JPH05112603A - Inhibit0r of polymer scale deposition, polymerizer capable of preventing polymer scale from depositing and production of polymer using the same - Google Patents

Abstract

PURPOSE:To obtain the subject inhibitor, containing a specific condensation product and capable of effectively preventing polymer scales from depositing even near the interface between a vapor-phase part and a liquid-phase part in a polymerizer and providing high-quality product polymers with extremely rare fish eye. CONSTITUTION:The objective inhibitor, containing a condensation product of (A) an aromatic amine compound (e.g. aniline) with (B) a quinone compound (preferably benzoquinones) and (C) an aromatic hydroxy compound (e.g. phenol) and useful for polymerizing ethylenic double bond-containing monomers. The condensation product is preferably obtained by reacting the component (A) with the components (B) in an amount of 0.03-1mol based on 1mol component (A) and the component (C) in an amount of 0.5-10mol based on 1mol component (A) in an organic solvent-based medium at pH 4-10 at ambient temperature to 200 deg.C for 0.5-100hr. Furthermore, the inhibitor is preferably used by adding an alkali metallic salt or ammonium salt of a sulfonated substance prepared from the condensation product to the condensation product for further improving preventing effects on scales.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a scale adhesion preventive agent for polymerizing a monomer having an ethylenic double bond, a polymerization vessel and a method for producing a polymer using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for polymerizing vinyl monomers, suspension polymerization method, emulsion polymerization method, solution polymerization method, gas phase polymerization method,
Alternatively, a bulk polymerization method or the like is known. In any of these polymerization methods, the polymer scale is likely to be attached to the inner wall of the polymerization vessel, the stirring device, or the like where the monomer comes into contact.

When the polymer scale adheres, the yield of the polymer, the cooling capacity of the polymerization vessel and the like decrease, and the scale is peeled off and mixed in the product, which brings about a disadvantage that the quality of the product is deteriorated. In addition, not only excessive labor and time are required to remove the adhered polymer scale,
Since unreacted monomer is contained in this scale,
There is a risk of human injury due to monomers (such as vinyl chloride), which has become a very serious problem in recent years.

As for the prevention of adhesion of polymer scale to the inner wall of a polymerization vessel, polarities of amine compounds, quinone compounds, aldehyde compounds, etc. have been heretofore used, for example, in some cases in suspension polymerization of vinyl chloride. A method of applying an organic compound or a method of adding such a compound to an aqueous medium is known (Japanese Patent Publication No. 30343/1985). However, these methods show a scale-preventing effect when repeating polymerization up to about 5 to 6 batches, but have a disadvantage that the preventive effect disappears when the number of polymerization batches is larger than that (inferior in sustainability). .. In this respect, the use of a water-soluble catalyst has a particularly remarkable effect and is not industrially satisfactory.

In order to overcome this disadvantage, JP-A-60-30681
In the publication, a condensation product of an aromatic amine compound and an aromatic nitro compound is proposed. A coating film of a condensation product of this aromatic amine compound and an aromatic nitro compound,
When it is formed on the inner wall of the polymerization vessel where the monomer comes into contact, the scale does not adhere to the liquid phase portion inside the polymerization vessel even if the polymerization is repeated about 100 to 200 batches. Further, even when a water-soluble catalyst is used, the scale adhesion in the liquid phase part is similarly prevented.

[0006]

However, there is a drawback that scale adheres to the vicinity of the interface between the gas phase portion and the liquid phase portion located in the upper layer portion in the polymerization vessel. Once the scale adheres to the vicinity of the interface between the gas phase part and the liquid phase part, the scale that adheres gradually grows as the polymerization is repeated, and eventually it may peel off and enter the product polymer. .. Then, when the scale is mixed in the product polymer in this way, when the product polymer is processed into a molded article such as a sheet, many fish eyes are generated in the molded article, and the quality of the molded article is significantly deteriorated. Will end up.

Further, the coating film composed of the condensation product of the aromatic amine compound and the aromatic nitro compound may be peeled off or dissolved and mixed into the product polymer, and then the product polymer is transparent sheet or the like. When it is molded and processed, the initial colorability of the molded product is impaired and the quality of the molded product deteriorates.

Therefore, an object of the present invention is to effectively prevent the adhesion of polymer scale not only in the liquid phase part in the polymerization vessel but also in the vicinity of the interface between the gas phase part and the liquid phase part. The obtained product polymer is of high quality, has very few fish eyes after molding, and has good initial colorability.
An object is to provide a polymer scale adhesion preventive agent, a polymerization vessel using the inhibitor, and a method for producing a polymer.

[0009]

[Means for Solving the Problems] That is, the present invention achieves the above object by providing a condensation product of (A) an aromatic amine compound, (B) a quinone compound, and (C) an aromatic hydroxy compound. Provided is a polymer scale anti-adhesion agent for polymerization of a monomer having an ethylenic double bond.

Further, according to the present invention, the above-mentioned (A),
Provided is a polymerization vessel having a coating film containing the condensation products of (B) and (C). Furthermore, a method for producing a polymer by polymerization in a polymerization vessel of a monomer having an ethylenic double bond, wherein in a polymerization vessel having the above coating film on the inner wall surface,
Provided is a method for producing a polymer, the method including the step of performing the polymerization.

The above condensation product, which is an essential component of the polymer scale inhibitor of the present invention, comprises (A) an aromatic amine compound and
It is a substance obtained by condensing the (B) quinone compound and the (C) aromatic hydroxy compound. The raw materials and the synthesis will be described below.

(A) Aromatic Amine Compound The aromatic amine compound (A) has, for example, the following general formula:
It is a compound represented by (1) to (3).

[Chemical 1]

[Wherein R ¹ is --H, --NH ₂ , --Cl,-
_{OH, -NO 2, -COCH 3,} - OCH 3, represents a -N (CH _{3) 2} or an alkyl group having 1 to 3 carbon atoms, R ² is, -H, -
_{NH 2, -OH, -CH 3,} -COOH, represents a -SO ₃ H. ]

Specifically, aniline, ortho, meta or para-phenylenediamine, ortho, meta or para-aminophenol, ortho, meta or para-
Chloroaniline, ortho, meta or para-nitroaniline, ortho, meta or para-methylaniline,
N, N-dimethylparaphenylenediamine, 4-chloro-
Orthophenylenediamine, 4-methoxyorthophenylenediamine, 2-amino-4-chlorophenol,
Examples are 2,3-diaminotoluene, 5-nitro-2-aminophenol, 2-nitro-4-aminophenol, 4-amino-2-aminophenol, ortho, meta or para-aminosalicylic acid.

[Chemical 2]

[Here, two R ¹ may be the same or different and are as described above, and two R ² may be the same or different and are as described above. ] Specifically, 4-aminodiphenylamine, 2-aminodiphenylamine, 4,4'-diaminodiphenylamine, 4-amino-3'-methoxydiphenylamine, 4
Examples include diphenylamines such as -amino-4'-hydroxydiphenylamine.

[Chemical 3]

[Here, the two R ^{1 s} may be the same or different and are as described above, and R ² is also as described above. ] Specifically, α-naphthylamine, β-naphthylamine, 1,5-diaminonaphthalene, 1-amino-5-hydroxynaphthalene, 1,8-diaminonaphthalene, 2,3-
Examples include diaminonaphthalene.

(B) Quinone Compound The quinone compound (B) is, for example, ortho, meta or para-benzoquinone, tol-para-quinone, ortho-xylo-para-quinone, thymoquinone, 2-methoxybenzoquinone, gentisylquinone, polyporic acid. , Ubiquinone n
Benzoquinones and their derivatives; 6-methyl-
1,4-naphthoquinone, 2-methyl-1,4 naphthoquinone,
Naphthoquinones such as naphthoquinone, yugulone, lawson, plumbagin, alkannin, echinochrom A, vitamin K ₁ , vitamin K ₂ , shikonin, β, β′-dimethylacryl shikonin, β-hydroxyisowarer shikonin, and teracryl shikonin, and derivatives thereof. Tectoquinone, 3-hydroxy-2-methylanthraquinone,
Anthraquinones such as anthraquinone, 2-hydroxyanthraquinone, alizarin, xanthopurpurine, rubiadine, mundistine, chrysophonic acid, carminic acid, kermesic acid, and laccaic acid A and derivatives thereof;
Examples thereof include phenanthrenequinones such as phenanthrenequinone. Among these, benzoquinones are particularly preferable.

(C) Aromatic Hydroxy Compound The aromatic hydroxy compound (C) can be represented by, for example, the general formula (4):
It is a compound represented by (5).

[Chemical 4]

[Here, R ⁴ is -H, -Cl, -OH,-
_{COCH 3, - OCH 3, -COOH} , -SO 3 H or -C 1
Represents ~ 3 alkyl group, R ⁵ is, -H, -Cl, -OH,
- OCH _3, represents a -OC ₂ H ₅ or -COOH. ]

Specifically, phenol, hydroquinone,
Resorcinol, catechol, hydroxyhydroquinone, pyrogallol, ortho, meta or para-chlorophenol, ortho, meta or para-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid Acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid,
Examples include phenol derivatives such as (2,5-, 2,6-, 3,5-) dihydroxytoluene.

[Chemical 5]

[Here, R ⁴ and R ⁵ are as described above. ] Specifically, α-naphthol, β-naphthol, (1,3
-, 1,4-, 1,5-, 2,3-, 2,6-, 2,7-) dihydroxynaphthalene, 1-hydroxy-2-naphthoic acid,
Examples thereof include naphthol derivatives such as 3-hydroxy-2-naphthoic acid.

Condensation Reaction The above-mentioned condensation of the aromatic amine compound (A), quinone compound (B) and aromatic hydroxy compound (C) is carried out in an organic solvent medium, if necessary, in the presence of a condensation catalyst. .. The organic solvent-based medium has a pH in the range of 1 to 13, preferably pH 4 to 10. The pH adjusting agent can be used without particular limitation, and as the acidic compound, for example,
Phosphoric acid, sulfuric acid, phytic acid, acetic acid and the like are used, and examples of the alkaline compound include LiOH, KOH, NaOH and Na ₂
An alkali metal compound such as CO ₃ , Na ₂ SiO ₃ , Na ₂ HPO ₄ , NH ₄ OH or an ammonium compound, an organic amine compound such as ethylenediamine, monoethanolamine, triethanolamine or the like is used.

As the medium of the condensation reaction, organic solvents such as alcohols, ketones, esters, etc .; a mixed solvent of water and an organic solvent miscible with water are preferable. Examples of the medium miscible with water include alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate.

If necessary, a condensation catalyst may be used. Examples of the condensation catalyst include α, α′-azobisisobutyronitrile, α, α′-azobis-2,4-dimethylvaleronitrile and the like. Azo catalyst, elemental or molecular elemental halogen such as iodine, bromine, chlorine, hydrogen peroxide, sodium peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, peracetic acid, cumene hydroperoxide, perbenzoic acid, p Examples thereof include peroxides such as menthane hydroperoxide, and oxyacids or oxyacid salts such as iodic acid, periodate, potassium periodate and sodium perchlorate. Since the quinone compound acts as a condensation catalyst, the condensation reaction can be performed without using a condensation catalyst.

At least one or more of the aromatic amine compound (A), at least one or more of the quinone compound (B) and at least one or more of the aromatic hydroxy compound (C) in the above-mentioned organic solvent medium, If necessary, a condensation product is obtained by reacting at room temperature to 200 ° C. for 0.5 to 100 hours under a condensation catalyst.

The condensation product is affected by the types of aromatic amine compounds, quinone compounds and aromatic hydroxy compounds, the composition ratio, the reaction temperature and the reaction time.
Aquinone compound per mole of aromatic amine compound (A)
It is preferable that the content of (B) is 0.03 to 1.0 mol. If the amount of the quinone compound is too small, even if the condensation product is used as a scale adhesion preventing agent, the initial colorability of the polymer obtained by the polymerization will be poor, and if it is too large, the effect of preventing scale adhesion will be reduced.
Further, the aromatic hydroxy compound (B) is preferably 0.5 to 10.0 mol per 1 mol of the aromatic amine compound (A). If the amount of the aromatic hydroxy compound is too small, even if the condensation product is used as a scale adhesion preventing agent, the initial colorability of the polymer obtained by the polymerization will be poor, and if it is too large, the scale adhesion preventing effect will be reduced.

Preferred among the condensation products are those containing an aromatic amine compound of the general formula (1) and an aromatic hydroxy compound of the general formula (5) as reaction components; an aromatic amine compound of the general formula (2). Containing an aromatic hydroxy compound of the general formula (4) and / or (5) as a reaction component; and reacting an aromatic amine compound of the general formula (3) with an aromatic hydroxy compound of the general formula (4) It is a condensation product containing as a component. Among these, more preferred are those of the general formula
(2) and / or (3) the aromatic amine compound and the general formula (4)
Is a condensation product containing as a reaction component the aromatic hydroxy compound of.

In a preferred embodiment of the scale inhibitor of the present invention, an alkali metal salt or an ammonium salt of a sulfonated product obtained by sulfonation of the condensation product is added to the condensation product. By this,
The scale prevention effect of the polymer scale inhibitor of the present invention is further improved. The addition amount is preferably 10 to 1000 parts by weight of the sulfonate salt, and further 50 per 100 parts by weight of the condensation product.
~ 500 parts by weight are preferred.

The sulfonated salt can be obtained by drying the condensation product obtained in the above-mentioned synthesis to remove the solvent, sulfonation, and then conversion to an alkali metal salt or ammonium salt.

That is, first, the sulfonation of the condensation product may be carried out according to a conventionally known method. For example, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or the like is used as a sulfonating agent, and the sulfonation is performed at room temperature to 95 ° C. A sulfonated product can be obtained by reacting the concentration of the agent as 2 to 15 times (weight) of the condensation product. This sulfonate,
The desired sulfonate salt can be obtained by reacting with an alkali metal compound or an ammonium compound. As the reaction method, for example, the sulfonated compound is dispersed in water, and NaOH, KOH,
Alkali metal compounds such as Na ₂ CO ₃ or NH ₄ OH, (
A predetermined amount of ammonium compound such as NH ₄ ) ₂ CO ₃ may be added and reacted.

Since the salt of this sulfonate is water-soluble, it can be obtained in the form of being dissolved in an aqueous medium, but it may be stored or used as it is, or once evaporated to dryness and pulverized. It may be in powder form, which is convenient for storage and transportation.

Preparation of Coating Solution The solvent used for preparing the coating solution of the scale inhibitor of the condensation product of the components (A), (B) and (C) is, for example, water; methanol, ethanol. , Propanol, butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-propanol, 3-methyl-
Alcohol solvents such as 1-butanol, 2-methyl-2-butanol, 2-pentanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters of methyl formate, ethyl formate, methyl acetate, methyl acetoacetate, etc. System solvent; 4-methyldioxolane,
Examples thereof include ether solvents such as ethylene glycol diethyl ether; furans; aprotic solvents such as dimethylformaside, dimethylsulfoxide, and acetonitrile. These are appropriately used alone or as a mixed solvent of two or more kinds.

The concentration of the condensation product of the component (A), the component (B) and the component (C) in the coating solution is not particularly limited as long as the total coating amount described below can be obtained, but is usually 0.001 to 15% by weight. %degree,
It is preferably 0.01 to 1% by weight. Further, as long as the scale preventing effect is not impaired in this coating solution, for example, cationic, nonionic and anionic surfactants; phosphoric acid,
A pH adjusting agent such as perchloric acid, sulfuric acid, hydrochloric acid, nitric acid, phytic acid, acetic acid, paratoluenesulfonic acid, or tannic acid can be added.

If necessary, a water-soluble polymer such as a hydroxyl group-containing polymer compound, a cationic polymer compound, an anionic polymer compound or an amphoteric polymer compound may be added to this coating solution. it can.

Examples of the hydroxyl group-containing polymer compound include starches such as amylose, amylopectin, dextrin, oxidized starch, acetyl starch, nitro starch, methyl starch, carboxymethyl starch and derivatives thereof; pectic acid, protopectin, Hydroxyl group-containing plant qualities such as pectinic acid, alginic acid, laminarin, fucoidin, agar, carrageenin; hyaluronic acid, chondroitin sulfate, heparin,
Hydroxyl group-containing animal slime such as keratosulfate, chitin, chitosan, caronine sulfate, limacoitin sulfate; nucleic acids such as ribonucleic acid and deoxyribonucleic acid; methylcellulose;
Ethyl cellulose, carboxymethyl cellulose, glycol cellulose, benzyl cellulose, cyanoethyl cellulose, methylene ether of cellulose, triphenylmethyl cellulose, formyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose sulfonate, cellulose carbamate. , Cellulose derivatives such as nitrocellulose, cellulose phosphate, and cellulose xanthate; hemicelluloses such as xylan, mannan, alabogalactan, galactan, and araban; alcohol lignin, dioxane lignin, phenol lignin, hydrotrobic lignin, mercapto lignin, Thioglycolic acid lignin, lignin sulfonic acid, alkaline Nin, thio alkali lignin, acid lignin, copper oxide - ammonia lignin, such as periodate lignin; phenol - formaldehyde resins, partially saponified polyvinyl alcohol, polyvinyl alcohol and the like.

Examples of the cationic polymer compound include polyvinylamine, polyethyleneamine, polyethyleneimine, polyacrylamide, N-vinyl-2-pyrrolidone-acrylamide copolymer, cyclopolymer of dimethyldiamylammonium chloride, and dimethyl. Cyclic polymer of diethylammonium bromide, Cyclic polymer of diallylamine hydrochloride, Cyclic copolymer of dimethyldiallylammonium chloride and sulfur dioxide, Polyvinylpyridine, Polyvinylpyrrolidone, Polyvinylcarbazole, Polyvinylimidazoline, Polydimethylaminoethyl acrylate , Polydimethylaminoethylmethacrylate, polydiethylaminoethylacrylate, polydiethylaminoethylmethacrylate, etc. have a nitrogen atom in the side chain and Atoms cationic polyelectrolyte bearing a charged positively, and the like.

Examples of the amphoteric polymer compound include amphoteric polymer compounds such as glue, gelatin, casein and albumin. As the anionic polymer compound,
For example, sulfomethylated polyacrylamide; polyacrylic acid; alginic acid, acrylamide-vinyl sulfonic acid copolymer, polymethacrylic acid, polystyrene sulfonic acid, or the like, or alkali metal salts or ammonium salts thereof; for side chains such as carboxymethyl cellulose. Examples thereof include anionic polymer compounds having a carboxyl group or a sulfonic acid group.

Further, an inorganic compound may be appropriately added to the coating solution, if necessary, as long as it does not impair the scale preventing action. Examples of inorganic compounds that can be added include orthosilicic acid, metasilicic acid, mesodisilicate, mesotrisilicic acid, mesotetrasilicic acid, sodium metasilicate, sodium orthosilicate, sodium disilicate, sodium tetrasilicate, and water glass. Silicic acids or silicates; oxyacid salts of metals selected from alkaline earth metals such as magnesium, calcium and barium, zinc group metals such as zinc, aluminum group metals such as aluminum, and platinum group metals such as platinum, acetic acid Examples thereof include metal salts such as salts, nitrates, hydroxides and halides; inorganic colloids such as ferric hydroxide colloid, silicic acid colloid, barium sulfate colloid and aluminum hydroxide colloid. The above-mentioned inorganic colloid may be prepared by, for example, mechanical grinding, irradiation with ultrasonic waves, electrical dispersion and chemical method.

Formation of coating film To form a coating film on the inner wall surface of the polymerization vessel using the coating solution prepared as described above, first, the coating solution is applied to the inner wall surface of the polymerization vessel, and then, for example, at room temperature. After thoroughly drying in the temperature range from 1 to 100 ° C, further wash with water if necessary.

Further, it is preferable that the coating solution is applied not only to the inner wall surface of the polymerization vessel, but also to other portions where the monomer contacts during the polymerization. For example, stirring blade, stirring shaft, baffle,
Examples include capacitors, headers, search coils, bolts and nuts. More preferably, the coating liquid is a site other than the site where the monomer comes into contact during the polymerization, but a site where the polymer scale may be attached, for example, the inner surface of the device and piping of the recovery system of the unreacted monomer. For example, it is better to form the coating film. Specifically, a monomer distillation column, a condenser,
The inner surface of the monomer storage tank, valve, etc. may be mentioned.

In this way, when a coating film is formed on the site where the monomer contacts during the polymerization and the site where the other polymer scale may adhere, the adhesion of the polymer scale to those sites. Is prevented. The method of applying the coating liquid to the inner wall surface of the polymerization vessel is not particularly limited, and examples thereof include brush coating, spray coating, a method of withdrawing after filling the polymerization vessel with the coating solution, and others.
No. 55-36288, Special Publication No. 56-501116, No. 56-50
The automatic coating method described in 1117, JP-A-59-11303, etc. can also be used.

The method of drying the wet surface by applying the coating solution is not limited, and the following method can be used, for example. That is, after applying the coating solution, a method of applying an appropriately heated warm air to the coating surface, or the inner wall surface of the polymerization vessel and the other surface to be coated with the coating solution are heated to, for example, 30 to 80 ° C. in advance. The method of directly applying the coating solution to the heated surface can be used. After drying the coated surface, the coated surface is washed with water as needed.

The coating film thus obtained has a total coating amount after drying of usually 0.001 g / m ² or more, particularly 0.05 to ²
It is preferably g / m ² . The above coating work is 1
It may be carried out for every 10 to several batches of polymerization. The formed coating film has high durability and the action of preventing the polymer scale from adhering is maintained, so that it is not always necessary to perform it for each batch of polymerization. Therefore, the productivity of the product polymer is improved.

Polymerization As described above, after applying a coating treatment to the inner wall of the polymerization vessel, and preferably to other portions where the monomer contacts during polymerization, a coating film is formed, and then in the polymerization vessel, it is subjected to a conventional method. Polymerize. That is, in addition to a monomer having an ethylenic double bond and a polymerization initiator (catalyst), if necessary, a polymerization medium such as water, and a suspending agent, a solid dispersant, a nonionic or anionic emulsifier, etc. A dispersant and the like are charged, and then polymerization is performed by a conventional method.

Examples of the monomer having an ethylenic double bond to be polymerized by applying the method of the present invention include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid. , Methacrylic acid, and their esters or salts; maleic acid, fumaric acid, and their esters or anhydrides; butadiene, chloroprene, isoprene, and other diene-based monomers; styrene, acrylonitrile, vinylidene halide, vinyl ether, and the like. Be done.

The type of polymerization to which the method of the present invention is applied is not particularly limited, and suspension polymerization, emulsion polymerization, solution polymerization,
It is effective in both bulk polymerization and vapor phase polymerization, and is particularly suitable for polymerization in an aqueous medium such as suspension polymerization and emulsion polymerization.

The general polymerization method will be specifically described below by taking suspension polymerization and emulsion polymerization as examples. First,
Water and a dispersant are charged into a polymerization vessel, and then a polymerization initiator is charged. Next, after exhausting the inside of the polymerization vessel to reduce the pressure to 0.1 to 760 mmHg, the monomer was charged (at this time, the internal pressure of the polymerization vessel was
Usually 0.5 to 30 kgf / cm ² · G), then 30 to 150
Polymerize at reaction temperature of ° C. During the polymerization, if necessary,
One or more of water, a dispersant, and a polymerization-facilitating agent are added. Further, the reaction temperature at the time of polymerization varies depending on the kind of the monomer to be polymerized. For example, in the case of vinyl chloride polymerization,
Polymerization is carried out at 30-80 ° C, and in the case of styrene polymerization, 50-
Polymerize at 150 ° C. For polymerization, the internal pressure of the polymerization vessel is 0 to 7 kgf /
When the temperature falls to cm ² · G, or when there is almost no difference between the inlet temperature and the outlet temperature of the cooling water that flows in and out of the jacket mounted on the outer periphery of the polymerization vessel (that is, when the heat generated by the polymerization reaction disappears). ), It is judged that it is completed. Water, a dispersant, and a polymerization initiator charged during polymerization are usually 20 to 500 parts by weight of water, 0.01 to 30 parts by weight of a dispersant, and 0.01 to 5 parts by weight of a polymerization initiator with respect to 100 parts by weight of a monomer. It is a department.

In the case of solution polymerization, an organic solvent such as toluene, xylene or pyridine is used as a polymerization medium instead of water. A dispersant is used as needed. Other polymerization conditions are generally the same as those for suspension polymerization and emulsion polymerization. Further, in the case of bulk polymerization, after evacuating the inside of the polymerization vessel to a pressure of about 0.01 to 760 mmHg, charging a monomer and a polymerization initiator into the polymerization vessel,
Polymerize at a reaction temperature of -10 to 250 ° C. For example, it is carried out at 30 to 80 ° C. in the case of vinyl chloride polymerization and at 50 to 150 ° C. in the case of styrene polymerization.

When the polymer scale adhesion preventing method of the present invention is applied to carry out polymerization, the polymer scale adhesion can be prevented regardless of the material of the inner wall surface of the polymerization vessel. The adhesion of polymer scale can be prevented even when the polymerization is carried out in a steel or other steel-made polymerization vessel, a glass-lined polymerization vessel, or the like.

What is added to the polymerization system can be used without any restrictions. That is, for example, t-butyl peroxy neodecanoate, bis (2-ethylhexyl) peroxydicarbonate, 3,5,5-trimethylhexanoyl peroxide, α-cumylperoxy neodecanoate, cumene hydroper Oxite, cyclohexanone peroxide, t-butyl peroxypivalate, bis (2-ethoxyethyl) peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate , Α,
Polymerization initiators such as α'-azobisisobutyronitrile, α, α'-azobis-2,4-dimethylvaleronitrile, potassium peroxodisulfate, ammonium peroxodisulfate and p-menthane hydroperoxide; partially saponified polyvinyl Suspending agents for alcohols, polyacrylic acid, copolymers of vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropylmethyl cellulose, natural or synthetic polymer compounds such as gelatin; solid dispersants such as calcium phosphate and hydroxyapatite; Nonionic emulsifiers such as sorbitan monolaurate, sorbitan trioleate, and polyoxyethylene alkyl ether; sodium alkylbenzene sulfonates such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate; sodium dioctylsulfosuccinate Anionic emulsifiers such as lithium; fillers such as calcium carbonate and titanium oxide; stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, dioctyltin mercaptide; lubricants such as rice wax, stearic acid and cetyl alcohol; D
OP: plasticizer such as DBP; mercaptans such as t-dodecyl mercaptan; chain transfer agent such as trichlorethylene; pH
Even in a polymerization system in which a regulator or the like is present, the method of the present invention can effectively prevent the adhesion of polymer scale.

The polymer scale adhesion preventive agent of the present invention may be used for forming a coating film on the inner wall surface of the polymerization vessel or the like, and may be directly added to the polymerization system, whereby the scale prevention effect is improved. You can also let it. In that case, the addition amount of the polymer scale anti-adhesion agent is appropriately about 10 to 1000 ppm with respect to the total weight of the charged monomers. When adding, care should be taken not to affect the quality of the product polymer such as fisheye, bulk specific gravity and particle size distribution.

[0052]

EXAMPLES Production Example 1 Production of condensation product No. 1 A pressure resistant reactor was charged with 300 mol of methanol, 1 mol of 1,8-diaminonaphthalene, 0.5 mol of parabenzoquinone and 2.5 mol of pyrogallol and heated to 80 ° C. with stirring. The temperature was raised.
The mixture was reacted at 80 ° C. for 5 hours and then cooled to obtain a methanol solution of a condensation product.

Production of Condensation Products Nos. 2 to 20 Using the aromatic amine compound, quinone compound, aromatic hydroxy compound and solvent shown in Table 1 at the reaction temperature and reaction time shown in the same table, Condensation reaction was carried out in the same manner as the product No. 1 to obtain condensation products No. 2 to 20. However, Nos. 2, 3 and 4 are comparative examples.

[0054]

[Table 1]

Example 1 (Experiment Nos. 101 to 121) Polymerization was carried out as follows using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 1000 liters. The condensation products and solvents used in each experiment are shown in Table 2. First, the condensation product was dissolved in a solvent to a concentration shown in Table 2 to prepare a coating liquid. These coating solutions were applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blades, and other parts where the monomers come into contact with each other during the polymerization, and were heated and dried at 40 ° C for 15 minutes to form a coating film, and then washed with water.

However, in the experiments No. 102 to 104, (A)
This is a comparative example in which a coating liquid containing two components of components (B) and (C) was applied. In addition, No. 121 experiment
This is a comparative example in which the coating liquid containing the condensation product No. 1 of the aniline and nitrobenzene described in the Example of 30681 was applied.

Then, 400 kg of water, 200 kg of vinyl chloride, 250 g of partially saponified polyvinyl alcohol, 25 g of hydroxypropylmethylcellulose and 3,5,5-trimethylhexahexyl were placed in a polymerization vessel in which a coating film was formed by the above coating treatment. Charge 70 g of Noyl peroxide and stir 66 while stirring.
Polymerization was carried out at ℃ for 6 hours. After the polymerization was completed, the produced polymer and unreacted monomer were recovered, and the inside of the polymerization vessel was washed with water to remove the residual resin.

Then, the operation of coating and polymerizing the coating solution as described above was set as one batch, and thereafter, the same operation was repeated 20 batches, and the scale adhesion amount of the 20th batch was examined. The results are shown in Table 2. However, the scale deposition amount in each experiment is
The liquid phase portion in the polymerization vessel and the vicinity of the interface between the gas phase portion and the liquid phase portion were separately weighed. The results are shown in Table 2. Further, the fish eye when the polymer obtained in each experiment was molded into a sheet was measured by the following method. The results are shown in Table 2.

Measurement of fisheye A mixture prepared by mixing 100 parts by weight of polymer, 50 parts by weight of DOP, 1 part by weight of dibutyltin dilaurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of titanium oxide and 0.05 part by weight of carbon black. Using a 6-inch roll at 150 ° C for 7
After kneading for a minute, a sheet having a thickness of 0.2 mm was formed, and the number of fish eyes contained in 100 cm ^{2 of the} obtained sheet was examined by a light transmission method. Further, the brightness index (L value) when the polymer obtained in each experiment was molded into a sheet was measured by the following method. The results are shown in Table 2.

Measurement of lightness index (L value) 100 parts by weight of the obtained polymer, stabilizer (TS manufactured by Akishima Chemical Co., Ltd., TS
-101) 1 part by weight, stabilizer (C-100 J, manufactured by Katsuta Kako Co., Ltd.)
0.5 parts by weight and 50 parts by weight of dioctyl phthalate as a plasticizer are kneaded in a two-roll mill at 160 ° C. for 5 minutes, and then formed into a sheet having a thickness of 1 mm. Next, put the formed sheet into a 4 x 4 x 1.5 cm mold, and keep it at 160 ℃ and 65 to 70 kgf / cm.
^A sample for measurement is prepared by heating and pressure molding in ² . For this sample, the lightness index L in the Hunter color difference formula described in JIS Z 8730 (1980) was determined, and the larger the L value, the higher the whiteness.

The L value is obtained as follows. JIS Z 8722
The standard value C, photoelectric colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., Z-1001DP colorimetric color difference meter) is used to obtain the stimulus value Y of the XYZ color system by the stimulus value direct reading method. As the geometric condition of illumination and light reception, condition d described in JIS Z 8722, section 4.3.1 was adopted. From the obtained stimulation value Y,
The L value is calculated by the formula: L = 10 Y ^1/2 described in JIS Z 8730 (1980).

[0062]

[Table 2]

Production Example 2 Production of Sulfone Compound Salt No. 31 of Condensation Product No. 100 g of condensation product No. 1 and 200 g of concentrated sulfuric acid were mixed at 30 ° C. or lower and then heated to 50 ° C. The mixture was stirred for 5 hours and sulfonated. This reaction solution was poured into 1000 ml of water, and the precipitated sulfonated product was filtered, washed with water and dispersed in 1000 ml of water. At 90 ° C, 11.3 g of 40 wt% NaOH aqueous solution was added and dissolved, and then evaporated to dryness and ground. As a result, 82.5 g of a sulfonated product of condensation product No. 31 (sodium metal salt) was obtained.

Condensation product sulfonate salt Nos. 32-37
Each of the produced condensation products No. 5 to No. 10 was sulfonated using the sulfonating agent shown in Table 3 at the reaction temperature and reaction time shown in the same table. Then, using the alkaline compounds shown in the table, sulfonated compounds No. 32 to 37 (alkali metal salts) of condensation products were obtained in the same manner as the sulfonated compound No. 31 of the condensation product.

[0065]

[Table 3]

Example 2 (Experiment Nos. 201 to 207) In each experiment, a coating product prepared by using the condensation product / sulfonated product, the pH adjusting agent and the solvent shown in Table 4 to have the pH and the concentration shown in the same table. Polymerization was performed in the same manner as in Example 1 except that the liquid was used. After the polymerization was completed, the amount of scale attached was examined. The results are shown in Table 4. Further, with respect to the polymer obtained in each experiment, the fisheye and the lightness index (L value) were measured in the same manner as in Example 1. The results are shown in Table 4.

[0067]

[Table 4]

Example 3 (Experiment Nos. 301 to 310) Polymerization was carried out as follows using a stainless steel polymerization vessel with an internal volume of 20 liter equipped with a stirrer. In each experiment, the coating solution was prepared using the condensation product / sulfonated product, the pH adjusting agent and the solvent shown in Table 5 so as to have the pH and the concentration shown in the same table. As in Example 1, these coating solutions were applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blades, and other portions where the monomers come into contact with each other during the polymerization, to form a coating film and wash with water. However, N
The experiments of o.302 to 304 are comparative examples in which a coating solution containing two components among components (A), (B) and (C) was applied.

Next, 9 kg of water and sodium dodecylbenzenesulfonate 2 were placed in the polymerization vessel thus coated.
After charging 25 g, t-dodecyl mercaptan 12 g and potassium peroxodisulfate 13 g and substituting with nitrogen gas, 1.3 kg of styrene and 3.8 kg of butadiene were charged and polymerization was carried out at 50 ° C. for 20 hours. After the polymerization was completed, the produced polymer and unreacted monomer were recovered, and the inside of the polymerization vessel was washed with water to remove the residual resin.

Thereafter, the operation of coating and polymerizing the coating liquid as described above was repeated 10 batches, and after 10 batches, the amount of scale adhered to the liquid phase part in the polymerization vessel and the scale near the interface between the gas phase part and the liquid phase part The amount of adhesion was measured. The results are shown in Table 5.
Further, the brightness index (L value) when the polymer obtained in each experiment was molded into a sheet was measured by the following method. The results are shown in Table 5.

Measurement of lightness index (L value) To 1 kg of the obtained polymer was added 1 kg of a 2% magnesium sulfate solution.
Is added to carry out coagulation precipitation, and then the precipitate is separated by filtration. The precipitate separated by filtration was washed with hot water at 80 to 90 ° C. for 2 to 3 times,
A resin was obtained by drying at 40 ° C. for 25 hours using a vacuum dryer.
Put the obtained resin in a 9 × 9 cm, 0.1 cm thick mold,
5 ° C., and heated at 50 to 60 kgf / cm ^2, to prepare a measurement sample by pressing at final pressure 80 kgf / cm ^2. The lightness index L value of this sample was determined in the same manner as described above.

[0072]

[Table 5]

[0073]

According to the present invention, the adhesion of polymer scale can be effectively prevented not only in the liquid phase part in the polymerization vessel but also in the vicinity of the interface between the gas phase part and the liquid phase part. The resulting product polymer has significantly less post-mold fisheye. Further, the coating film formed on the inner wall surface of the polymerization vessel according to the present invention does not peel off during the polymerization or dissolve in the polymerization system, so that there is little deterioration in the initial colorability of the product polymer after molding. Become.

When polymerization is carried out by applying the present invention, it is not necessary to carry out the work of removing the polymer scale for each polymerization, thereby improving the productivity.

Claims (4)

[Claims] 1. A method for polymerizing a monomer having an ethylenic double bond, which comprises a condensation product of (A) an aromatic amine compound, (B) a quinone compound, and (C) an aromatic hydroxy compound. Polymer scale anti-sticking agent. 2. The polymer scale anti-adhesion agent according to claim 1, further comprising a sulfonate alkali obtained by sulfonation of the condensation products of (A), (B) and (C). An inhibitor containing a metal salt and / or an ammonium salt. 3. An ethylenic double bond on the inner wall of which a coating film containing a condensation product of (A) an aromatic amine compound, (B) a quinone compound, and (C) an aromatic hydroxy compound is formed. A polymerization vessel for polymerizing the monomer having. 4. A method for producing a polymer by polymerizing a monomer having an ethylenic double bond in a polymerization vessel.
There is a step of performing the polymerization in a polymerization vessel having a coating film containing a condensation product of (A) an aromatic amine compound, (B) a quinone compound, and (C) an aromatic hydroxy compound on the inner wall of the polymerization vessel. In this way, a production method in which the adhesion of polymer scale in the polymerization vessel is prevented.