JPH08311108A - Polymer scale anti-adhesion agent and method for producing polymer using the same - Google Patents

Abstract

(57) [Summary] [Structure] A polymer scale anti-adhesion agent for polymerization of a monomer having an ethylenically unsaturated double bond, which contains a reaction product of a condensate of an aminonaphthalene compound and p-benzoquinone. [Effect] Even in a polymerization system containing a monomer such as styrene, α-methylstyrene, acrylic acid, acrylic ester, acrylonitrile, etc., which has a remarkably high solubility in a coating film composed of a conventional polymer scale anti-adhesive, It is possible to reliably prevent the adherence of.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer scale anti-adhesion agent used for polymerizing a monomer having an ethylenically unsaturated double bond and a method for producing a polymer using the same.

[0002]

2. Description of the Related Art It is known that when a monomer having an ethylenically unsaturated double bond is polymerized, a polymer scale tends to adhere to the inner wall surface of a polymerization vessel. If the polymer scale adheres, the yield of the polymer, the cooling capacity of the polymerization vessel, etc. will decrease, and as a result of the polymer scale peeling and mixing into the polymer, the molding obtained by molding such a polymer The disadvantage is that the quality of the product is reduced. Also,
The work of removing the adhered polymer scale requires not only an excessive amount of labor and time, but also unreacted monomers present in the polymer scale may cause damage to the human body.

Conventionally, for example, in a method of suspension polymerization of a vinyl halide monomer, in order to prevent the polymer scale from adhering to the inner wall surface of the polymerization vessel, the polymer scale is attached to the inner wall surface of the polymerization vessel. A method of forming a coating film comprising an inhibitor is known. Examples of the polymer scale adhesion preventive agent used in this method include a specific polar compound (Japanese Patent Publication No. 45-30343), a dye or a pigment (Japanese Patent Publication No. 45-3).
0835, 52-24953), aromatic amine compounds (JP-A-51-50887), reaction products of phenol compounds with aromatic aldehydes (JP-A-55-54317), aromatic Amine condensates (Japanese Patent Publication No. 60-30681) are known. However, coating films composed of these polymer scale anti-adhesion agents include, for example, styrene, α-methylstyrene,
It has a drawback that it is easily dissolved in monomers such as acrylic acid ester, acrylonitrile and vinyl acetate. Therefore,
When polymerizing a monomer mixture containing these monomers, it is possible to effectively prevent the polymer scale from adhering to the inner wall surface of the polymerization vessel or the like even if the above polymer scale anti-adhesion agent is used. I can't. In particular, when the concentration of the above-mentioned monomer is high, or when the concentration is low and the polymerization time is long, the polymer scale tends to adhere.

[0004]

The object of the present invention, even when polymerizing a monomer mixture having an ethylenically unsaturated double bond mainly composed of the above-mentioned monomers such as styrene, An object of the present invention is to provide a polymer scale adhesion preventive agent capable of sufficiently preventing the polymer scale from adhering to the inner wall surface of the polymerization vessel and the like, and a method for producing a polymer using the same.

[0005]

That is, the present invention provides a polymer for polymerization of a monomer having an ethylenically unsaturated double bond containing a reaction product of a condensate of an aminonaphthalene compound and p-benzoquinone. An integrated scale anti-adhesive agent is provided.

The present invention also provides a polymer having a step of polymerizing a monomer having an ethylenically unsaturated double bond in a polymerization vessel having a coating film having a polymer scale adhesion preventing property on the inner wall of the polymerization vessel. In the method for producing a polymer, the coating film having the polymer scale anti-adhesion property comprises the polymer scale anti-adhesion agent. Hereinafter, the present invention will be described in detail.

(Polymer scale anti-adhesion agent) The polymer scale anti-adhesion agent of the present invention contains a reaction product of the condensate of the aminonaphthalene compound and p-benzoquinone. As the condensate of the aminonaphthalene compound used in the reaction product, for example, the following general formula:

[0008]

Embedded image

[In the formula, R ¹ is -H, -COOH, -OH, -NH
A monovalent atom or group selected from ₂ and —CH ₃ , and R
² -NH _2, is a monovalent atom or group selected from -COOH and -H, m is 1-2 integer, n represents an integer of 1 to 4. ] The condensate of the amino naphthalene compound shown by these is mentioned. Specific examples of the aminonaphthalene compound represented by the general formula include, for example, β-naphthylamine,
3-amino-2-naphthoic acid, 3-amino-2-naphthol, 5-amino-1-naphthol, 1-amino-2-
Examples thereof include naphthol, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene and 4-amino-2-methyl-1-naphthol. Preferred among these are 3-amino-2-naphthol,
These are 5-amino-1-naphthol, 1-amino-2-naphthol, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene and 2,3-diaminonaphthalene. You may use these individually by 1 type or in combination of 2 or more type.

Examples of the method for condensing the aminonaphthalene compound include a solution condensation method in which the aminonaphthalene compound is condensed in a solvent in the presence of a catalyst.

Examples of the solvent include polar solvents such as dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, N-methylpyrrolidone and nitrobenzene. These may be used alone or in combination of two or more. You may use it in combination. Further, when a low molecular weight condensate is obtained, water, alcohol or the like may be used in combination with these solvents.

Examples of the catalyst include iron chloride (II
I), aluminum chloride, copper (II) chloride, metal salts such as potassium permanganate; persulfates such as ammonium persulfate;
Inorganic peroxides such as hydrogen peroxide; oxidants of organic peroxides such as benzoyl peroxide.

The condensation reaction of the aminonaphthalene compound is carried out at a temperature not higher than the boiling point of the solvent, and usually 10 to 150 ° C., preferably
Perform at 30-120 ° C. The reaction time is usually 1 to 30 hours,
It is preferably 1 to 15 hours. After completion of the reaction, the reaction solution is put into a poor solvent in an amount of 1 to 20 times by weight of the solution to precipitate a condensate, and the condensate is filtered and dried to obtain a condensate of an aminonaphthalene compound. . The poor solvent for depositing the condensate, for example, water, saline,
Ether, benzene, n-hexane, isopropanol, etc. are mentioned.

The reaction product of a condensate of an aminonaphthalene compound and p-benzoquinone includes, for example, a condensate of an aminonaphthalene compound and p-benzoquinone, a condensate of an aminonaphthalene compound, p-benzoquinone and a reaction product thereof. The reaction proceeds in a homogeneous system in which the product is completely dissolved in the reaction solvent, or in a state in which the condensation product of the aminonaphthalene compound, p-benzoquinone and their reaction products are dispersed in the reaction solvent. It can be obtained by reacting in a homogeneous system. Examples of the solvent include polar solvents such as dimethylformamide, N, N-dimethylacetamide and acetonitrile; cyclic ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methylethylketone; alcohols such as methanol, ethanol and isopropanol; Water and the like can be used, and these can be used alone or in combination of two or more.

The weight ratio of the condensate of aminonaphthalene compound / p-benzoquinone is usually 100/1 to 1/10, preferably 20/1 to 1/5. The total concentration of the condensate of aminonaphthalene compound and p-benzoquinone in the solvent is preferably 1 to 50% by weight. The reaction temperature is not higher than the boiling point of the solvent, preferably 20 to 100 ° C. The reaction time is usually 1 minute to 30 hours, preferably 1 to 10 hours. The reaction rate can be adjusted, for example, by adding mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid; bases such as NaOH, KOH; preferably phosphoric acid to the reaction system. After completion of the reaction, the obtained reaction solution may be used as it is as a polymer scale adhesion preventing agent. Further, the reaction solution was put into a poor solvent in an amount of 1 to 20 times the amount of the solution to precipitate a reaction product, and the reaction product was filtered and dried to be used as a polymer scale anti-adhesive agent. Good. Examples of the poor solvent for precipitating the reaction product include water, saline, ether, benzene, n-hexane, isopropanol and the like.

The polymer scale adhesion preventive agent of the present invention preferably contains an inorganic colloid in addition to the reaction product. Examples of the inorganic colloid include gold colloid, silver colloid, sulfur colloid, ferric hydroxide colloid, stannic acid colloid, silicic acid colloid, manganese dioxide colloid, molybdenum oxide colloid, barium sulfate colloid, and water. Aluminum oxide colloid,
Examples thereof include a vanadium pentoxide colloid and a lithium silicate colloid. These can be used alone or in combination of two or more. Of these, preferred are silicic acid colloids and aluminum hydroxide colloids. Particularly suitable silicic acid colloids are aqueous silica sol, methanol silica sol, butanol silica sol,
Ethylene glycol silica sol and DMF silica sol. The blending amount of the inorganic colloid is such that the weight ratio (in terms of solid content) of the inorganic colloid / the reaction product is usually 100/1 to 1/100,
The amount is preferably 10/1 to 1/10. If the amount of the inorganic colloid is too small, the advantage of using it together may not be obtained.

The reaction product obtained by reacting such a condensate of an aminonaphthalene compound with p-benzoquinone has a low activity of the amino group contained therein as compared with a conventional aromatic amine condensate, and Large molecular weight. When the activity of the amino group is low, the effect of the reaction product on the polymerization system of the monomer is small, and when the molecular weight is high, the amount of dissolution by the monomer is small. Therefore, it is presumed that the polymer scale anti-adhesion agent of the present invention exhibits a remarkable scale anti-adhesion property.

(Process for Producing Polymer Using Polymer Scale Anti-Adhesion Agent) The process for producing a polymer of the present invention is performed in a polymerization vessel having a coating film comprising the polymer scale deposition inhibitor on the inner wall of the polymerization vessel. , A method of polymerizing a monomer having an ethylenically unsaturated double bond.

For the coating film, for example, a reaction solution containing the reaction product of the above-mentioned aminonaphthalene compound condensate and p-benzoquinone is applied as it is or a coating solution prepared as follows is applied to the inner wall of the polymerization vessel and dried. Can be formed.

Preparation of Coating Solution A coating solution is obtained by dissolving or dispersing the reaction product of the aminonaphthalene compound condensate and p-benzoquinone, and optionally an inorganic colloid in a suitable solvent.

The solvent for preparing the coating solution is, for example,
Water; alcohol solvents such as methanol and isobutyl alcohol; aromatic hydrocarbon solvents such as benzene, toluene, xylene; methylene chloride, dichloroethylene, 1,1,2
-Halogenated hydrocarbon solvents such as trichloroethane; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as methyl formate and ethyl acetate; ether solvents such as 1,4-dioxane and ethylene glycol monomethyl ether; dimethylformamide, Examples thereof include polar solvents such as N, N-dimethylacetamide and N-methylpyrrolidone. These can be used alone or in combination of two or more. Among them, water is preferred.
The solvent is methanol, isobutyl alcohol, acetone, dimethylformamide or a mixture thereof. The concentration of the reaction product of the condensate of aminonaphthalene compound and p-benzoquinone in the coating solution may be usually 0.001 to 10% by weight, preferably 0.01 to 2% by weight. Further, the coating liquid further containing an inorganic colloid preferably contains 0.01 to 5% by weight as the total amount of the reaction product and the inorganic colloid (calculated as solid content). As a method of adding an inorganic colloid to the reaction product, after dissolving or dispersing the reaction product in the solvent, water is previously added to the solution or dispersion, the solvent used in the coating liquid, the inorganic. An inorganic colloid having a concentration of 1 to 10% by weight is mixed with a colloid (solid content conversion) dispersion medium or the like.

Formation of Coating Film To form a coating film on the inner wall surface of the polymerization vessel using the prepared coating solution, first, the coating solution is applied to the inner wall surface of the polymerization vessel, and then
For example, after sufficiently drying in the temperature range from room temperature to 100 ° C., the inner wall surface of the polymerization vessel is further washed with water if necessary. Further, the coating film is preferably formed not only on the inner wall surface of the polymerization vessel, but also on other portions where the monomer contacts during the polymerization,
Examples of such parts include stirring blades, stirring shafts, baffles, condensers, headers, search coils, bolts, nuts, and the like. Further, even at a site other than the site where the monomer comes into contact during the polymerization, the site where the polymer scale may be attached, for example, the inner surface of the equipment and piping of the recovery system of the unreacted monomer, etc. It is preferable to form a film. Examples of such a part include inner surfaces of a monomer distillation column, a condenser, a monomer storage tank, a valve, and the like. The coating film may be formed at the location in the same manner as when it is formed on the inner wall surface of the polymerization vessel.

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 may occur. To be prevented. The method of applying the coating liquid to the inner wall surface of the polymerization vessel is not particularly limited, and includes, for example, brush coating, spray coating, a method of withdrawing after filling the polymerization vessel with the coating solution, and the like.
It is also possible to use the automatic coating methods described in JP-B No. 55-36288, JP-B No. 56-501116, JP-B No. 56-501117, JP-A No. 59-11303, and the like.

The method of drying after coating is not limited, and examples thereof include a method of applying hot air having a suitable temperature after coating to the coating surface, the inner wall surface of the polymerization vessel to be coated with the coating liquid and other surfaces. Is heated in advance to, for example, 30 to 80 ° C,
A method of directly applying the coating solution to the heated surface can be used. When the boiling point of the solvent or dispersion medium of the coating liquid exceeds 80 ° C, it may be dried under reduced pressure if necessary. After drying, the coated surface can be washed with water if necessary. The coating film thus obtained has a total coating amount after drying of usually 0.001 to 5 g / m 2.
² is preferable, and 0.01 to 3 g / m ² is particularly preferable.

The above coating operation may be carried out for every one to several batches of polymerization. The coating film formed has high durability,
Since the action of preventing the polymer scale from adhering continues, it is usually sufficient to perform the coating operation once every several batches. Thereby, the polymerization vessel can be repeatedly used without adhering the polymer scale to the inner wall of the polymerization vessel or the like.

Polymerization As described above, the inner wall of the polymerization vessel and other portions where the monomers come into contact with each other during the polymerization are subjected to coating treatment to form a coating film, and then polymerization is carried out in the polymerization vessel by a conventional method. That is,
In addition to a monomer having an ethylenically unsaturated double bond and a polymerization initiator (catalyst), a polymerization medium such as water, a suspending agent, a solid dispersant, a dispersant such as a nonionic or anionic emulsifier, if necessary. Etc. are charged, and then polymerization is performed.

Examples of the monomer having an ethylenically unsaturated double bond which is 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, etc. Styrene; acrylonitrile; vinylidene halide; vinyl ether; isobutene and the like.

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 for both bulk polymerization and gas phase polymerization, and is more suitable for polymerization in an aqueous medium such as suspension polymerization and emulsion polymerization. The method of the present invention is particularly preferably applicable to suspension polymerization or emulsion polymerization of a vinyl chloride-based monomer mixture; production of beads, latex such as polystyrene, polymethylmethacrylate, polyacrylonitrile; SBR, NBR , Production of synthetic rubber by emulsion polymerization of CR, IR, IIR, etc .; production of ABS resin; and production of AS resin by suspension polymerization using a solid dispersant. Less than,
A general polymerization method will be specifically described.

First, water and a dispersant are charged into a polymerization vessel, and then a polymerization initiator is charged. Next, exhaust the inside of the polymerization vessel.
After reducing the pressure to 0.1 to 760 mmHg, the monomers are charged (at this time, the internal pressure of the polymerization vessel is usually 0.5 to 30 kgf / cm ² · G), and then the polymerization is carried out at a reaction temperature of 30 to 150 ° C. During the polymerization, if necessary, 1 of water, a dispersant and a polymerization initiator is added.
Seed or two or more types are added. Further, the reaction temperature during the polymerization depends on the type of the monomer to be polymerized, for example,
In the case of vinyl chloride polymerization, the polymerization is carried out at 30 to 80 ° C, and in the case of styrene polymerization, it is carried out at 50 to 150 ° C. Polymerization is performed when the internal pressure of the polymerization vessel drops to 0 to 7 kgf / cm ² · G,
Or flow into the jacket equipped around the polymerizer,
It is judged to be completed when there is almost no difference between the inlet temperature and the outlet temperature of the cooling water to be discharged (that is, when the heat generation due to the polymerization reaction is eliminated). Water, a dispersant and a polymerization initiator charged at the time of polymerization are usually 20 to 500 parts by weight of water, 0.01 to 30 parts by weight of a dispersant, and 100 parts by weight of a monomer.
The amount of the polymerization initiator is 0.01 to 5 parts by weight.

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 or emulsion polymerization.

In the case of bulk polymerization, the inside of the polymerization vessel is
After evacuation to a pressure of 0.01 to 760 mmHg, a monomer and a polymerization initiator are charged in the polymerization vessel, and polymerization is carried out at a reaction temperature of -10 to 250 ° C. For example, in the case of vinyl chloride polymerization,
It is carried out at 80 ° C. and, in the case of styrene polymerization, at 50 to 150 ° C.

When polymerization is carried out using the method for preventing adhesion of polymer scale of the present invention, adhesion of polymer scale can be prevented regardless of the material of the inner wall surface of the polymerization vessel and the like. For example, when the polymerization is carried out in a stainless steel or other steel polymerization vessel, a glass-lined polymerization vessel, etc., the polymer scale can be prevented from adhering. What is added to the polymerization system can be used without any restrictions. For example, t-butyl peroxy neodecanoate, bis (2-ethylhexyl) peroxydicarbonate, 3,5,5-trimethylhexanoyl peroxide, α-cumylperoxy neodecanoate, cumene hydroperoxide , Cyclohexanone peroxide, t-butylperoxypivalate, bis (2-ethoxyethyl) peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, α , Α'-azobisisobutyronitrile, α, α'-azobis-2,4-dimethylvaleronitrile, potassium persulfate, ammonium persulfate, p-menthane hydroperoxide, and other polymerization initiators; partially saponified polyvinyl alcohol , Polyacry Suspending agents for copolymers of acid, vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropylmethyl cellulose and natural or synthetic polymer compounds such as gelatin; solid dispersants such as calcium phosphate and hydroxyapatite; sorbitan mono Nonionic emulsifiers such as laurate, sorbitan trioleate and polyoxyethylene alkyl ethers;
Anionic emulsifiers such as sodium alkylbenzene sulfonates such as sodium lauryl sulfate and sodium dodecylbenzene sulfonate, sodium dioctyl sulfosuccinates; fillers such as calcium carbonate and titanium oxide; tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, dioctyl Stabilizers such as tin mercaptide; lubricants such as rice wax, stearic acid and cetyl alcohol; plasticizers such as DOP and DBP; mercaptans such as t-dodecyl mercaptan and chain transfer agents such as trichlorethylene; pH regulators; rongalit, sulfuric acid Even in a polymerization system in which a reducing agent such as iron 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 further added directly to the polymerization system. It can also be improved. In that case, it is appropriate that the addition amount of the polymer scale anti-adhesion agent is 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.

[0034]

EXAMPLES The present invention will be described more specifically by showing Examples and Comparative Examples. (A) Preparation of condensate ( preparation of condensate of aminonaphthalene compound)

[Preparation Example 1] A 200 mL three-necked flask equipped with a stirring blade and a reflux condenser was charged with 31.6 g of 1,5-diaminonaphthalene and 50 mL of nitrobenzene to start stirring. Next, a solution prepared by dissolving 2.4 g of AlCl ₃ .6H ₂ O in 40 mL of DMF was added, and the reaction was carried out at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was poured into 1000 mL of ether, the precipitated condensate was filtered under reduced pressure, thoroughly washed with water, and then dried at 50 ° C. The condensate thus obtained is called condensate (A) -1.

Preparation Example 2 In a three-necked flask similar to that used in Preparation Example 1, 1,8-diaminonaphthalene 31.6
and 50 mL of NMP were charged and stirring was started. Then, 30% H
30 mL of ₂ O ₂ was added and the reaction was carried out at 80 ° C. for 10 hours. After completion of the reaction, the reaction solution was poured into 500 mL of 10% by weight saline, washed thoroughly with water, and dried at 50 ° C. The condensate thus obtained is called condensate (A) -2.

Preparation Example 3 In a three-necked flask similar to that used in Preparation Example 1, 5-amino-1-naphthol 31.
8 g and nitrobenzene 50 mL were charged and stirring was started.
Next, a solution of 1.7 g of CuCl ₂ · 2H ₂ O dissolved in 50 mL of NMP was added, and the reaction was carried out at 50 ° C for 10 hours. After completion of the reaction, the reaction solution was put into 300 mL of benzene, the precipitated condensate was filtered under reduced pressure, further thoroughly washed with water, and then vacuum dried at room temperature. The condensate thus obtained is called condensate (A) -3.

Preparation Example 4 In a three-necked flask similar to that used in Preparation Example 1, 1,5-diaminonaphthalene 15.8 was added.
g, 5-amino-1-naphthol 15.9 g, DMF 50 mL
Then, the stirring was started. Next, anhydrous aluminum chloride
A solution prepared by dissolving 1.3 g in 30 mL of DMF was added, and the reaction was carried out at 100 ° C for 5 hours. After the reaction is complete, add 1
The mixture was poured into 000 mL, the precipitated condensate was filtered under reduced pressure, washed thoroughly with water, and then dried at 50 ° C. The condensate thus obtained is called condensate (A) -4.

Preparation Example 5 A reactor similar to that used in Preparation Example 1 was charged with 15.8 g of 1,5-diaminonaphthalene, 15.8 g of 1,8-diaminonaphthalene and DMF.
70 mL was charged and stirring was started. Then, FeCl ₃ · 6H ₂ O
A solution prepared by dissolving 2.7 g in 30 mL of water was added, and the reaction was carried out at 80 ° C for 10 hours. After the reaction was completed, the reaction solution was poured into 300 mL of isopropanol, and the precipitated condensate was filtered under reduced pressure.
After further thoroughly washing with water, it was vacuum dried at room temperature. The condensate thus obtained is called condensate (A) -5.

(B) Preparation of Reaction Product ( Preparation of Reaction Product of Condensate of Aminonaphthalene Compound and p-Benzoquinone) Condensates (A) -1 to (A) obtained in Preparation Examples 1 to 5 -5 and p-benzoquinone were mixed in the proportions shown in Table 1, then:
The reaction products (a) to (h) were produced by reacting under the conditions (reaction solvent, catalyst, reaction temperature and reaction time) shown in Table 1.
For comparison, instead of the condensate of the aminonaphthalene compound, an uncondensed aminonaphthalene compound was added.
Reaction products (i) to (k) were prepared by reacting with benzoquinone. The reaction product was obtained in a solution state. Reaction product
(b) and (f) were used in the examples described later as they were in the solution state. Reaction products (a), (c) to (e), (g) and
(h) is 5% by weight, which is 10 times the volume of the reaction solution after the reaction is completed.
The mixture was poured into a saline solution to precipitate a condensate, and the condensate was separated from the solution and made into a powder, which was used in Examples described later. In addition, in Table 1, the reaction products marked with * do not satisfy the conditions of the present invention, and are used for Comparative Examples described later.

[0041]

[Table 1]

(C) Preparation of coating liquid As shown in Table 2, the component (I) selected from the reaction products (a) to (k) is dissolved or dispersed in the solvent in the amount shown in the same table, and further, In some cases, the inorganic colloid component (II) shown in the same table is added to and mixed with the solvent so that the compounding ratio (solid content conversion) and the concentration (concentration of the total amount of the reaction product and the inorganic colloid) shown in the same table, Coating liquid Nos. 1 to 25 were prepared. However, coating liquid
In Nos. 4 and 8, the reaction product was not used, but the condensate (A) -1 was used instead. The coating liquids marked with * do not satisfy the conditions of the present invention, and were used in the comparative examples described later.

[0043]

[Table 2]

Examples 1 to 9 and Comparative Examples 1 to 4 (when a polymerization test is performed only for one batch) The inner wall of a stainless steel polymerization vessel equipped with a stirrer (internal volume: 1000 L), a stirring shaft, a stirring blade, and other single amounts Apply the coating solution of the number (No.) shown in Table 3 (see Table 2) to the part where the body contacts,
After drying at 50 ° C. for 15 minutes, it was washed with water to form a coating film.
However, in Comparative Example 1, the coating liquid was not applied. 400 kg of water, 200 kg of vinyl chloride, 250 g of partially saponified polyvinyl alcohol, 25 g of hydroxypropylmethylcellulose and 75 g of diisopropyl peroxydicarbonate were charged into this polymerization vessel, and polymerization was carried out at 57 ° C. for 6 hours while stirring. After the completion of the polymerization, the scale adhesion amount (g / m ² ) per unit area of the inner wall surface of the polymerization vessel was measured as follows. Table 3 shows the results.

Measurement method of polymer scale : After all scales attached to an area of 10 cm square can be visually confirmed, after scraping off with a spatula made of stainless steel and weighing,
The measured value was multiplied by 100 to obtain the scale adhesion amount per 1 m ² .

[0046]

[Table 3]

Examples 10 to 16 and Comparative Examples 5 to 7 (when a polymerization test was carried out only for one batch) A coating solution having a number (No.) shown in Table 4 (Table 2) was used using a polymerization vessel having an internal volume of 20 L. A coating film was formed on the polymerization vessel in the same manner as in Example 1 except that the coating) was applied. However, in Comparative Example 5, the coating liquid was not applied. Water 8k in this polymerization vessel
g, styrene monomer 5.2 kg, methacrylic acid monomer 2.8
kg, partially saponified polyacrylamide 8 g and α,
24 g of α'-azobisisobutyronitrile was charged and polymerized at 90 ° C for 5 hours while stirring. After the polymerization, the amount of polymer scale attached was measured in the same manner as in Example 1. The results are shown in Table 4.

[0048]

[Table 4]

Examples 17 to 25 and Comparative Examples 8 to 11 (1
Polymerization test was carried out in the same manner as in Example 1 except that a polymerization vessel having an internal volume of 22 L was used and a coating solution (No.) shown in Table 5 was applied (see Table 2). A coating film was formed on the container. However, in Comparative Example 8, the coating liquid was not applied. Water 10k in this polymerization vessel
g, styrene 2.5 kg, acrylonitrile 1.0 kg, SBR
2.4 kg of latex, 50 g of synthetic rubber emulsifier manufactured by Harima Kasei Co., Ltd. (Bandis T-100P, trade name), NaOH 2.0
g, 30 g of t-dodecyl mercaptan and 5.0 g of ammonium persulfate were charged, and polymerization was carried out at 70 ° C. for 2 hours while stirring. After the polymerization was completed, the amount of polymer scale attached was measured in the same manner as in Example 1. The results are shown in Table 5.

[0050]

[Table 5]

Examples 26 to 32 (When Repeated Polymerization Test was Performed ) A polymerization vessel having an internal volume of 20 L was used, and the coating liquid of No. shown in Table 6 (see Table 2) was coated. A coating film was formed on the polymerization vessel in the same manner as in Example 1. Water 9 k in this polymerization vessel
g, sodium dodecylbenzenesulfonate 225 g, t
After charging 12 g of dodecyl mercaptan and 13 g of potassium persulfate and purging 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 completion of the polymerization, the polymer slurry was extracted and then the inside of the polymerization vessel was washed with water. After 15 batch polymerizations, the steps from coating of the coating liquid, polymerization, and washing with water were defined as one batch, and then the polymer scale adhesion amount was measured in the same manner as in Example 1. Table 6 shows the results. In addition, in the present example, the amount of scale deposition was measured for a portion located in the liquid phase portion during polymerization and a portion located near the gas-liquid interface.

Comparative Examples 12 to 15 (When Repeated Polymerization Test was Performed) Coating liquid was applied to a polymerization vessel in the same manner as in Example 1 except that coating liquids No. 26 to No. 29 prepared as described below were used. A film was formed. Then, using this polymerization vessel, styrene and butadiene were polymerized in the same manner as in Example 20, and after the completion of the polymerization, the amount of polymer scale adhesion was measured in the same manner as in Example 1. Table 6 shows the results.

[Preparation of Coating Solution No. 26] 100 mL of a solution of methanol in a weight ratio of 1,5-diaminonaphthalene / nitrobenzene of 100/200 and a concentration of 1.0% by weight at 80 ° C. The reaction was carried out by stirring for 3 hours. To 20 mL of this reaction solution, 30 mL of methanol and 50 mL of water were added and mixed, and the pH was adjusted to 3.0 with HCl to obtain a coating solution.

[Preparation of Coating Solution No. 27] The weight ratio of 1,5-diaminonaphthalene / 1,8-diaminonaphthalene / p-benzoquinone was 30/30/40 and the concentration was 2.0% by weight. Solution 100 dissolved in 80 mL of methanol and 20 mL of water
mL was reacted at 30 ° C. for 10 hours with stirring. This reaction liquid 10m
To L, add 80 mL of methanol and 10 mL of water, mix, and add NaOH
The pH was adjusted to 11.0 with to prepare a coating solution.

[Preparation of Coating Liquids No. 28 and No. 29] 3 g of an aqueous silica sol (20% by weight) was added to the above coating liquids No. 26 and No. 27 and mixed to obtain coating liquid No. 28, The coating liquid was No. 29.

[0056]

[Table 6]

EFFECTS OF THE INVENTION According to the polymer scale adhesion preventing method of the present invention, it is difficult to prevent the adhesion of the polymer scale due to its large solubility in the coating film formed of the polymer scale adhesion preventing agent. In polymerization or copolymerization of a monomer having an ethylenically unsaturated double bond, it is possible to effectively prevent the polymer scale from adhering to the inner wall surface of the polymerization vessel or the like. In particular, even in a polymerization system containing a monomer such as styrene, α-methylstyrene, acrylic acid, acrylic acid ester, acrylonitrile, etc., which has a remarkably large solubility in the conventional coating film, it is possible to reliably prevent adhesion of polymer scale. it can. In addition, the formed coating film has high durability, and since the polymer scale adhesion preventing action lasts, it is possible to repeatedly use the polymerization vessel once the coating film has been formed, and thus the production It is possible to improve the sex. Further, in the conventional polymer scale anti-adhesion agent, the polymer scale of which the inner wall surface was glass lined was easier to attach the polymer scale than the stainless steel polymerization vessel, but the polymer scale anti-adhesion agent of the present invention By using, it is possible to effectively prevent the adhesion of the polymer scale regardless of the material of the inner wall of the polymerization vessel.

Claims (3)

[Claims] 1. A condensate of an aminonaphthalene compound and p-
A polymer scale anti-adhesion agent for polymerization of a monomer having an ethylenically unsaturated double bond containing a reaction product with benzoquinone. 2. The polymer scale adhesion preventive agent according to claim 1, which further contains an inorganic colloid in addition to the reaction product. 3. A method for producing a polymer, comprising a step of polymerizing a monomer having an ethylenically unsaturated double bond in a polymerization vessel having a coating film having a polymer scale adhesion preventing property on the inner wall of the polymerization vessel. The method for producing a polymer, wherein the coating film having the polymer scale adhesion preventing property comprises the polymer scale adhesion preventing agent according to claim 1 or 2.