy-1
, 2-naphthoquinone, 7-oxy-1,2-naphthoquinone, 2-oxy-1,4-naphthoquinone, 2,3-dioxy-1,4-naphthoquinone, 2,3-dioxy-6-methyl-1,4- Naphthoquinone, 2,6-cyoxyl.
4-naphthoquinone, 2,5-dioxy-3-methyl-1
, 4-naphthoquinone, 2,7-cyoxy-1,4-naphthoquinone, 2,8-dioxy-3-methyl-1,4-naphthoquinone, 2,5-dioxy-1,4-naphthoquinone, 5,8-dioxy- 2-Methyl-1,4-naphthoquinone, 2,8-dioxy-1,4-naphthoquinone, 5.6
-cyoxy-1,4-naphthoquinone, 5,8-dioxy-1,4-naphthoquinone, 6,7-cyoxy-1,4-
Naphthoquinone, 2,3.6-) Rioxy 1,4-naphthoquinone, 2.5.8-) Rioxy 3-methyl-1,4-naphthoquinone, 2,5.8-trioxy-1,
4-naphthoquinone, 2,3,5.8-tetraoxy-1
, 4-naphthoquinone, 2,3,6.8-tetraoxy-
Examples include 1,4-naphthoquinone.

Examples of anthraquinone derivatives include 1-oxyanthraquinone, 2-oxyanthraquinone, 1,2-dioxyanthraquinone, 1,3-dioxyanthraquinone, 1,4-dioxyanthraquinone/1,5-dioxyanthraquinone, 1 , 6-dioxyanthraquinone,
1.7-dioxyanthraquinone, 1.8-dioxyanthraquinone, 2,3-dioxyanthraquinone, 2.
6-dioxyanthraquinone, 2,7-dioxyanthraquinone, 1,2,3-trioxyanthraquinone, 1
, 2.4-trioxyanthraquinone, 1,2.5-
) dioxyanthraquinone, 1,2.6-1-dioxyanthraquinone, 1.2.7-) dioxyanthraquinone, 1,2.8-trioxyanthraquinone, 1,4.
5-trioxyanthraquinone, 1,4.6-) dioxyanthraquinone, 1,2.3.4-tetraoxyanthraquinone, 1.2,4.6-tetraoxyanthraquinone, 1,2,5.6-tetra Oxyanthraquinone, 1,2.5.8-tetraoxyanthraquinone, 1,
2,6.7-tetraoxyanthraquinone, 1,2,7
．． 8-tetraoxyanthraquinone, 1,3,5.7-
Examples include tetraoxyanthraquinone, L4,5.8-tetraoxyanthraquinone, 1.2,3.5.7-pentaoxyanthraquinone, and the like.

As the heterocyclic compound containing a hydroxyl group, examples of the oxygen-containing heterocyclic compound include belargonidine,
Anthocyanins such as cyanidin, delphinidin, peonidin, malvidin, hirsutidine, monardin, abigenin; coumarons such as sakuranetin, boncillin, neohesveridin, fuscin, callanin, taxifolin, ambebutin; catechin, epicatechin, gallocatechin, epigallocatechin, epiafzelechin, etc. Catchkins; xanthones such as mangiferin, liquexanthone, and labenelin; xanthines such as α-orcinophthalene, launin, eosin, and erythrosin; and the like. Examples of nitrogen-containing heterocyclic compounds include dioxindole, 3-indoglycerin, 3-methyl-5
, 6-dioxindole and other indoles. Examples of the sulfur-containing heterocyclic compound include thiophenes such as 2゜3-dioxythiophene and 3-oxy-4-diophenecarboxylic acid; and thianaphthenes such as 3-oxy-2-thianaphthenecarboxylic acid. It will be done.

Among the organic compounds containing hydroxyl groups mentioned above,
Gallotannins and catechol are preferred.

In a preferred embodiment of the present invention, coating liquid (a)
further contains at least one selected from the group consisting of anionic dyes, metal salts, and inorganic colloids. According to this embodiment, the effect of preventing scale formation is further enhanced.

Examples of the anionic dye that can be used as a component of the coating liquid (a) include C,1, Acid Yellow 38
iC, 1, Acid Red 1B, 52, 73° 80,
87 ;C,! , acid violet 11°78iC
,1, Acid Blue 1.40,59゜113.116
, 120.158; C, 1, Acid Orange 3. 7
;C, 1, acid black 1.2°124 ;C,
1, Direct Orange 2, 10, 26°97iC,!
, Direct Red 1,31,92°186 ,C,1
, Direct Violet 1, 22; C, 1, Direct Blue 1.6, 71, 86106; C, R, Direct Black 2, 19.32° 38, 77; C, 1
, Direct Green 1, 26; C, 1, Direct Yellow 1. C, 1, Direct Brown 1. 37.
101; C, 1, Food Yellow 3: C, 1, Reactive Yellow 3ic, l Reactive Blue 2. 4
．． 1 B, C,! , Mordant Violet 5;C
，! , Mordant Black 5iC, Mordant Yellow 26iC, 1, Fluorescent Brightening Agent 30. 32; C,1, Solbilized Butt Black 1; C,1, Azoic Brown 2, and the like. These may be used alone or in combination of two or more. Among these, C0■ and Acid Black 2 are preferred.

When an anionic dye is used as a component of the coating liquid (a), the weight ratio of anionic dye/cationic dye in the coating liquid (a) is usually 100/10.1 to 100/10.
00, more preferably 100/3 to 100/250. If this weight ratio is too small, the dye in the coating solution (a) will coagulate and precipitate, making it difficult to obtain a uniform coating film.
If the size is too large, even if the coating liquid is applied to the inner wall surface of the polymerization vessel and dried, there is a risk that the coating film will be dissolved by washing with water.

Metal salts used as components of coating liquid (a) include:
For example, alkali metals such as sodium and potassium; alkaline earth metals such as magnesium, calcium, and barium; zinc group metals such as zinc; aluminum group metals such as aluminum; tin group metals such as titanium and tin; Iron group metals; chromium group metals such as chromium and molybdenum; manganese group metals such as manganese; copper group metals such as copper and silver; silicates, carbonates, and phosphates of metals such as platinum group metals such as platinum; sulfates, nitrates, borates, acetates, hydroxides,
Examples include oxides and halides. Furthermore, examples of inorganic colloids that can be used as a component of the coating liquid (a) include gold colloid, silver colloid, sulfur colloid, ferric hydroxide colloid, stannic acid colloid, silicate colloid, and manganese dioxide colloid. , mechanical crushing of molybdenum oxide colloid, barium sulfate colloid, vanadium pentoxide colloid, aluminum hydroxide colloid, lithium silicate colloid, etc., ultrasonic irradiation,
Mention may be made of colloids prepared by electrical dispersion, chemical treatment, etc.

Among the metal salts and inorganic colloids mentioned above, ferric hydroxide colloids and aluminum hydroxide colloids are preferred.

When a metal and/or inorganic colloid is used as a component of coating liquid (a), the proportion with at least one selected from cationic dyes/metal salts and inorganic colloids is usually
The weight ratio is preferably in the range of 10010.1 to 1001500, particularly preferably 10015 to 100/200. When this weight ratio is within the above range, the adhesion of the coating film to the inner wall surface of the polymerization vessel will be strong. Further, the total concentration of these components in the coating liquid (a) is not particularly limited as long as the coating amount described below can be obtained, but it is usually preferably about 0.001 to 5%. The dry coating weight of the coating film obtained in this way is usually preferably from o,oot to 5 g/m''.

In one of the most preferred embodiments of the present invention, the coating liquid (a) contains an anionic dye as well as a cationic dye;
At least one selected from the group consisting of metal salts and inorganic colloids. In this embodiment, even higher scale adhesion prevention effects are achieved.

In the method of the present invention, the coating solution (
Apply a) to the inner wall surface of the polymerization vessel and other parts that come into contact with the monomer during polymerization, such as the stirring shaft and stirring blades. Coating liquid (
A) is prepared by dissolving or dispersing one or more of the above-mentioned components in a suitable solvent to a concentration of 0.01 to 5% by weight. This coating liquid (a) may be applied to the inner wall of the polymerization vessel, etc., and then dried at a temperature of about room temperature to 100°C. Solvents used to prepare the coating solution (a) include water and water-miscible solvents, such as alcohol solvents such as methanol, ethanol, and n-propyl alcohol; ketone solvents such as acetone and methyl ethyl ketone; methyl formate. , ester solvents such as methyl acetate; aprotic solvents such as dimethylformamide, dimethyl sulfoxide, and acetonitrile; aliphatic hydrocarbon solvents such as n-hexane and n-pentane; aromatic hydrocarbon solvents such as toluene and xylene. , 1,1.1-trichloroethylene, 1,1
, halogenated hydrocarbon solvents such as 1,2-tetrachloroethylene; ether solvents such as tetrahydrofuran and 1,4-dioxane. These solvents can be used alone or as a mixed solvent of two or more.

Next, coating liquid (b) is applied onto the coating film of coating liquid (a) thus formed. In this coating operation, for example, the coating liquid (b) is prepared by dissolving one or more of the above-mentioned components in an appropriate solvent to a concentration of, for example, about 0.01 to 5.0% by weight. This coating liquid Φ) is used as the coating liquid (a).
It may be applied to the coating surface of , and then dried at a temperature of about room temperature to 100°C. It is necessary to form a coating film by sufficient drying. The temperature of the inner wall of the polymerization vessel during coating work (
The coating temperature is preferably from room temperature to about 100''C.

Examples of the solvent for preparing the coating liquid (b) include:
Water and organic solvents that are easily miscible with water include, for example, alcohol solvents, ester solvents, ketone solvents, etc., and these may be used alone or as a mixed solvent of two or more. The dry coating amount of the coating film of the coating liquid Φ) obtained in this way is usually 0.001 to 5 g/m.
is preferred.

In this way, after the two-step coating process is completed on the inner wall of the polymerization vessel and other parts that come into contact with the monomer during polymerization, the monomer having an ethylenic double bond is applied to the polymerization vessel in accordance with a conventional method. A polymerization initiator, other necessary polymerization media, and additives such as monomer dispersion aids may be charged and polymerization may be carried out.

Examples of monomers having an ethylenic double bond to which the method of the present invention is applied include vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, meccrylic acid, and their like. Examples include esters or salts, maleic acid or fumaric acid, and their esters or anhydrides, diene monomers such as butadiene, chloroprene, and isoprene, as well as styrene, acrylonitrile, vinylidene halides, and vinyl ethers.

Further, the method of polymerization to which the method of the present invention is applied is not particularly limited, and any polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization is effective.

Therefore, any commonly used additives added to the polymerization system can be used without any restrictions. That is,
For example, suspending agents such as partially saponified polyvinyl alcohol, methyl cellulose, and polyacrylate; solid dispersing agents such as calcium phosphate and hydroxyapatite; anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium dioctyl sulfosuccinate; fillers such as calcium carbonate and titanium oxide, stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, dioctyltin mercaptide, rice wax, stearic acid, etc. Lubricant, DOP, DBP
plasticizers such as trichlorethylene, chain transfer agents such as mercaptans, pH regulators, diisopropyl peroxydicarbonate, α,α゛-azobis-2,4 dimethylvaleronitrile, lauroyl peroxide, potassium persulfate, cumene hydroperoxide Even in a polymerization system in which a polymerization catalyst such as P-menthane hydroperoxide is present, the method of the present invention can effectively prevent polymer adhesion.

Polymerization in which the method of the present invention is particularly suitably carried out is, for example, suspension polymerization or emulsion polymerization of vinyl halides such as vinyl chloride, vinylidene halides, or monomer mixtures mainly containing these. We also manufacture beads and latex of polymers such as polystyrene, polymethyl methacrylate, and polyacrylonitrile in stainless steel polymerization cans, SBR, NBRXCR, IR, I IH
It is also suitable for the production of synthetic rubbers such as (these synthetic rubbers are usually produced by emulsion polymerization) and the polymerization for producing ABS resins.

〔Example〕

Next, the method of the present invention will be explained using Examples and Comparative Examples. In the following, coating liquid A and coating liquid B are specific examples of the aforementioned coating liquid (a) and coating liquid (b), respectively. In addition, in each table below, experiment N marked with *
o is a comparative example, and the other experiments Nα are examples of the present invention.

Example 1 Polymerization was carried out in the following manner using a stainless steel polymerization vessel with an internal volume of 100 i and equipped with a stirrer.

In each experiment, first, a coating solution [Coating Solution A] was prepared by dissolving a cationic dye in methanol to a concentration of 0.5% by weight, and this was applied to the inner wall of the polymerization vessel and other areas that the monomers came into contact with during polymerization. It was applied, left to stand at room temperature for 30 minutes, dried, and then washed with water. Next, a coating liquid [coating liquid B] prepared by dissolving an anionic polymer compound or an amphoteric polymer compound in water was applied, and after drying, it was washed with water. However, in experiments Nα1-3, no coating liquid was applied, or only one of coating liquids A and B was applied. Table 1 shows the cationic dye and anionic or amphoteric polymer compound used in each experiment, as well as the concentration of coating solution B and the coating and drying conditions.

Thereafter, 400 g of water was added to the polymerization vessel coated in this way.
kg, styrene 260kg, acrylonitrile 140kg
g, 400 g of partially saponified polyacrylamide and α,
1.2 kg of α'-azobisisobutyronitrile was charged and polymerized at 90°C for 5 hours with stirring. The amount of polymer attached as scale to the inner wall surface of the polymerization vessel was measured. The results are shown in Table 1.

Example 2 In a stainless steel polymerization vessel with an internal volume of 1,002 mm and equipped with a stirrer, in the same manner as in Example 1, coating liquid A was applied in methanol at a concentration of 0.5% by weight, and then coating liquid B was applied. However, in experiments Nα14 to Nα16, coating liquid was not applied or coating liquid A was applied.
Or only one of B was applied. Table 2 shows the cationic dye, anionic or amphoteric polymer compound used in each experiment, the concentration of coating solution B, and the coating and drying conditions.

Next, in the polymerization vessel treated in this manner, 40 g of water, 500 g of sodium oleate, 13 kg of polybutadiene latex (solid content 45%), 9.0 g of styrene, 1 kg of acrylonitrile, and 40 g of t-dodecyl mercaptan were added.
and 140g of cumene hydroperoxide,
After raising the internal temperature to 65°C, 200 g of grapes, 1st sulfuric acid
2 g of iron and 100 g of sodium pyrophosphate were charged, and then polymerization was carried out at 65°C for 5 hours without stirring. The amount of polymer attached as scale to the inner wall surface of the polymerization vessel was measured. The results are shown in Table 2.

Example 3 Polymerization was carried out in the following manner using a stainless steel polymerization vessel with an internal volume of 1000 f and equipped with a stirrer.

In each experiment, firstly, the cationic dye was dissolved in methanol to a concentration of 0.5% by weight, and thirdly, the metal salt or inorganic colloid shown in the table was dissolved at a weight ratio of cationic dye/(metal salt or inorganic colloid). A coating liquid [Coating liquid A] was prepared by adding the additives so that the values shown in Table 3 were obtained, and this was applied to the inner wall of the polymerization vessel and other parts that would come into contact with the monomer during polymerization.
After drying for 15 minutes, it was washed with water. However, experiment N
α20 to α25 are comparative examples, in which no coating was performed as shown or only one of coating liquid A or coating liquid B was applied. Next, a coating liquid [coating liquid B] prepared by dissolving an anionic polymer compound or an amphoteric polymer compound in water was applied, dried, and washed with water.

The cationic dye, metal salt or inorganic colloid, anionic or amphoteric polymer compound used in each experiment, the concentration of coating solution B, and the coating and drying conditions were
Shown in the table.

Thereafter, 400 g of water was added to the polymerization vessel treated in this way.
kg, styrene 260 kg, acrylonitrile 140 kg
kg, 400 g of partially saponified polyacrylamide and α
.

1.2 kg of α'-azobisisobutyronitrile was charged and polymerized at 90°C for 5 hours without stirring. After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured. The results are shown in Table 3.

Example 4 In a stainless steel polymerization vessel with an internal volume of 1000 N and a stirrer,
Coating liquid A (0.5% by weight, methanol) was applied in the same manner as in Example 3, and then coating liquid B was applied.

However, in experiments Nα36 to 40, no coating was performed or
Or this is a comparative example in which only one of coating liquids A and B was applied. Table 3 shows the concentration of the cationic dye, metal salt or inorganic colloid, anionic or amphoteric polymer compound used in each experiment, and the coating and drying conditions of coating solution B.

Thereafter, 40 kg of water was added to the polymerization vessel treated in this way.
, 500 g of sodium oleate, 13 kg of polybutadiene latex (solid content 45%), 9.0 kg of styrene,
Acrylonitrile 5.0 kg, t-dodecyl mercaptan 40 g, and cumene hydroperoxide 1
40g was charged. After raising the internal temperature to 65°C, grape P
i200g, ferrous sulfate 2g and sodium pyrophosphate 10g
0 g was charged and polymerization was carried out at 65°C for 5 hours without stirring. After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured.

Example 5 Coating liquids A and 4 prepared in Example 3 or 4 in the same manner as in Example 3 were applied to the inner wall of the polymerization vessel of a stainless steel weigher with an internal volume of 100 z and other parts that come into contact with the monomer during polymerization. B was applied, dried at 50°C for 15 minutes, and then washed with water. Coating solutions A and B used in each experiment were the same as those used in experiment Nα shown in Table 5.

Using the polymerization vessel in which the coating film was formed on the inner walls and other surfaces, polymerization was carried out in the same manner as in Example 3. After the polymerization was completed, the reaction product was taken out, the interior of the polymerization vessel was washed with water, and the coating solution was again poured into the vessel. The operations from application to preparation, polymerization, and washing with water were repeated in the same manner. At this time, the amount of scale deposited in the polymerization vessel is Ig/
The number of times polymerization could be repeated until the rrf was exceeded (number of times of scale prevention) was measured and used as an index of scale adhesion prevention effect. The results are shown in Table 5.

Table 5 Example 6 Polymerization was carried out in the following manner using a stainless steel polymerization vessel with an internal volume of 100 z and equipped with a stirrer.

In each experiment, first, a coating solution [Coating Solution A] was prepared by dissolving a cationic dye in methanol to a concentration of 0.5% by weight, and this was applied to the inner wall of the polymerization vessel and other areas that the monomers came into contact with during polymerization. It was applied, left at 50°C for 15 minutes, dried, and then washed with water. Next, a coating liquid [Coating liquid B
) was applied and dried. However, actual KINα55-57
In this case, no coating liquid was applied at all, or only one of coating liquids A and B was applied. Cationic dyes and hydroxyl group-containing organic compounds used in each experiment,
Table 6 also shows the concentration of coating liquid B, coating and drying conditions.

After that, 400 kg of water was added to the polymerization vessel coated in this way.
, 260 kg of styrene, 140 kg of acrylonitrile,
400 g of partially saponified polyacrylamide and α, α′
- Prepare 1.2 kg of azobisisobutyronitrile,
Polymerization was carried out at 90°C for 5 hours without stirring. The amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured. 6th result
Shown in the table.

Example 7 Coating liquid A was applied to the inner wall of a stainless steel polymerization vessel with an internal volume of 1002 mm and equipped with an agitator in the same manner as in Example 6, and then coating liquid B was applied thereto. However, in experiments Nα69 to Nα71, no coating liquid was applied, or only one of coating liquids A and B was applied. Table 7 shows the cationic dye, the organic compound containing a hydroxyl group, the concentration of coating liquid B, and the coating and drying conditions used in each experiment.

Next, in the polymerization vessel treated in this manner, 40 kg of water, 500 g of sodium oleate, 13 kg of '-polybutadiene latex (solid content 45%), 9.0 kg of styrene, 5.0 kg of acrylonitrile, and 40 g of t-dodecyl mercaptan were added. and cumene hydroperoxide 140g
After raising the internal temperature to 65°C, add 200 g of glucose.
, 2 g of ferrous sulfate, and 100 g of sodium pyrophosphate were charged, and then polymerization was carried out at 65°C for 5 hours without stirring. After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured. The results are shown in Table 7.

Example 8 Polymerization was carried out in the following manner using a stainless steel polymerization vessel with an internal volume of 1000 A and equipped with a stirrer.

In each experiment, first, an anionic dye and a cationic dye were added to a mixed solvent of water and methanol (volume ratio of water 7/methanol: 90/10) so that the total concentration of the anionic dye and cationic dye was 0.5. % by weight to prepare a coating liquid [Coating liquid A], apply this to the inner wall of the polymerization vessel and other parts that will come into contact with the monomer during polymerization, and leave it at 60"C for 15 minutes to dry. Then, the hydroxyl group-containing organic compound was dissolved in methanol, and water was added (
Water/methanol volume ratio: 80/20) The prepared coating liquid [Coating liquid B] was applied, dried, and washed with water. however,
In experiments Nα77 to 80, no coating liquid was applied, only one of coating liquids A and B was applied, or only coating liquid A containing only one of anionic dye and cationic dye was applied. Table 8 shows the anionic dye, cationic dye, and hydroxyl group-containing organic compound used in each experiment, the weight ratio of the anionic dye/cationic dye used, the concentration of coating liquid B, and the coating and drying conditions.

Thereafter, 400 k of water was added to the polymerization vessel coated in this way.
g, styrene 260 kg, acrylonitrile 140 kg
g, 400 g of partially saponified polyacrylamide and α,
1.2 kg of α'-azobisisobutyronitrile was charged and polymerized at 90°C for 5 hours with stirring. After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured. The results are shown in Table 8.

Example 9 Coating liquid A was applied in the same manner as in Example 8, and then coating liquid B was applied to a stainless steel polymerization vessel with an internal volume of 1002 mm and equipped with a stirrer. However, in experiments Nα91 to Nα94, either no coating liquid was applied, or only one of coating liquids A or B was applied.
Alternatively, only coating liquid A containing only either an anionic dye or a cationic dye was applied. Table 9 shows the anionic dye and cationic dye used in each experiment, their mixed weight ratio, the hydroxyl group-containing organic compound, the concentration of coating liquid B, and the coating and drying conditions.

Next, 400 kg of water was added to the polymerization vessel treated in this way.
Sodium oleate 500g, polybutadiene latex (solid content 45% H3kg, styrene 9.0kg, acrylonitrile 5.0kg, t-dodecyl mercaptan 40g1 and cumene hydroperoxide 140g
After preparing grapes and raising the internal temperature to 65°C, grape Fi200
g, 2 g of the first sulfuric acid, and 100 g of sodium birophosphate were charged, and then polymerization was carried out at 65°C for 5 hours without stirring. After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured.

The results are shown in Table 9.

Example 10 In each experiment, the inner wall surface of a stainless steel polymerization vessel with an internal volume of 1000 f and a stirrer and other parts that come in contact with the monomer during polymerization were used in Experiment Nα in Examples 8 and 9 shown in Table 10. The same coating liquid as above was applied, and after drying, it was washed with water. Next, a coating solution [coating solution B] prepared by dissolving the hydroxyl group-containing organic compounds shown in Table 10 in water to a concentration of 0.5% by weight was applied and dried at 50° C. for 15 minutes.

However, in experiment Nα102, coating liquid A was not applied, but only coating liquid B was applied.

Next, polymerization was carried out in the same manner as on the day of the example in the polymerization vessel coated in this manner. After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured. Table 1 shows the results.
0.

Table 10 Example 11 Polymerization was carried out in the following manner using a stainless steel polymerization vessel with an internal volume of 1000 I2 and equipped with a stirrer.

In each experiment, first, the anionic dye and the cationic dye were dissolved in methanol to a concentration of 0.5% by weight, and then the metal salt or inorganic colloid shown in Table 11 was added (metal salt or inorganic colloid)/(anionic dye). Coating liquid C and cationic dye) were added so that the weight ratio was as shown in Table 11 to prepare Coating liquid C, Coating liquid A], and this was applied to the inner wall of the polymerization vessel and other parts that come into contact with the monomer during polymerization. Apply and heat at 50°C for 20
After drying for a minute, it was washed with water. Next, a coating liquid [coating liquid B] prepared by dissolving an anionic polymer compound or an amphoteric polymer compound in water was applied, dried at 60° C. for 15 minutes, and then washed with water. However, actual UNα109 to 113 are comparative examples, and are examples in which no coating was performed, or only one of coating liquid-containing coating liquid and coating liquid B was coated. used in each experiment (
(a) Anionic dye, (b) Cationic dye, (c) Metal salt or inorganic colloid, and anionic or amphoteric polymer compound, and (a)/(b)
Table 11 shows the weight ratio of , the weight ratio of (c)/[(a) + (b)], and the concentration of coating liquid B.

Thereafter, 40 ml of water was added to the polymerization vessel coated in this way.
0 kg, styrene 260 kg, acrylonitrile 1
40 kg, 400 g of partially saponified polyacrylamide
and α, α′-azobisisobutyronitrile 1.2 kg
was charged and polymerized at 90"C for 5 hours while stirring.

After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured. The results are shown in Table 11.

Example 12 Coating liquid A was applied in the same manner as in Example 11, and then coating liquid B was applied to a stainless steel polymerization vessel with an internal volume of 10,002 mm and equipped with a stirrer. However, experiments NcL123 to NcL127 are comparative examples in which no coating was performed or only one of coating liquids A and B was applied. (a) used in each experiment
Anionic dye, (b) cationic dye, (c) metal salt or inorganic colloid, anionic or amphoteric polymer compound, and the weight ratio of (a)/(b), (c)/[
(a) + (b)] and the concentration of coating liquid B.
Shown in the table.

Next, 40k of water was added to the polymerization vessel coated in this way.
g, sodium oleate 500 g, polybucdiene latex (solid content 45%) 13 kg, styrene 9.0 k
g, acrylonitrile 5.0 kg, t-dodecyl mercaptan 40 g, and cumene hydroperoxide 140 g. After raising the internal temperature to 65°C, add 13,200 g of grapes, 2 g of ferrous sulfate, and 1 portion of sodium pyrophosphate.
00g was charged and polymerization was carried out at 65°C for 5 hours without stirring. After the polymerization was completed, the amount of polymer scale attached to the inner wall surface of the polymerization vessel was measured. The results are shown in Table 12.

Example 13 Coating liquid A prepared in Example 11 or 12 and the coating solution A prepared in Example 11 or 12 in the same manner as in Example 11 was applied to the inner wall of the polymerization vessel of a stainless steel weight weigher with an internal volume of 1000 f and other parts that come into contact with the monomer during polymerization. B was applied, dried at 50°C for 15 minutes, and then washed with water. Coating liquids A and B used in each experiment were the same as those used in experiment No. shown in Table 13.

However, Experiment No. 137 is a comparative example in which no coating is performed.

Using the polymerization vessel in which the coating film was formed on the inner walls and other surfaces in this way, polymerization was carried out in the same manner as in Example 11. After the polymerization was completed, the reaction product was taken out, the inside of the polymerization vessel was washed with water, and the coating solution was added again. The operations from application to preparation, polymerization, and washing with water were repeated in the same manner. At this time, the amount of scale deposited in the polymerization vessel was 1
The number of times polymerization could be repeated until exceeding g/rrr (number of scale prevention times) was measured and used as an index of scale adhesion prevention effect. The results are shown in Table 13.

Table 13 [Effects of the Invention] According to the method of the present invention, it is possible to effectively prevent polymer scale from adhering to the inner wall surface of a polymerization vessel during the polymerization of monomers having ethylenic double bonds, which has been difficult in the past. It can be prevented. In particular, monomers with high solubility, such as styrene,
Adhesion of polymer scale can be prevented even in the case of polymerization of a polymerization system containing α-methylstyrene, acrylic acid ester, and acrylonitrile. By applying the coating to every batch or every few batches, the polymerization vessel can be used repeatedly without causing polymer scale to adhere.

Claims (1)

[Claims] 1. A method for preventing the adhesion of a monomer having an ethylenic double bond in a polymerization vessel, the method comprising: First, a coating solution containing (a) a cationic dye is applied to the other parts that will be in contact with each other, and then (b) an anionic polymer compound, an amphoteric polymer compound, and a hydroxyl group-containing organic compound are applied to the resulting coating film. A method for preventing adhesion of polymers, which comprises carrying out the polymerization in a polymerization vessel coated with at least one compound selected from the group consisting of compounds. 2. The method according to claim 1, wherein the coating liquid (a) further contains at least one selected from the group consisting of metal salts and inorganic colloids. 3. The method according to claim 1, wherein the coating liquid (a) further contains an anionic dye. 4. The method according to claim 3, wherein the coating liquid (a) further contains at least one selected from the group consisting of metal salts and inorganic colloids. 5. The method according to claim 3, wherein the weight ratio of anionic dye/cationic dye in the coating liquid (a) is 10.
A method that is between 0/0.1 and 100/1000.