JPH0425507A - Prevention of deposition of polymer scale - Google Patents

Abstract

PURPOSE:To prevent effectively the deposition of polymer scale on the inside wall, etc., of a polymerizer for polymerizing a specified ethylenically unsaturated monomer by forming specified coating layers in two stages on the inside wall of the polymerizer. CONSTITUTION:The ethylenically unsaturated monomer to be polymerized is represented by the formula: CH2=CXY [wherein X is hydrogen or methyl; Y is hydrogen or a group of -CnH2n+1, -COOH or -COOM (wherein M is an alkali metal or an ammonium ion); and n is an integer]. A first coating layer is formed on the inside wall of a polymerizer by applying thereto a first coating fluid containing a water-soluble anionic dye and a cationic dye. A second coating layer is formed on the first layer by applying thereto a second coating fluid containing at least one component selected from among an alkaline earth metal compound, a water-soluble anionic dye and an inorganic colloid.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention prevents the adhesion of polymer scale to the inner wall surface of a polymerization vessel during the polymerization of a monomer having an ethylenic double bond in a polymerization vessel. Regarding the method.

[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.

When polymer scale adheres to the inner wall surface of the polymerization vessel, the yield of the polymer decreases, the cooling capacity of the polymerization vessel decreases, and the quality of the product polymer decreases due to the adhered polymer scale peeling off and contaminating the product. In addition, there are disadvantages such as a great deal of effort and time required to remove the polymer scale. Moreover, the polymer scale contains unreacted monomers, which can expose workers and cause physical injury.

Conventionally, as a method for preventing polymer scale from adhering to the inner wall surface of a polymerization vessel during the polymerization of monomers having ethylenic double bonds, a suitable substance was used as a polymer scale adhesion inhibitor to prevent polymer scale from adhering to the inner wall surface of the polymerization vessel. There are known methods of applying it to

Substances suitable as polymer scale adhesion inhibitors include:
For example, specific polar compounds (Japanese Patent Publication No. 45-30343), dyes or pigments (Japanese Patent Publication No. 45-30835), aromatic amine compounds (Japanese Patent Publication No. 51-50887), and combinations of phenolic compounds and aromatic aldehydes. Reaction products (JP-A-55-54317) and the like are disclosed.

The method for preventing the adhesion of polymer scale using these substances is effective for preventing the adhesion of polymer scale in the polymerization of vinyl halide monomers such as vinyl chloride, or monomer mixtures mainly composed of these monomers. It is valid.

[Problem to be solved by the invention]

However, when the monomer having an ethylenic double bond to be subjected to polymerization has the general formula (■) including styrene, α-methylstyrene, acrylic ester, and acrylonitrile, CTo=CXY (1) [where, X is a hydrogen atom or a methyl group, and V is a hydrogen atom or has the formula: -CnHz, -+, -COOH.

-COOM (where H is an alkali metal such as Na, Li, or ammonium ion L-COOCf
iHz-+.

-CN, =CbHs, -C&H4Z (;-koi'
Z is a hydrogen atom, -011, -Cl, or -
CH=CHz), -0COC,H
It is a group represented by z-+, -QC-Hz-+ or cu=cuz, where n is an integer, usually an integer from 1 to 4.

] In the case of monomers represented by the above, since these monomers have a large dissolving power for the coating film formed by the above-mentioned adhesion prevention method, part or all of the coating film may be dissolved. As a result, it is not possible to effectively prevent polymer scale from adhering to the inner wall surface of the polymerization vessel. Among them, styrene, α-methylstyrene, acrylic acid ester, and acrylonitrile have extremely high solubility in a coating film made of a scale inhibitor, so that the desired scale prevention effect could not be obtained. Furthermore, especially when a stainless steel polymerization vessel is used, polymer scale is particularly likely to adhere to the inner wall surface of the polymerization vessel.

[Means to solve the problem]

An object of the present invention is to provide a method for polymerizing or copolymerizing a monomer having a specific ethylenic double bond represented by the general formula (1) above, without causing any damage to the inner wall surface of the polymerizer, regardless of the material of the inner wall of the polymerizer. The object of the present invention is to provide a method that can effectively prevent the deposition of polymer scale.

That is, the present invention achieves the above object by providing the following formula: General formula: % Formula % [Here, X is a hydrogen atom or a methyl group, and Y is
Hydrogen atom or formula: -C, Hz,, +, -CO
O[(.

C00M (where N is an alkali metal such as Na, Li, etc. or ammonium ion), -COOC
nH, □1゜-CN, -Chis, -CJ4Z (
: Iron Z is a hydrogen atom or -0)1. -C1, or -CH=CH (a group represented by !) + -
0COC, L-1, -QClIHz-++ or -c
A group represented by o=cttz, where n is an integer, usually 1
It is an integer of ~4. ] A method for preventing the adhesion of polymer scale during polymerization of a monomer having an ethylenic double bond expressed by (B) A first coating solution containing a cationic dye is applied to form a first coating film, and (C) an alkaline earth metal compound and (D) a water-soluble The polymerization process is carried out in a polymerization vessel in which a second coating solution containing at least one component selected from the group consisting of anionic dyes and (E) inorganic colloids is applied to form a second coating film. Provided is a method for preventing the adhesion of polymer scale, which comprises the steps of:

The present invention will be explained in detail below.

The coating film of process No. -0 is formed using a first coating liquid containing a water-soluble anionic dye as the component (A) and a cationic dye as the component (B).

(A'... Anion S In the present invention, water-soluble anionic dyes used as component (A) of the first coating solution include, for example, those described in U.S. Pat. No. 4,173,696. Examples include.

Specifically, for example, c, r, acid yellow 38
;C, 1, Acid Red 1B, 52.73.80.
87; C, 1, acid violet 11.78; C
,1, Acid Blue 1 ,40.59.113.11
6.120.158. C, l acid orange 3.
7. C, 1, acid blank 2, 124; C
, 1, Direct Orange 2.10.26°97; C
,1, Direct Red 1, 3L 92.186,
C.

1, Direct Violet 1, 22; c, r, Direct Blue L 6.7L 86.106, C
, 1, Direct Black 2.19.32.38.77
; C, 1, Direct Green 1, 26. C,1
, Direct Yellow 1; C, I.

Direct Brown L, 37.101, C,1
, Food Yellow 3; Reactive Yellow 3; c,
l Reactive Blue 2. 4.18; C, 1, Mordant Hiolet 5. C, 1, Mordand Black 5
．． C,1, Mordant Yellow 26; C,1, Fluorescent Brightening Agent 30.32; C
, 1, Solbilized Butt Black 1; C, 1, Azoic Brown 2, etc. These water-soluble anionic dyes can be used alone or in combination of two or more.

Among these water-soluble anionic dyes, particularly preferred are C,1, Acid Blue 1, 40.59; c.

■, Acid Black 1.2.124. C, 1, Direct Blue 1, 6.7L 86.106. C,1
, Direct Black 2.19.32.38.77;
C, 1, Direct Brown 1, 37; C, 1, Reactive Blue 2. 4.18;C1! , Mordand Black 5. C, 1, solbilized hat black 1
;C, 1, Azoic Brown 2.

(B Cation Panco In the present invention, the cationic dyes used as the component (B) of the first coating solution include, for example, C,1, Paysic Red 2; C,1, Paysic Blue 16;
, 1, Paysic Black 2. C, 1, Solvent Black 5. azine dyes such as C,1, Paysic Orange 14.15, acridine dyes such as C,1, Paysic Blue 1. 5. 7.26; C,1, triphenylmethane dye such as Paysic Violet 3.14, C9
■, Paythic Blue 9.24.25; C,1, Paythic Yellow 1; C,1, thiazine dye such as Paythic Green 5, C,1, Paythic Red 12; C,
1, Methine dye such as Paysic Yellow 11, C,1,
Paysic Yellow 2; Solvent Violet 8; C
, 1, diphenyl and triphenylmethane dyes such as Solvent Blue 2, 73, C, 1, Paysic Blue 6
Oxazine dye such as °12, C,1, Solvent Yellow 2, 6.14.15.16.19.2L 56;
C, 1, Solvent Red L 8.23.24. '2
5.27. 100.109. 121; C, 1, Solvent Brown 3. 5.20.37; C,1, Solvent Black 3.22.23; C,1, Paythic Orange 2; C,1, Azo dye such as Paythic Brown 1; C,1, Paythic Violet 10; ,1,
Xanthine dyes such as Paysic Red 1, phthalocyanine dyes such as C,1, Solvent Blue 55, C,1, Solvent Blue 11.12.36. Examples include anthraquinone dyes such as C,1, Solvent Violet 1.13.14; C,R, Deathverse Violet; and C,1, Solvent Green 3. These cationic dyes can be used alone or in combination of two or more.

Among these cationic dyes, particularly preferred are:
C,1, Basic Red 2; C,1, Basic Blue-16; C,1, Paythic Black 2. C, 1, azine dye such as Solvent Black 5, 7, c, i, acridine dye such as Paysic Orange 14.15, C1■
, thiazine dyes such as Paysic Blue 9.24.25,
C,1, oxazine dye such as Paysic Blue 6.12, C,1, phthalocyanine dye such as Solvent Blue 55, C,1, Solvent Blue 11.12.36;
, 1, Solvent Green 3, and other anthraquinone dyes.

-゛'s Soda 1 In the present invention, the first coating liquid contains one or more of the water-soluble anionic dye as the component (A) and the cationic dye as the component (B) in an appropriate manner. It is prepared by dissolving or dispersing it in a solvent.

In this case, the content ratio of component (A) and component (B) is a weight ratio (A):(B) of 100:1 to 100:1.
0000.

Preferably it is 100:10-100:1000. If component (B) is too small compared to component (A),
There is a possibility that the effect of preventing polymer scale adhesion that can be obtained by using component (B) in combination may not be obtained. Also,(
If the amount of component B) is too large compared to component (A), component (A) may aggregate, making it impossible to obtain a uniform coating film.

Further, the total concentration of components (A) and (B) in the first coating liquid is not particularly limited as long as the dry coating amount described below can be obtained, but is usually 0.005 to 10% by weight, preferably It is 0.01 to 5% by weight.

Examples of the solvent used for preparing the first coating solution include water; methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol,
ec-butyl alcohol, t-butyl alcohol, n-
Alcohol solvents such as amyl alcohol, isoamyl alcohol, 5eC-amyl alcohol, and t-amyl alcohol; aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene, benzene, and xylene. ; Halogenated hydrocarbon solvents such as methylene chloride, 1-chlorobutane, amyl chloride, dichloroethylene, 1,1,2-)lichloroethane; Ketone solvents such as acetone and methyl ethyl ketone; Methyl formate, ethyl acetate, methyl acetate, acetic acid Ester solvents such as diethylene glycol methyl ether; ethyl ether, 1-4
~Ether solvents such as dioxane and ethylene glycol methyl ether; aprotic solvents such as dimethylformamide, dimethyl sulfoxide, and acetonitrile; and the like. These solvents can be used alone or as a mixed solvent of two or more.

Among these solvents, particularly preferred are water, methanol, ethanol, acetone, and mixed solvents thereof.

Further, the pH of the first coating amount is adjusted to an appropriate range as necessary. For example, when the water-soluble anionic dye described above is used as the component (A), the pH is preferably adjusted to 7 or less by adding a pH adjuster as necessary.

pHm used when adjusting the pH of the first coating liquid
Examples of the conditioner include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, carbonic acid, perchloric acid, molybdic acid, tungstic acid, phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid,
Tungstic acid, formic acid, acetic acid, oxalic acid, lactic acid, maleic acid, glycolic acid, thioglycolic acid, P-)luenesulfonic acid and phytic acid, and acid salts thereof. Among these, particularly preferred are hydrochloric acid, phosphoric acid, perchloric acid, molybdic acid, tungstic acid, phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungsten fat, p-)luenesulfonic acid, phytic acid, and their acid salts.

These pH adjusters are desirably prepared in advance as an aqueous solution with an appropriate concentration when adjusting the pH of the first coating liquid.

The second coating solution is applied to the inner wall of the polymerization vessel, thoroughly dried, and if necessary, washed with water to form the first coating film. In this case, drying is carried out, for example, from room temperature to 10
It may be carried out within the temperature range up to 0°C.

In addition, it is preferable to apply the first coating liquid to parts other than the inner wall surface of the polymerization vessel, as long as the monomers come into contact with them during polymerization. , it is better to apply it to bolts, nuts, etc.

In particular, stirring blades, stirring shafts, and 8-furs should normally be coated.

More preferably, the first coating liquid is applied to parts of the unreacted monomer recovery system where polymer scale may adhere, such as the inner surfaces of monomer distillation columns, condensers, monomer storage tanks, valves, etc. Ru.

Note that there are no particular restrictions on the method of applying the first coating liquid to the inner wall of the polymerization vessel, etc., and examples include brush coating, spray coating, and a method of filling the polymerization vessel with the first coating liquid and then drawing it out. In addition, JP-A No. 57-61001, No. 5
No. 5-36288, Special Publication No. 56501116, No. 56-
501117, JP-A-59-11303, etc., automatic coating methods can also be used.

Further, the method of drying the surface that is wet due to the application of the first coating liquid is not limited, and for example, the following method can be used. That is, after applying the first coating liquid, a method in which appropriately heated hot air is applied to the coating surface, or the inner wall surface of the polymerization vessel and other surfaces to which the first coating liquid is to be applied are preliminarily tilted at an angle of, for example, 30 to 80 degrees. It is possible to use a method in which the first coating liquid is directly applied to the heated surface after heating to C. After the coated surface is dried, the coated surface is washed with water if necessary.

The dry coating amount of the first coating film obtained in this way is usually 0.001 to 5 g/bottom, particularly 0.01 to Ig/bottom.
/rrf is preferred.

20〇noe King's second coating film contains an alkaline earth metal compound as the component (C), a water-soluble anion dye as the component (D), and at least one type selected from the inorganic colloid as the component (E). A second coating solution is used to form a coating film on the first coating film formed as described above.

(C) Alkaline I A In the present invention, examples of the alkaline earth metal compound used as component (C) of the second coating solution include silicates of alkaline earth metals such as magnesium, calcium, and barium, and carbonate. Examples include salts, phosphates, sulfates, nitrates, borates, acetates, hydroxides, oxides, halides, and the like. These alkaline earth metal compounds can be used alone or in combination.

Among these alkaline earth metal compounds, particularly preferred are magnesium carbonate, calcium carbonate, magnesium phosphate, calcium phosphate, barium phosphate, calcium sulfate, calcium borate, magnesium hydroxide,
They are calcium hydroxide, barium hydroxide, magnesium chloride, and calcium chloride.

(D)'...Anionic dyes In the present invention, water-soluble anionic dyes used as component (D) of the second coating solution include, for example, those exemplified as component (A) of the first coating solution. can be used. These water-soluble anionic dyes can be used alone or in combination of two or more.

Among these water-soluble anionic dyes, particularly preferred are C,1, Acid Blue 1, 40.59. C.

■, acid black 1, 2.124; c, r, direct blue 1.6.71.86.106. C1l
Direct bra 7ri 2.19.32.38.77; c
, r, Direct Brown 1 , 37. C, 1, Reactive Blue 2. 4.18; c, r, modern blank s; c, r, solbilized hat black 1
;c, r, Azoic Brown 2.

Cloak 1! JLL Promotion■ In the present invention, the inorganic colloids used as component (E) of the second coating solution include, for example, gold colloids, silver colloids, sulfur colloids, ferric hydroxide colloids, stannic acid colloids, and stannic acid colloids. Examples include acid colloid, manganese dioxide colloid, molyfden oxide colloid, vanadium pentoxide colloid, aluminum hydroxide colloid, lithium silicate colloid, and the like. These may be manufactured by known methods such as mechanical crushing, ultrasonic irradiation, electrical dispersion, and chemical methods. These inorganic colloids can be used alone or in combination of two or more.

Among these inorganic colloids, particularly preferred are gold colloid, silicic acid colloid, aluminum hydroxide colloid, and lithium silicate colloid.

In the present invention, the second coating liquid is composed of one or more alkaline earth metal compounds as component (C), a water-soluble anionic dye as component (D), and component (E). It is prepared by dissolving or dispersing at least one selected from certain inorganic colloids in an appropriate solvent. Preferably, (D
When component ) and component (E) are used in combination, a more improved effect of preventing polymer scale adhesion can be obtained.

The content ratio of component (C) and components (D) and (E) is the weight ratio (C): [(D) and (E)] of 10
0:1-100:5000, even 100:1
The range of 0 to 100:1000 is preferable. If components (D) and (E) are too large or small compared to component (C), the effect of preventing polymer scale adhesion obtained by using components (D) and (E) together may not be obtained. It disappears.

When using component (D) and component (E) together, (D)
Component = (E) The weight ratio of the component is 100:1 to 100:
10000, even 100: 10-100:
A range of 1000 is preferred. If the weight ratio is outside this range, it is difficult to obtain the effect of combined use.

Furthermore, the component (C) in the second coating liquid and the component (D)
The total concentration of component (E) and (E) is not particularly limited as long as the dry coating amount described below is obtained, but it is usually 0.005
-10% by weight, preferably 0.01-5% by weight.

The solvent used for preparing the second coating liquid includes water and organic solvents that are easily miscible with water, such as alcohol-based solvents and ester-based solvents among the solvents exemplified as the solvents used for preparing the first coating liquid. , ketone solvents, etc. These solvents can be used alone or as a mixed solvent of two or more.

Among these solvents, particularly preferred are water alone, water/methanol, water/ethanol, water/n-propyl alcohol, water/n-butyl alcohol, water/isobutyl alcohol, water/sec butyl alcohol, and water/sec. l
- A mixed solvent such as butyl alcohol, water/acetone, etc.

In addition, when preparing the second coating solution, make sure that the alkaline earth metal compound (C) component is sufficiently dissolved and that a uniform and strong coating film is obtained when applied. It is desirable to adjust the pH of the coating liquid to 6 or less, preferably 5 or less.

Examples of the pH adjusting agent used to adjust the pH of the second coating liquid include those exemplified as the pH adjusting agent for the first coating liquid.

Among these, particularly preferred are hydrochloric acid, phosphoric acid, perchloric acid, molybdic acid, tungstic acid, phosphomolybdic acid,
These are phosphotungstic acid, silicomolybdic acid, silicotungstic acid, P-toluenesulfonic acid, phytic acid, and acid salts thereof.

These pH adjusters are desirably prepared in advance as an aqueous solution with an appropriate concentration when adjusting the pH of the second coating solution.

The second coating liquid is applied onto the first coating film formed on the inner wall of the polymerization vessel and the like. Then, the second coating film is formed by sufficiently drying and further washing with water if necessary. In this case, drying is carried out at temperatures ranging from room temperature to 100°C, for example.
It should be done within the temperature range up to.

Note that there is no particular restriction on the method of applying the second coating liquid, and for example, the method exemplified as the method of applying the first coating liquid, that is, brush coating, spray coating, or coating the polymerization vessel with the coating liquid, is not particularly limited. This can be done by filling and then drawing out, or by automatic coating.

Furthermore, the method of drying the surface that is wet due to the application of the second coating liquid is not limited, and for example, the method exemplified as the method of drying the first coating film may be used. I can do it.

The dry coating amount of the second coating film obtained in this way is usually 0.001 to 5 g/po, particularly 0.01 to Ig/po.
It is preferable that it is 10f.

After the two-step coating process is applied to the inner wall of the polymerization vessel and other parts that come into contact with the monomer during polymerization as described above, and the first and second coating films are formed. , polymerization is carried out in the polymerization vessel according to a conventional method. That is, a monomer having an ethylenic double bond represented by the above general formula (1), a polymerization medium used as necessary, a dispersant for dispersing the monomer, etc. are charged, and then, Polymerization is carried out according to conventional methods.

Examples of the monomer of general formula (1) to which the method of the present invention is applied include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, and esters or salts thereof; butadiene, chloroprene, Diene monomers such as isoprene; examples include styrene, acrylonitrile, α-methylstyrene, and vinyl ether.

Furthermore, the method of the present invention is not limited to any type of polymerization, and is effective in any of suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, and gas phase polymerization.

To explain more specifically, in the case of suspension polymerization and emulsion polymerization, the polymerization is generally carried out by, for example, charging water and a dispersant into a polymerization vessel, and then charging a polymerization initiator (catalyst) and monomers ( The internal pressure of the polymerization vessel is usually O~10kgf/crA-
G), the polymerization is carried out by adding one or more of water, a dispersant, and a polymerization initiator, if necessary, during the polymerization. Polymerization is judged to be complete when the desired reaction rate is reached (usually when the reaction rate reaches 80-100%).

In this case, water is usually used in an amount of about 50 to 500 parts by weight per 100 parts by weight of the monomer, and the dispersant is used in an amount of about 0.6 to 0.6 parts by weight.
The polymerization initiator is used in an amount of about 0.01 to 30 parts by weight, and the polymerization initiator is used in an amount of about 0.01 to 5 parts by weight.

In the case of solution polymerization, an organic solvent such as toluene, xylene or pyridine is used instead of water as the polymerization medium. A dispersant is used as necessary. Other conditions are generally the same as those for suspension polymerization and emulsion polymerization.

In the case of bulk polymerization, the inside of the polymerization vessel is replaced with nitrogen gas or evacuated to a pressure of approximately 0.01 to 760 mm) Ig, then monomers and catalyst are charged, and the temperature is heated at -10 to 250°C.
Polymerization takes place.

The method of the present invention is effective regardless of the material of the inner wall surface of the polymerization vessel, and is also effective for, for example, stainless steel polymerization vessels, glass-lined polymerization vessels, and the like.

Those added to the polymerization system can be used without any restrictions. That is, for example, t-butylperoxyneodecanoate, bis(2-ethylhexyl)peroxydicarbonate, 3,5°5-trimethylhexanoyl peroxide, α-cumylperoxyneodecanoate, cumene hydroperoxide. , cyclohexanone peroxide, t-butyl peroxypivalate, bis(2-ethoxyethyl) peroxydicarbonate,
Benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, α,α′-azobisisobutyronitrile, α,α′-azobis-2,4-
dimethylvaleronitrile, potassium beroxonisulfate,
Polymerization initiators such as ammonium peroxodisulfate and p-menthane hydroperoxide; natural or synthetic materials such as partially saponified polyvinyl alcohol, polyacrylic acid, copolymers of vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropyl methylcellulose, and gelatin. Suspension of polymer compounds, etc.; Solid dispersion of calcium phosphate, hydroxyapatite, etc.; Nonionic emulsifiers, such as sorbitan monolaurate, sorbitan triolate, polyoxyethylene alkyl ether; Sodium lauryl sulfate, sodium dodecylhenzenesulfonate, etc. Anionic emulsifiers such as sodium alkylbenzene sulfonate and sodium dioctyl sulfosuccinate;
Fillers such as calcium carbonate and titanium oxide; stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, and dioctyltin methylcaptide; lubricants such as rice wax, stearic acid, and cetyl alcohol;
Even in polymerization systems in which plasticizers such as DOP and DBP; mercaptans such as t-dodecyl mercaptan; chain transfer agents such as trichlorethylene; can do.

Particularly suitable polymerizations when the method of the present invention is applied include, for example, copolymerization of acrylonitrile and styrene by suspension polymerization using a solid dispersant, and homopolymerization of styrene. We also manufacture beads and latex of polymers such as polystyrene, polymethyl methacrylate, and polyacrylonitrile in stainless steel polymerization vessels, and SBR.
It is also suitable for the emulsion polymerization of synthetic rubbers such as , NBR, CR, IR, and IIR, and for the polymerization of ABS resins.

Further, in carrying out the method of the present invention, the coating operation of the coating liquid may be carried out suitably every batch to every several dozen batches of polymerization. The formed coating film has high durability and maintains its ability to prevent polymer scale from adhering, so it is usually sufficient to apply the coating once every few batches or tens of batches. The polymerization vessel can be used repeatedly without causing polymer scale to adhere to the interior walls of the vessel.

〔Example〕

Hereinafter, the present invention will be explained in detail by giving Examples and Comparative Examples. In addition, in each table below, the experiment numbers marked with *
, are comparative examples, and the other experiments Nα are examples of the present invention.

- No. 1 i, i Dissolve or disperse component (A) (water-soluble anionic dye) and component (B) (cationic dye) shown in Table 1 in a solvent, adjust the pH to 3 with hydrochloric acid, and apply. Solutions Nα1 to 15 were prepared.

Table 1 shows coating liquid No., types of (A) component and (B) component used in 1 to 15, and (A) in the coating liquid.
The total concentration of the components and the (B) component, the weight ratio of the (A) component and the (B) component, and the type of solvent used are shown.

Prepolymer i. I+ The prepolymer used in Example 1 was prepared in the following manner.

In a polymerization vessel, 6000 g of styrene, 720 g of polybutadiene rubber, mineral oil (manufactured by Idemitsu Kosan, CP-5)
0) 480 g and n-dodecyl mercaptan 60
00g was charged and reacted at 115°C for 5 hours to prepare a prepolymer.

Pig 1”0- In each experiment, the internal volume is 20I! Polymerization was carried out in the following manner using a stainless steel polymerization vessel equipped with a stirrer.

In Experiment Na102 and Experiment Nos. 104-127,
Coating liquids Nα1 to 15 shown in Table 1 as the first coating liquid were applied to the inner wall of the polymerization vessel, stirring shaft, stirring blades, baffles, and other parts that come into contact with monomers during polymerization, and heated at 50°C. The first coating film was formed by heating and drying for 15 minutes.

Next, (C) component (alkaline earth metal compound), (D)
Component (water-soluble anionic dye) and component (E) (inorganic colloid) are dissolved or dispersed in water at a total concentration of 0.5% by weight, and the pH is adjusted with a pH adjuster as necessary to obtain a second A coating solution was prepared.

Then, the second coating solution prepared in this manner was applied onto the first coating film, heated and dried at 50° C. for 15 minutes, and then washed with water to form a second coating film.

However, Experiment Nos. 101 to 103 are comparative examples in which no coating liquid was applied or only either the first coating liquid or the second coating liquid was applied.

Table 2 shows the coating liquid number of the first coating liquid used in each experiment, the (C) component used in the preparation of the second coating liquid, and the (D
), the type of component (E), and the pH adjuster, the weight ratio of component (C), component (D), and component (E) in the second coating solution, and the pH of the second coating solution.

Next, add 7,000 ml of water to the polymerization vessel in which the coating film was formed.
g, 7000 g of the prepolymer obtained in the above prepolymer preparation example, 70 g of hydroxyapatite, and 0.14 g of sodium dodecylhenzenesulfonate.

17.5 g of benzoyl peroxide and 10.5 g of t-phthyl perbenzoate were charged, and then reacted at 92°C for 3.5 hours and then at 135°C for 1 hour to produce a polymer. After the polymerization was completed, the produced polymer was taken out from the polymerization vessel, and the interior of the polymerization vessel was washed with water.

Thereafter, in the same manner as above, the operations of forming a coating film by applying the first and second coating liquids, charging the monomer, polymerizing, and washing the inside of the polymerization vessel with water are repeated, and the coating adheres to the inner wall surface. The number of polymerizations that could be performed until the amount of polymer scale exceeded 1 g/rrf (referred to as the number of times of scale adhesion prevention) was measured. The results are shown in Table 2.

The first coating liquid and the second coating liquid were applied to a stainless steel polymerization vessel with an internal volume of 3002 mm and equipped with a stirrer in the same manner as in Example 1 to form a coating film.

However, experiments Nα201 to Nα203 are comparative examples in which no coating liquid was applied or only either the first coating liquid or the second coating liquid was applied.

Table 3 shows the coating liquid composition of the first coating liquid used in each experiment, the type of component (C), component (D), component (E), and pH adjuster used in the preparation of the second coating liquid. , as well as the weight ratio of component (C), component (D), and component (E) in the second coating solution, and the pH of the second coating solution.

Next, styrene 6
0kg, acrylonitrile 40kg, water 100kg, hydroxyapatite 2kg, sodium lauryl sulfate 4
300 g of 0g5 t-dodecyl mercaptan and 400 g of lauroyl peroxide were charged, stirred at 70°C for 1 hour, and then heated from 70°C to 80°C over 2 hours. Next, a polymer was produced by reacting at 80° C. for 1 hour. After the polymerization was completed, the produced polymer was taken out from the polymerization vessel and the inside of the polymerization vessel was washed with water.

Thereafter, in the same manner as above, the operations of forming a coating film by applying the first and second coating liquids, charging the monomer, polymerizing, and washing the inside of the polymerization vessel with water are repeated, and the coating adheres to the inner wall surface. The number of polymerizations that could be performed until the amount of polymer scale exceeded 1 g/% (referred to as the number of times of scale adhesion prevention) was measured. The results are shown in Table 3.

[Effects of the Invention] According to the method for preventing polymer scale adhesion of the present invention, polymer scales formed with conventional scale inhibitors, such as the monomer having an ethylenic double bond represented by the general formula (I), In the polymerization and copolymerization of monomers, where it has been difficult to effectively prevent polymer scale from adhering due to its large solubility in paint films, it is effective in reducing the adhesion of polymer scale to the inner walls of polymerization vessels. can be prevented. In particular, even in polymer systems containing styrene, α-methylstyrene, acrylic acid ester, acrylonitrile, etc., which have extremely high solubility in the coating film, the adhesion of polymer scale can be effectively prevented.

Further, when the present invention is applied, the coating operation of the coating liquid may be performed once every several batches or every several dozen batches. Therefore, the polymerization vessel can be used repeatedly without adhering polymer scale to the inner walls of the polymerization vessel, etc., thereby improving productivity.

Further, according to the present invention, even when a stainless steel polymerization vessel is used, which is more likely to have polymer scale attached than a glass-lined polymerization vessel, the deposition of polymer scale can be effectively prevented.

Claims (1)

[Claims] General formula: CH_2=CXY [Here, X is a hydrogen atom or a methyl group, and Y is
Hydrogen atom, or formula: -C_nH_2_n_+_1, -
COOH, -COOM (where M is an alkali metal or ammonium ion), -COOC_nH_2_
n_+_1, -CN, -C_6H_5, -C_6H_4
Z (here, Z is a hydrogen atom, -OH, -CH_3
or a group represented by -CH=CH_2), -
OCOC_nH_2_n_+_1, -OC_nH_2_
It is a group represented by n_+_1 or -CH=CH_2, where n is an integer. ] A method for preventing the adhesion of polymer scale during polymerization of a monomer having an ethylenic double bond expressed by (B) A first coating solution containing a cationic dye is applied to form a first coating film, and (C) an alkaline earth metal compound and (D) a water-soluble The polymerization process is carried out in a polymerization vessel in which a second coating solution containing at least one component selected from the group consisting of anionic dyes and (E) inorganic colloids is applied to form a second coating film. A method for preventing adhesion of polymer scale, comprising the steps of: