JPH05230111A - Agent for preventing deposition of polymer scale, polymerizer effective in preventing deposition of polymer scale and production of polymer using the polymerizer - Google Patents

Abstract

PURPOSE:To provide an agent for preventing the deposition of polymer scale, containing a condensation product of an aliphatic diamine, an aromatic amine and a quinone compound and useful for the polymerization of a monomer having ethylenic double bond. CONSTITUTION:The objective agent for preventing the deposition of polymer scale and useful for the polymerization of a monomer having ethylenic double bond contains a condensation product produced by reacting (A) 1 pt.wt. of an aliphatic diamine compound (preferably 2,3-diaminobutane, etc.), (B) 0.01-15 pts.wt. of an aromatic amine compound (preferably o- or p-aminophenol, etc.) and (C) 0.01-15 pts.wt. of a quinone compound (preferably o-benzoquinone, etc.) in an organic solvent (preferably alcohol) optionally in the presence of a condensation catalyst at room temperature to 200 deg.C for 0.5-100hr. A polymerizer effective in preventing the deposition of polymer scale not only in the liquid phase but also near the interface can be produced by applying a coating film containing the deposition preventing agent to the inner wall surface of the polymerizer.

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 coloring peculiar to the polymer, which occurs when the polymer is processed into a molded product without adding a coloring agent or the like, is called initial coloring, and the smaller the value, the more preferable. However, 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, whereby the initial colorability is deteriorated.

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 product polymer obtained is of high quality, has very few fish eyes after molding, and has good initial colorability, a polymer scale anti-adhesive agent, a polymerization vessel and polymer production using the inhibitor. To provide a method.

[0009]

Means for Solving the Problems That is, in order to achieve the above object, the present invention provides a condensation product of (A) an aliphatic diamine compound, (B) an aromatic amine compound, and (C) a quinone 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, is obtained by condensing (A) an aliphatic diamine compound, (B) an aromatic amine compound and (C) a quinone compound. The substance obtained. The raw materials and the synthesis will be described below.

(A) Aliphatic Diamine Compound The aliphatic diamine compound (A) is, for example, methylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, 2,3-diaminobutane, pentamethylenediamine, 2,4- Examples thereof include diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine and the like. Among these, preferred are methylenediamine, ethylenediamine, trimethylenediamine, 2,3-diaminobutane and 2,4-diaminopentane. In the present invention,
The above aliphatic diamine compounds can be used alone or as a mixture of two or more kinds.

(B) Aromatic Amine Compound The aromatic amine compound (B) 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,
2,3-diaminotoluene, 5-nitro-2-aminophenol, 2-nitro-4-aminophenol, 4-amino-2-aminophenol, ortho, meta or para-aminobenzenesulfonic acid, ortho, meta or para -Aminosalicylic acid, ortho, meta or para-aminobenzoic acid and the like are exemplified. Preferred among these are ortho or para-aminophenol, ortho or para-aminobenzenesulfonic acid, ortho or para-aminosalicylic acid, ortho or para-aminobenzoic 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. 〕In particular,
4-aminodiphenylamine, 2-aminodiphenylamine, 4,4'-diaminodiphenylamine, 4-amino-3'-methoxydiphenylamine, 4-amino-4 '
Examples include diphenylamines such as hydroxydiphenylamine. Among these, preferred are 4-aminodiphenylamine, 2-aminodiphenylamine,
It is 4,4'-diaminodiphenylamine.

[Chemical 3]

[Here, 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,
Examples include 2,3-diaminonaphthalene and the like. Among these, preferred are α-naphthylamine and 1-amino-
5-hydroxynaphthalene and 1,8-diaminonaphthalene. In the present invention, the aromatic amine compound is
They can be used alone or as a mixture of two or more kinds.

(C) Quinone Compound The quinone compound (C) is represented by, for example, the following general formula (4)
It is a compound represented by (7).

[Chemical 4]

[Chemical 5]

[Here, R ¹ and R ² may be the same or different and are as described above. Specific examples include ortho or para-benzoquinone, oxy-para-benzoquinone, chloro-para-benzoquinone, bromo-para-benzoquinone, juroquinone, chloranil and the like. Among these, preferable are ortho-benzoquinone, para-benzoquinone, oxy-para-benzoquinone and duroquinone.

[Chemical 6]

[Chemical 7] [Here, R ¹ and R ² may be the same or different,
As described above. R ³ is -H, -OH, -C
_{H 3, -Cl, -COCH 3,} - OCH 3, -COOH, represents a -SO ₃ H. ]

Specific examples thereof include 6-methyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, lawson, juglone, plumbagin, α-naphthoquinone and β-naphthoquinone. Among these, the preferred one is
Lawson, juglone, plumbagin, α-naphthoquinone. In the present invention, the quinone compound may be used alone or as a mixture of two or more kinds.

Condensation Reaction The condensation of the above-mentioned aliphatic diamine compound (A), aromatic amine compound (B) and quinone compound (C) is carried out in an organic solvent system medium, if necessary, in the presence of a condensation catalyst. .. The pH of the organic solvent medium is usually in the range of 1-13. The pH adjusting agent can be used without particular restrictions.

As a medium for 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. When using a mixed solvent of water and an organic solvent having miscibility with water,
The organic solvent is preferably 50% by weight or less, further,
It is preferably 30% by weight or less. As a medium miscible with water, for example, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate can be used, and preferred ones among them are used. Are alcohols.

If necessary, a condensation catalyst is used. Examples of the condensation catalyst include oxyacids such as iodic acid, periodate, potassium periodate, sodium perchlorate, etc. or oxyacid salts; hydrogen peroxide. , Peroxides such as sodium peroxide, potassium persulfate, ammonium persulfate; iodine, bromine,
Chlorine and fluorine halogens, ferrous chloride, ferric chloride,
Metal salts such as copper sulfate and cuprous chloride; organic peroxides such as benzoyl peroxide, peracetic acid, cumene hydroperoxide, perbenzoic acid and para-menthane hydroperoxide; α, α′-azobisisobutyrate Ronitrile,
Azo catalysts such as α, α'-azobis-2,4-dimethylvaleronitrile, nitrobenzene, ortho, meta or para-oxynitrobenzene, ortho, meta or para-nitroanisole, ortho, meta or para-chloronitrobenzene, ortho, Aromatic nitro compounds such as meta or para-nitrobenzoic acid, ortho, meta or para-nitrobenzene sulfonic acid, etc. are exemplified. Since the quinone compound acts as a condensation catalyst, the condensation reaction can be performed without using a condensation catalyst.

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

The condensation product is affected by the type, composition ratio, reaction temperature and reaction time of the aliphatic diamine compound, the aromatic amine compound and the quinone compound. In the present invention, 1 weight of the aliphatic diamine compound (A) is used. The amount of the aromatic amine compound (B) is preferably 0.01 to 15 parts by weight, and more preferably 0.1 to 5 parts by weight, per part. Further, the quinone compound (C) is added per 1 part by weight of the aliphatic diamine compound (A).
It is preferably 0.01 to 15 parts by weight, and further 0.1 to 5
It is preferable to use parts by weight.

Preparation of Coating Liquid The coating liquid containing the condensation product produced by the above condensation reaction may be prepared, for example, by adding the following solvent to the condensation product containing solution which has undergone the above condensation reaction. .. Also,
After removing the solvent of the condensation product-containing solution, pulverizing and adding the following solvent, or by pouring the condensation product-containing solution into cold water to precipitate the condensation product, the precipitate is filtered off, It may be prepared by adding the following solvent to the dried product. Examples of the solvent used for preparing the coating solution of the scale inhibitor of the condensation product of the component (A), the component (B) and the component (C) include water; methanol, ethanol, propanol, butanol, 2- Butanol, 2-methyl-1
-Propanol, 2-methyl-propanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 2
-Alcohol solvents such as pentanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ester solvents such as methyl formate, ethyl formate, methyl acetate, methyl acetoacetate; 4-methyldioxolane, ethylene glycol diethyl ether, etc. Ether solvents; furans; aprotic solvents such as dimethylformaside, dimethylsulfoxide, acetonitrile and the like. These are appropriately used alone or as a mixed solvent of two or more kinds.

The pH of the coating solution is preferably 3.0 to 13.0, particularly preferably 8.0 to 13.0. The pH adjuster can be used without particular limitation, and examples thereof include phosphoric acid, perchloric acid, sulfuric acid, hydrochloric acid, nitric acid, phytic acid, acetic acid,
Acidic compounds such as paratoluene sulfonic acid, tannic acid,
LiOH, KOH, NaOH, Na ₂ CO ₃ , Na ₂ SiO ₃ , Na ₂ HPO
₄ , alkali metal compounds such as NH ₄ OH or ammonium compounds, ethylenediamine, tetramethylenediamine,
Examples thereof include alkaline compounds such as ethanolamine, diethanolamine, triethanolamine, guanidine, diethylenediamine, and triethylenetetramine. 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 usually about 0.001 to 15% by weight, Preferably 0.01
~ 1% by weight.

Further, for example, cationic, nonionic and anionic surfactants can be added to the coating solution as long as the effect of preventing scale is not impaired. If necessary, hydroxyl group-containing polymer can be added. Water-soluble polymers such as compounds, cationic polymer compounds, anionic polymer compounds and amphoteric polymer compounds can be added.

Examples of the hydroxyl group-containing polymer compound include starches such as amylose, amylopectin, dextrin, oxidized starch, acetyl starch, nitrostarch, 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, dimethyl diamyl ammonium chloride cyclized polymer, and dimethyl. Cyclic polymer of diethylammonium bromide, cyclized polymer of diallylamine hydrochloride, cyclized 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 compounds 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 liquid 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 adherence of the polymer scale to those sites is formed. 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.

There is no limitation on the method of drying the wet surface due to the application of the coating liquid, 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, a coating film is formed by applying a coating treatment to the inner wall of the polymerization vessel, and preferably to the other portions where the monomer contacts during the polymerization, and then the coating is formed in the polymerization vessel by 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; diene-based monomers such as butadiene, chloroprene, isoprene; styrene, acrylonitrile, vinylidene halide, vinyl ether, etc. 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 initiator 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 the polymerization, the polymer scale adhesion can be prevented regardless of the material of the inner wall 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 anti-adhesion 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 further added directly to the polymerization system to improve the scale prevention effect. 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 fish eye, bulk specific gravity and particle size distribution.

[0046]

EXAMPLES Production Example 1 Production of condensation product No. 1 A pressure resistant reactor was charged with 975 g of methanol, 10 g of ethylenediamine as an aliphatic diamine compound and 10 g of para-aminobenzoic acid as an aromatic amine compound, and stirred at room temperature to obtain ethylenediamine. And para-aminobenzoic acid were dissolved in methanol. Next, 5 g of para-benzoquinone as a quinone compound was added to the above methanol solution and the temperature was raised to 50 ° C. After reacting at 50 ° C. for 10 hours, it was cooled to obtain a solution of a condensation product. This solution was designated as condensation product No. 1.

Production of Condensation Products Nos. 2 to 12 Using the aliphatic diamine compound, aromatic amine compound, quinone compound and solvent shown in Table 1 at the reaction temperature and reaction time shown in the same table, the condensation product Condensation reaction was carried out in the same manner as the product No. 1 to obtain condensation products No. 2 to 12. However,
Experiment Nos. 2, 3, and 4 marked with * in Table 1 are comparative examples.

[0048]

[Table 1]

Example 1 (Experiment Nos. 101 to 112) Polymerization was carried out in the following manner using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 2000 liters. The condensation products used in each experiment are shown in Table 2. First, after adding the solvent so that the solvent ratio and the concentration of the condensation product shown in Table 2 are obtained, the pH adjusting agent shown in Table 2 is added to adjust the pH shown in Table 2 before coating. A liquid was prepared. These coating solutions were applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade and other portions where the monomers come into contact with each other during the polymerization, heated at 50 ° C. for 15 minutes and dried to form a coating film, and then washed with water.

However, Experiment No. 102 marked with * in Table 2
Nos. 104 to 104 are comparative examples in which a coating liquid containing two components of the components (A), (B) and (C) was applied.

Then, in a polymerization vessel in which a coating film was formed by applying the coating treatment in this way, 800 kg of water, 400 kg of vinyl chloride, 500 g of partially saponified polyvinyl alcohol, 50 g of hydroxypropylmethyl cellulose and 3,5,5-trimethylhexahexa Charge 140 g of Noyl peroxide and stir.
Polymerization was carried out at 66 ° C 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.

The operation from the formation of the coating film through the polymerization to the washing of the inner wall of the polymerization vessel with water is defined as one batch, and the same operation is repeated for 15 batches thereafter. The amount was examined in two parts, the liquid phase part and the vicinity of the interface between the gas phase part and the liquid phase part. After scraping off the scale adhering to 10 cm ² of the predetermined area of each part with a spatula, and weighing. The measured value was multiplied by 100 to determine the scale adhesion amount per 1 m ² . The results are shown in Table 2. Moreover, the fish eye when the polymer obtained in each experiment was formed into a sheet was measured by the following method. The results are shown in Table 2.

Measurement of fish eye 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, it was formed into a sheet having a thickness of 0.2 mm, 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.
Heat the sample at ² for 0.2 hours and press-mold it to make a sample for measurement. For this sample, the lightness index L in the Hunter color difference formula described in JIS Z 8730 (1980) was obtained, and the larger the L value, the higher the whiteness, that is, the better the initial colorability.

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).

[0056]

[Table 2]

Example 2 (Experiment Nos. 201 to 212) Polymerization was carried out as follows using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 20 liters. The condensation products used in each experiment are shown in Table 3. First, after adding a solvent so that the solvent ratio and the concentration of the condensation product shown in Table 3 are obtained, the pH shown in Table 3 is adjusted to adjust the pH shown in Table 3.
A coating solution was prepared by adding a regulator. These coating solutions were applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade and other portions where the monomers come into contact with each other during the polymerization, heated at 50 ° C. for 15 minutes and dried to form a coating film, and then washed with water. However, Experiment Nos. 202 to 204 marked with * in Table 3 are 2 of the components (A), (B) and (C).
It is a comparative example in which a coating liquid containing components was applied.

Next, 9 kg of water and sodium dodecylbenzenesulfonate 2 were placed in the coating 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.

Then, the operation from the formation of the above coating film to the washing of the inner wall of the polymerization vessel through the polymerization is regarded as one batch, and the same operation is repeated 15 batches thereafter. The amount was examined in the same manner as in Example 1 for two parts, the liquid phase part and the vicinity of the interface between the gas phase part and the liquid phase part. The results are shown in Table 3. 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 3.

Measurement of lightness index (L value) 1 kg of a 2% magnesium sulfate solution was added to 1 kg of the obtained polymer.
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,
Heat at 50 ℃ -60kgf / cm ² at 5 ℃ for 0.2 hours, final pressure 80kg
A sample for measurement is prepared by pressure molding at f / cm ² . The lightness index L value of this sample was determined in the same manner as described above.

[0061]

[Table 3]

[0062]

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 fish eyes after molding. Furthermore, 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. Good property.

Further, when the 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, whereby the productivity is improved.

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[Procedure amendment]

[Submission date] April 15, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

When the product polymer is processed into a molded article such as a sheet, the resulting molded article is required to have high whiteness. That is, even if the polymer is molded into a sheet or the like without adding any coloring agent, the obtained molded product is slightly colored. This coloring is called initial coloring, and it is desired that the coloring is as small as possible. However, since 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, the whiteness of the molded article is lowered, that is, the initial coloring. Sex deteriorates.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

Therefore, an object of the present invention is to polymerize a monomer having an ethylenic double bond 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. In addition to effectively preventing polymer scale from adhering, when molded into a sheet, etc., a product polymer is obtained in which a molded product with extremely few fish eyes and good initial coloring is obtained. It is an object of the present invention to provide a polymer scale adhesion preventive agent, a polymerization vessel using the inhibitor and a method for producing a polymer.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

(C) Quinone Compound The quinone compound (C) is represented by, for example, the following general formula (4)
It is a compound represented by (7).

[Chemical 4]

[Chemical 5]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

[Here, R ³ is --H, --NH ₂ , --Cl,-
_{Br, -OH, -NO 2, -COCH} 3, - OCH 3, -N (CH 3) 2
Or represents an alkyl group having 1 to 3 carbon atoms, R ⁴ is-
It represents _{H, -NH 2, -OH, -CH} 3, -COOH, and -SO ₃ H. Specific examples include ortho or para-benzoquinone, oxy-para-benzoquinone, chloro-para-benzoquinone, bromo-para-benzoquinone, juroquinone, chloranil and the like. Among these, preferable are ortho-benzoquinone, para-benzoquinone, oxy-para-benzoquinone and duroquinone.

[Chemical 6]

[Chemical 7] [Here, R ³ and R ⁴ may be the same or different,
As described above. R ⁵ is -H, -OH, -C
_{H 3, -Cl, -COCH 3,} - OCH 3, -COOH, represents a -SO ₃ H. ]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

The medium for the condensation reaction is preferably an organic solvent such as alcohols, ketones, ester water, etc .; a mixed solvent of water and an organic solvent miscible with water. When a mixed solvent of water and an organic solvent miscible with water is used, water is preferably 50% by weight or less, and further 30
It is preferably not more than weight%. As the organic solvent miscible with water, for example, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate can be used, and preferred among these. Things are alcohols.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Aliphatic diamine compound for carrying out condensation reaction
The ratio of (A), aromatic amine compound (B) and quinone compound (C) affects the type of aliphatic diamine compound, aromatic amine compound and quinone compound and the type of solvent used, reaction temperature, reaction time, etc. But the aliphatic diamine compound
(A) 0.01 to 0.01 parts by weight of the aromatic amine compound (B)
It is preferably 15 parts by weight, more preferably 0.1 to 5 parts by weight. In addition, the aliphatic diamine compound (A) 1
The amount of the quinone compound (C) is preferably 0.01 to 15 parts by weight, and more preferably 0.1 to 5 parts by weight, based on parts by weight. The polymer scale adhesion preventive agent of the present invention having the above condensation product as an essential component, for example, is formed as a coating film on the inner wall surface of the polymerization vessel or the like to prevent the adhesion of the polymer scale to the inner wall surface of the polymerization vessel or the like. To prevent. Normal,
When the coating film is formed on the inner wall surface of the polymerization vessel or the like, the polymer scale adhesion preventive agent is used in the state of a solution or a dispersion liquid, that is, as a coating liquid.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Preparation of Coating Liquid The coating liquid containing the condensation product produced by the above condensation reaction may be prepared, for example, by adding the following solvent to the condensation product containing solution which has undergone the above condensation reaction. .. Also,
After removing the solvent of the condensation product-containing solution, pulverizing and adding the following solvent, or by pouring the condensation product-containing solution into cold water to precipitate the condensation product, the precipitate is filtered off, It may be prepared by adding the following solvent to the dried product. Examples of the solvent used for preparing the coating solution for the scale inhibitor of the condensation product of the components (A), (B) and (C) include water; methanol, ethanol, propanol, butanol, 2-butanol. , 2-methyl-1
-Propanol, 2-methyl-2-propanol, 3-
Alcohol solvents such as methyl-1-butanol, 2-methyl-2-butanol, 2-pentanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl formate, ethyl formate, methyl acetate,
Examples include ester solvents such as methyl acetoacetate; ether solvents such as 4-methyldioxolane and ethylene glycol diethyl ether; furans; aprotic solvents such as dimethylformamide, dimethylsulfoxide, and acetonitrile. These are appropriately used alone or as a mixed solvent of two or more kinds.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

Examples of the hydroxyl group-containing polymer compound include starches such as amylose, amylopectin, dextrin, oxidized starch, acetyl starch, nitrostarch, methyl starch, carboxymethyl starch and derivatives thereof; pectic acid, protopectin, Hydroxyl group-containing vegetable slime such as pectinic acid, alginic acid, laminarin, fucoidin, agar, carrageenin; hydroxyl-containing animal slime such as hyaluronic acid, chondroitin sulfate, heparin, keratosulfate, chitin, chitosan, caronin sulfate, limacoitin sulfate;
Nucleic acids such as ribonucleic acid and deoxyribonucleic acid; methyl cellulose, 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 ester sulfonate, cellulose ester carbamic acid, nitrocellulose, phosphorus Cellulose derivatives such as acid cellulose 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, alkali lignin, thioalkali lignin, acid lignin, oxidation - Ammonia lignin, such as periodate lignin; phenol - formaldehyde resins, partially saponified polyvinyl alcohol, polyvinyl alcohol and the like.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

The operation from the formation of the coating film through the polymerization to the washing of the inner wall of the polymerization vessel with water is defined as one batch, and the same operation is repeated for 15 batches thereafter. The amount was examined in two parts, the liquid phase part and the vicinity of the interface between the gas phase part and the liquid phase part. After scraping off the scale adhering to the predetermined area of 10 x 10 cm on each part with a spatula, weigh the scale and multiply the measured value by 100 to 1 m.
The scale adhesion amount per ² was determined. The results are shown in Table 2. Moreover, the fish eye when the polymer obtained in each experiment was formed into a sheet was measured by the following method. The results are shown in Table 2.

Claims (3)

[Claims] 1. A method for polymerizing a monomer having an ethylenic double bond, which comprises (A) an aliphatic diamine compound, (B) an aromatic amine compound, and (C) a condensation product of a quinone compound. Polymer scale anti-sticking agent. 2. An ethylenic double bond having a coating film formed on its inner wall, which contains a condensation product of (A) an aliphatic diamine compound, (B) an aromatic amine compound, and (C) a quinone compound. A polymerization vessel for polymerizing the monomer having. 3. 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) an aliphatic diamine compound, (B) an aromatic amine compound, and (C) a condensation product of a quinone 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.