JPH07286001A - Polymer scale deposition inhibitor and production of polymer with aid thereof - Google Patents

Abstract

PURPOSE:To obtain an inhibitor used to inhibit the deposition of scales of a polymer of a specified monomer, to reduce fish eye formation in molding and to improve the initial coloration of the polymer by mixing a condensate of a quinone compound with an aromatic amine compound. CONSTITUTION:At least one benzoquinone compound of formula I or II (wherein R1 is -H, -NH2, -Cl, -Br, -OH, -NO2, -COCH3, -OCH3, -N(CH3)2, -COOH, -SO3H or a 1-3 C alkyl) or naphthoquinone compound is reacted at 20-150 deg.C in a solvent in a concbtration of 0.5-25wt.% to obtain a condensate (A) of a molecular weight of 400-50000. 100 pts.wt. component A and 0.1-1000 pts.wt. at least one aromatic amine compound are added to an organic solvent, the pH of the solution is optionally adjusted to 7.5-13.5, and the solution is mixed with at least one member selected from among a water-soluble polymer compound, an inorganic colloid and an alkali metal silicate to obtain a coating fluid. This fluid is applied to the inside wall of a polymerizar for polymerizing an ethylenically unsaturated monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer scale adhesion preventive agent 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 Conventionally, as a method for polymerizing a monomer having an ethylenically unsaturated double bond, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method and the like are known. ing. In any of these polymerization methods, adhesion of the polymer scale is likely to occur on the inner wall of the polymerization vessel, the agitator, and 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 polymer scale peels off and is mixed into the polymer. As a result, the polymer is molded. This has the disadvantage of reducing the quality of the resulting molding. Further, in order to remove the adhered polymer scale, not only excessive labor and time are required, but also unreacted monomer is contained in this polymer scale, which is a very serious problem in recent years. There is a risk of human injury due to the monomer.

As for the prevention of adhesion of the polymer scale to the inner wall of the polymerization vessel, the polarities of amine compounds, quinone compounds, aldehyde compounds, etc. have been used, as has been carried out, for example, in suspension polymerization of vinyl chloride. A method of applying a polymer scale anti-adhesion agent composed of an organic compound to the inner wall of a polymerization vessel to form a coating film, and a method of adding these compounds to an aqueous medium in which suspension polymerization is carried out are known (Japanese Patent Publication No. 45). -30343 publication).

However, although these methods show an effect of preventing polymer scale adhesion when repeating the polymerization up to about 5 to 6 batches, when the number of polymerization batches is larger than that, the preventive effect disappears (in terms of sustainability). Inferior). This point is not particularly industrially satisfactory because the effect is remarkable when a water-soluble catalyst is used in the polymerization.

[0006] In order to overcome this disadvantage, for example, JP-A-53
No. 13689 proposes a method of applying a polymer scale anti-adhesion agent containing a condensation product of an aromatic amine compound as an active ingredient on the inner wall of a polymerization vessel or the like. When such a polymer scale anti-adhesion agent is applied to a portion such as an inner wall of a polymerization vessel where a monomer comes into contact with the coating to form a coating film, the polymerization is performed at 100 to 200
The polymer scale does not adhere to the liquid phase part in the polymerization vessel even if it is repeated about a batch. Also, when the water-soluble catalyst is used, the polymer scale adhesion in the liquid phase part is similarly prevented.

[0007]

However, even when a coating film of a polymer scale anti-adhesive agent containing the condensation product of the aromatic amine compound as an active ingredient is formed, it is positioned in the upper layer portion in the polymerization vessel. There is a drawback that polymer scale adheres near the interface between the gas phase and the liquid phase. Once the polymer scale adheres to the vicinity of the interface between the gas phase and the liquid phase, the polymer scale that adheres gradually grows as the polymerization is repeated, and finally peels off and mixes into the polymer. Sometimes. When the polymer scale is mixed with the polymer in this way, when the polymer is processed into a molded product such as a sheet, many fish eyes are generated in the molded product, and the quality of the molded product is significantly deteriorated. become.

When the polymer obtained by polymerization is molded into a sheet or the like, the molded product obtained is required to have a 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 colored to some extent, but this coloring is called initial coloring, and it is desired that the coloring is as small as possible. However, when a coating film of a polymer scale anti-adhesive agent containing the condensation product of the aromatic amine compound as an active ingredient is formed, the coating film may be peeled off or dissolved and mixed into the polymer. The whiteness of the molded product may decrease, that is, the initial colorability may deteriorate.

Therefore, an object of the present invention is to polymerize a monomer having an ethylenically unsaturated double bond not only in the liquid phase portion in the polymerization vessel but also in the vicinity of the interface between the gas phase and the liquid phase. In addition to being able to effectively prevent the adhesion of polymer scale, when molded into a sheet or the like, it is possible to produce a polymer that has a very small number of fish eyes and that has good initial colorability. It is an object of the present invention to provide a polymer scale adhesion preventive agent and a method for producing a polymer using the same.

[0010]

Means for Solving the Problems In order to achieve the above object, the present invention provides (A) a condensation product having a molecular weight of 400 to 50000 obtained by condensing a quinone compound, and (B)
Provided is a polymer scale anti-adhesion agent for polymerization of a monomer having an ethylenically unsaturated double bond, which contains an aromatic amine compound.

The present invention also provides a method for producing a polymer by polymerizing a monomer having an ethylenically unsaturated double bond in a polymerization vessel, wherein (A) a quinone compound is condensed on the inner wall surface. A solution containing the condensation product having a molecular weight of 400 to 50000 obtained by (1) and (B) an aromatic amine compound is applied, and the polymerization is carried out in a polymerization vessel having a coating film formed by drying. In this way, a manufacturing method is provided in which the adhesion of polymer scale in the polymerization vessel is prevented.

Component (A) quinone compound Examples of the quinone compound include the following general formulas (1) and (2)
A benzoquinone compound represented by the following general formula (3)
And naphthoquinone compounds represented by (4).

[0013]

[Chemical 1]

[0014]

[Chemical 2] (In each formula, a plurality of R ¹ may be the same or different,
_{H, -NH 2, -Cl, -Br} , -OH, -NO 2, -COCH 3, -O
_{CH 3, -N (CH 3)} 2, -COOH, a -SO ₃ H or an alkyl group having 1 to 3 carbon atoms. )

[0015]

[Chemical 3]

[0016]

[Chemical 4] (In each formula, a plurality of R ¹ may be the same or different and are as described above. Further, a plurality of R ² may be the same or different, and —H, —Cl, —Br, —OH, — COCH ₃ , −OCH
_3, -CH _3, a -COOH or -SO ₃ H. )

Specific examples of the benzoquinone compound represented by the above general formulas (1) and (2) include o- and p-benzoquinone, hydroxy-p-benzoquinone, chloro-p-benzoquinone and bromo-p-. Examples thereof include benzoquinone, juroquinone, chloranil and the like.

Specific examples of the naphthoquinone compound represented by the above general formulas (3) and (4) include 6-methyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, lawson,
Examples include juglone, plumbagin, α-naphthoquinone, β-naphthoquinone and the like.

Among the above quinone compounds, preferred are o- and p-benzoquinone, α-naphthoquinone, β-naphthoquinone and lawson. The quinone compound is
They can be used alone or in combination of two or more.

Production of Condensation Product of Quinone Compound It is an essential component of the polymer scale anti-adhesive agent of the present invention.
The component (A) is obtained by condensing the quinone compound, and has a molecular weight in the range of 400 to 50,000, preferably 6
It is a condensation product in the range of 00 to 20000. When the molecular weight of the condensation product is less than 400, the polymer scale adhesion preventing effect is low, and when it exceeds 50,000, the solubility of the condensation product in water and an organic solvent is lowered, so that a uniform polymer scale adhesion preventing agent is prepared. Cannot be achieved, and the effect of preventing polymer scale adhesion is reduced.

The condensation product as described above is produced, for example, by reacting the above quinone compound in a suitable solvent at 20 to 150 ° C., preferably 25 to 100 ° C., and the reaction time is usually 2 to 200 hours. The concentration of the quinone compound in the solvent in the reaction is preferably 0.5
-25% by weight, more preferably 1-20% by weight
Is the range.

In order to accelerate the condensation reaction, the above reaction is preferably carried out in the presence of an alkaline compound. When the reaction is carried out in the presence of the alkaline compound, the reaction is usually carried out at 20 to 150 ° C, preferably 25 to 100 ° C. The reaction time is usually about 1 to 100 hours, preferably 7 to 70 hours. The amount of alkaline compound used is 0.01 to 100 per 100 parts by weight of the quinone compound.
The range of parts by weight is preferable, and the range of 0.1 to 40 parts by weight is more preferable. Examples of the alkaline compound include Li
Examples thereof include hydroxides of alkali metals such as OH, NaOH and KOH.

Further, in the above condensation reaction, an oxidizing agent can be used if necessary. Examples of such oxidizing agents include elemental or molecular simple halogens such as iodine, bromine, chlorine, and fluorine; for example, oxyacids and oxygen acids of halogens such as iodic acid, periodic acid, potassium periodate, and sodium perchlorate. Salts; for example, inorganic peroxides such as hydrogen peroxide, sodium peroxide, potassium persulfate, ammonium persulfate; for example, peracetic acid, benzoyl peroxide, cumene hydroperoxide, perbenzoic acid, p-menthane hydroperoxide, etc. Organic peroxides; for example, chlorides and sulfates of metals selected from iron and copper such as ferrous chloride, ferric chloride, copper sulfate, cuprous chloride, and the like; for example, α, α'-azo Bisisobutyronitrile,
Azo compounds such as α, α′-azobis-2,4-dimethylvaleronitrile; for example, nitrobenzene, o-, m- and p-oxynitrobenzene, o-, m- and p-nitroanisole,
Examples thereof include aromatic nitro compounds such as o-, m- and p-chloronitrobenzene, o-, m- and p-nitrobenzoic acid, o-, m- and p-nitrobenzenesulfonic acid.

As the solvent used in the above condensation reaction,
For example, it is preferable to use an organic solvent such as alcohols, ketones, and esters, and among them, an organic solvent miscible with water is used. Examples of the water-miscible organic solvent 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. Of these, alcohols are particularly preferable. It is also possible to use a mixed solvent of water and an organic solvent miscible with water.

In the case of preparing the coating liquid described below, as the component (A), the liquid containing the condensation product obtained by the condensation reaction of the above quinone compound can be used as it is. Further, it is also possible to use a product obtained by filtering and drying the condensation product precipitated by pouring cold water into the condensation product-containing liquid.

Examples of the aromatic amine compound (B) as the component (B) include compounds represented by the following general formula:
The compounds represented by (5) to (7) are mentioned.

[0027]

[Chemical 5] (In the formula, R ³ is —H, —NH ₂ , —Cl, —OH, —NO ₂ , —
COCH ₃ , -OCH ₃ , -N (CH ₃ ) ₂ or 1 to 3 carbon atoms
An alkyl group, R ⁴ _{is, -H, -NH 2, -OH,} -
CH _3, -COOH, or -SO ₃ H. )

[0028]

[Chemical 6] (In the formula, two R ³ may be the same or different and are as described above, and two R ⁴ may be the same or different and are as described above.)

[0029]

[Chemical 7] (In the formula, two R ^{3 s} may be the same or different and are as described above, and R ⁴ is also as described above.)

Specific examples of the compound represented by the above general formula (5) include aniline, o-, m- and p-phenylenediamine, o-, m- and p-aminophenol, o-, m. -And p-
Chloroaniline, o-, m- and p-nitroaniline, o-, m-
And p-methylaniline, N, N-dimethyl-p-phenylenediamine, 4-chloro-o-phenylenediamine, 4-methoxy-o-phenylenediamine, 2-amino-4-chlorophenol, 2,3-diaminotoluene , 5-nitro-2-aminophenol, 2-nitro-4-aminophenol, 4-nitro-2
-Aminophenol, o-, m- and p-aminosalicylic acid,
o-, m- and p-aminobenzoic acid, 2,4- and 3,5-diaminobenzoic acid, o-, m- and p-aminobenzenesulfonic acid,
Examples include 2,4-diaminobenzenesulfonic acid and the like.

Specific examples of the compound represented by the above general formula (6) include 4-aminodiphenylamine, 2-aminodiphenylamine, 4,4'-diaminodiphenylamine,
4-amino-3'-methoxydiphenylamine, 4-amino-
Examples include 4'-hydroxydiphenylamine and the like.

Specific examples of the compound represented by the above general formula (7) include α-naphthylamine, β-naphthylamine, 1,5-diaminonaphthalene, 1-amino-5-hydroxynaphthalene, 1,8- Examples include diaminonaphthalene and 2,3-diaminonaphthalene.

Among the aromatic amine compounds (B), preferred are o-, m- and p-aminophenol, aniline, 4-methoxy-o-phenylenediamine, 5-nitro-2-aminophenol, 2- Nitro-4-aminophenol, o-, m- and
p-aminosalicylic acid, p-aminobenzenesulfonic acid, 2,
4-diaminobenzenesulfonic acid, 4-aminodiphenylamine, 2-aminodiphenylamine, 4,4′-diaminodiphenylamine, α-naphthylamine, 1,5-diaminonaphthalene and 1,8-diaminonaphthalene.

The above aromatic amine compounds may be used alone or in combination of two or more.

In the polymer scale anti-adhesion agent of the present invention
The amount of the component (B) is usually in the range of 0.1 to 1000 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the component (A).
It is in the range of 300 parts by weight.

The polymer scale anti-adhesive agent of the present invention containing the above-mentioned components (A) and (B) as essential components is formed, for example, as a coating film on the inner wall surface of the polymerization vessel to obtain a coating film.
It prevents the polymer scale from adhering to the inner wall surface of the polymerization vessel. Usually, when the coating film is formed on the inner wall surface of the polymerization vessel, the polymer scale adhesion preventive agent is used in the form of a solution or dispersion, that is, as a coating solution.

Preparation of coating liquid The coating liquid as described above is prepared by adding the above-mentioned component (A) and component (B) to the following solvent to dissolve or disperse it. You may adjust to.

The solvent used for preparing the coating solution is, for example, water; for example, methanol, ethanol, propanol, butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 3- Alcohols such as methyl-1-butanol, 2-methyl-2-butanol, 2-pentanol; ketones such as acetone, methylethylketone, methylisobutylketone; methyl formate, ethyl formate, methyl acetate, ethyl acetate Examples include esters such as methyl acetoacetate; ethers such as 4-methyldioxolane and ethylene glycol diethyl ether; furans; aprotic solvents such as dimethylformamide, dimethylsulfoxide, and acetonitrile. These solvents are appropriately used alone or as a mixed solvent of two or more kinds.

Among the above solvents, water and a mixed solvent of water and an organic solvent miscible with water are preferable.
Among the above-mentioned organic solvents, examples of the organic solvent miscible with water include alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate. Examples thereof include types. When using a mixed solvent of water and an organic solvent miscible with water, the content of the organic solvent shall be such that there is no risk of ignition, explosion, etc., and there is no problem in handling safety such as toxicity. Is preferred, specifically,
The organic solvent is preferably 50% by weight or less, further,
It is preferably 30% by weight or less.

The coating solution is preferably alkaline, and more preferably has a pH in the range of 7.5 to 13.5.
A pH range of 8.0 to 13.0 is preferred. As the alkaline compound used for pH adjustment, for example, LiOH, NaOH, KOH, Na
Alkali metal compounds such as ₂ CO ₃ , Na ₂ HPO ₄ ;
Ammonium compounds such as NH ₄ OH; for example, organic amine compounds such as ethylenediamine, monoethanolamine, diethanolamine and triethanolamine.

Other Components Further , in order to further improve the polymer scale adhesion preventing effect, (C) a water-soluble polymer compound, (D) an inorganic colloid, and (E) an alkali metal silicate are added to the above coating solution. It is preferable to add at least one selected from the group consisting of
These additives (C) to (E) probably interact with the condensation product to increase the hydrophilicity of the coated surface ((C) water-soluble polymer compound) or to prevent the polymer scale from sticking. It is presumed that it has an effect of increasing the adhesion to the inner wall of the polymerization vessel ((D) inorganic colloid and (E) alkali metal silicate).

(C) Water-Soluble Polymer Compound As the water-soluble polymer compound (C), for example, gelatin,
Nonionic polymer compounds such as casein; for example, anionic polymer compounds such as polyacrylic acid, polystyrene sulfonic acid, carboxymethyl cellulose, alginic acid;
For example, cationic nitrogen-containing polymer compounds such as polyvinylpyrrolidone, chitosan, polyacrylamide;
Polyvinyl alcohol, hydroxyethyl cellulose,
Examples thereof include hydroxyl group-containing polymer compounds such as hydroxypropyl cellulose and pectin. Among the above water-soluble polymer compounds, gelatin, casein, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone and pectin are preferable.

The water-soluble polymer compound (C) can be used alone or in combination of two or more. The amount of component (C) added is usually 1 to 1000 per 100 parts by weight of component (A).
Parts by weight, preferably 5 to 200 parts by weight.

(D) Inorganic Colloid Inorganic colloid (D) is a particle colloid produced by a dispersion method using water as a dispersion medium or a condensation method, and the size of the colloid particles is 1 to 500 mμ. Specific examples of the inorganic colloid include colloids of oxides and hydroxides of metals selected from the group consisting of aluminum, thorium, titanium, zirconium, antimony, tin, iron, etc .; tungstic acid, vanadium pentoxide, gold. And silver colloid; silver iodide sol; colloids of selenium, sulfur, silica and the like.

Preferred among the above-mentioned inorganic colloids are colloids of oxides and hydroxides of aluminum, titanium, zirconium, tin and iron, and colloidal silica.

The inorganic colloid (D) may be used alone or in combination of two or more. The added amount of the component (D) is usually 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, per 100 parts by weight of the component (A).

(E) Alkali Metal Silicates Examples of the alkali metal silicates (E) include, for example, metasilicates (M ₂ SiO ₃ ) of alkali metals such as lithium, sodium and potassium, and orthosilicates ( M ₄ SiO ₄ ),
Disilicate (M ₂ Si ₂ O ₃ ), Trisilicate (M ₃ Si ₃ O _3
7 ), sesquisilicic acid (M ₄ Si ₃ O ₁₀ ), and the like (here, M represents an alkali metal such as lithium, sodium, and potassium), and water glass. The alkali metal silicate (E) may be used alone or in combination of two or more. The content of (E) component is (A) component
It is usually 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, per 100 parts by weight.

When the component (D) and the component (E) are used in combination, the total amount of the component (D) and the component (E) is 1 to 1000 parts by weight per 100 parts by weight of the component (A). And more preferably 5 to 500 parts by weight.

In order to improve the polymer scale adhesion preventing effect most, the water-soluble polymer compound (C) and the inorganic colloid are used.
It is preferably used in combination with (D) or in combination with the water-soluble polymer compound (C) and the alkali metal silicate (E). When used in combination with the component (C) and the component (D), it is preferable to use 5 to 3000 parts by weight of the component (D) per 100 parts by weight of the component (C), and further 50 to 1000 parts by weight. Partial use is preferred. When the component (C) and the component (E) are used in combination, it is preferable to use 5 to 3000 parts by weight of the component (E) per 100 parts by weight of the component (C), and further to add 50 to 10 parts by weight.
It is preferable to use 00 parts by weight.

The total concentration of the component (A) and the component (B) in the coating solution is not particularly limited as long as the total coating amount described below can be obtained, but it is usually about 0.01 to 10% by weight, preferably 0. .
It is about 1 to 3% by weight. When the components (C) to (E) are added, the total concentration of the components (A) to (E) is preferably about 0.1 to 20% by weight, and further about 0.2 to 6% by weight. Is preferred.

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, After thoroughly drying in the temperature range from room temperature 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, where polymer scale may be attached, for example, a device for recovering unreacted monomers and It is preferable to form the coating film on the inner surface of the pipe or the like. Specific examples include inner surfaces of a monomer distillation column, a condenser, a monomer storage tank, a valve, and the like.

The method of applying the coating solution to the inner wall surface of the polymerization vessel is not particularly limited, and examples thereof include brush coating, spray coating, and a method of withdrawing after filling the polymerization vessel with the coating solution. 57-61001, 55-36288
No. 5, Special Publication No. 56-501116, No. 56-501117, JP-A-59
The automatic coating method described in No. 11303 or the like can also be used.

The method of drying the wet surface by applying the coating liquid is not limited, and for example, the following method can be used. That is, after applying the coating liquid, 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 liquid are heated in advance to, for example, 30 to 80 ° C. Alternatively, a method of directly applying the coating liquid 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 to 5 g / m ² , and in particular,
It is preferably 0.05 to ² g / m ² .

The above coating operation may be carried out every 1 to 10 or more batches of polymerization. Since the formed coating film has high durability and the action of preventing the polymer scale from adhering continues, it is not always necessary to perform it for each batch of polymerization, so that the productivity 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 other portions where the monomer contacts during the polymerization, and then the coating film is formed in the polymerization vessel by a conventional method. Polymerize. That is, in addition to a monomer having an ethylenically unsaturated double bond and a polymerization initiator (catalyst), if necessary, a polymerization medium such as water, a suspending agent, a solid dispersant, a nonionic or an anionic emulsifier. Then, a dispersant and the like are charged, and then polymerization is performed by a conventional method.

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 and salts; maleic acid, fumaric acid, and their esters and anhydrides; Examples include diene-based monomers such as butadiene, chloroprene, and isoprene; styrene; acrylonitrile; vinylidene halide; vinyl ether and the like. These are used alone or in combination of two or more.

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.

A general polymerization method will be specifically described below by taking suspension polymerization and emulsion polymerization as examples. First,
Charge water and dispersant into the polymerizer. Next, the inside of the polymerization vessel is evacuated and the pressure is reduced to 0.1 to 760 mmHg, and then the monomer is charged. At this time, the internal pressure of the polymerization vessel is usually 0.5 to 30 kgf / cm ² · G. Further, the polymerization initiator is charged before and / or after charging the monomer. Then, polymerization is carried out at a reaction temperature of 30 to 150 ° C. During the polymerization, one or more kinds of water, a dispersant and a polymerization initiator are added, if necessary. The reaction temperature during polymerization depends on the type of monomer to be polymerized.For example, in the case of vinyl chloride polymerization, the polymerization is carried out at 30-80 ° C, and in the case of styrene polymerization 50-150 ° C. Polymerize with. As for polymerization, when the internal pressure of the polymerization vessel dropped to 0 to 7 kgf / cm ² · G, or there was almost no difference between the inlet temperature and the outlet temperature of the cooling water flowing in and out of the jacket equipped on the outer periphery of the polymerization vessel. When it is completed (that is, when the heat generated by the polymerization reaction disappears), it is judged to be completed. Water, a dispersant and a polymerization initiator charged at the time of polymerization are usually 20 to 500 parts by weight of water and 0.01 part of a dispersant per 100 parts by weight of the monomer.
˜30 parts by weight and 0.01 to 5 parts by weight of polymerization initiator.

In the case of solution polymerization, an organic solvent such as toluene, xylene or pyridine is used as the 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.

In the case of bulk polymerization, about 0.01 to about
After evacuating to a pressure of 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, 30-80 ℃
In the case of styrene polymerization, it is carried out at 50 to 150 ° C.

When polymerization is carried out by applying the method 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 for example, a glass lined polymerization vessel or the like. Of course, the adhesion of the polymer scale can be prevented even when the polymerization is carried out in a stainless steel or other steel polymerization vessel.

The additives 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 hydroperoxide,
Cyclohexanone peroxide, t-butyl peroxypivalate, bis (2-ethoxyethyl) peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate,
Polymerization initiators such as α, α′-azobisisobutyronitrile, α, α′-azobis-2,4-dimethylvaleronitrile, potassium peroxodisulfate, ammonium peroxodisulfate and p-menthane hydroperoxide; Suspending agents such as partially saponified polyvinyl alcohol, polyacrylic acid, copolymers of vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropylmethyl cellulose, natural and synthetic polymer compounds such as gelatin; for example, calcium phosphate, hydroxyapatite Solid dispersants such as; nonionic emulsifiers such as sorbitan monolaurate, sorbitan trioleate, polyoxyethylene alkyl ethers; sodium alkylbenzene sulfonates such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate Anionic emulsifiers such as sodium and dioctyl sodium sulfosuccinate; fillers such as calcium carbonate and titanium oxide; stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate and dioctyltin mercaptide; rice, for example Lubricants such as wax, stearic acid and cetyl alcohol; plasticizers such as DOP and DBP; mercaptans such as t-dodecyl mercaptan; chain transfer agents such as trichloroethylene; and pH control agents, etc. 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 to improve the scale prevention effect. You can also let it. In this case, the amount of the polymer scale anti-adhesion agent added 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 polymer such as fish eye, bulk specific gravity and particle size distribution.

[0067]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. In the tables below, the test numbers marked with * are comparative examples, and the other test numbers are examples of the present invention.

Production Example 1 Production of Condensation Product of Quinone Compound Production of Condensation Product No. 1 A reactor having an internal volume of 2 liter equipped with a reflux condenser was charged with a mixed solvent of 450 g of methanol and 450 g of water. Then, 100 g of α-naphthoquinone as a quinone compound and 10 g of sodium hydroxide were added. Next, 65 in the reactor.
The temperature was raised to 0 ° C., the mixture in the reactor was reacted at 65 ° C. for 10 hours, and then cooled to room temperature. In this way, a solution of the condensation product No. 1 was obtained. The condensation product No. 1 obtained above had a molecular weight of 3000 as measured by the following method.

Measurement of molecular weight It was measured by gel permeation chromatography (GPC). The molecular weight is represented by polystyrene equivalent number average molecular weight. The measurement conditions are as follows. Column: Guard column Product name shim-pack GPC-800DP, Shimadzu analytical column Product name shim-pack GPC-803D, 802D, Shimadzu mobile phase: 10mM LiBr / DMF Flow rate: 1.0 ml / min Detector: RI temperature: 60 ℃

Production of Condensation Products Nos. 2 to 9 In each production, the condensation product Nos. 1 were prepared in the same manner as in the production of condensation product No. 1 using the solvent, quinone compound and alkaline compound shown in Table 1. .2-9 were manufactured. In Table 1,
The concentration of the quinone compound in the solution (wt%), the ratio of the alkaline compound to the quinone compound (wt%), the reaction temperature and the reaction time are shown. The molecular weight of each condensation product was measured in the same manner as in condensation product No. 1. The results are shown in Table 1.

[0071]

[Table 1]

Example 1 (Experiment Nos. 101 to 110) In each experiment, a stainless steel polymerization vessel with an internal volume of 1000 liter and equipped with a stirrer was used as the polymerization vessel. In each experiment,
Conditions shown in Table 3 (solvent composition, condensation product (A) + (B) + (C) +
(D) + (E) total concentration, (A) :( B) :( C) :( D) :( E) weight ratio and p
H) becomes the condensation product (A), aromatic amine compound (B), water-soluble polymer compound (C), inorganic colloid (D) and alkali metal silicate (E) shown in Table 2. ), And the solvents and alkaline compounds shown in Table 3 were used to prepare coating solutions. The inorganic colloid of the component (D) used in this example and the following example 2 (a to a in Tables 2 and 6)
g) is as shown in Table 5.

In each experiment, the coating solution prepared as described above was applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade, and other portions where the monomer comes into contact during the polymerization, and the mixture was heated at 40 ° C. for 15 minutes and dried. After forming the coating film, the inside of the polymerization vessel was washed with water.

Then, in each experiment, polymerization was carried out as follows. 400 kg of water, 200 kg of vinyl chloride, 250 g of partially saponified polyvinyl alcohol, 25 g of hydroxypropylmethyl cellulose and 70 g of 3,5,5-trimethylhexanoyl peroxide are placed in the polymerization vessel where the coating film is formed by applying the coating as described above. The mixture was charged and polymerized at 66 ° C. for 6 hours while stirring. 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 coating operation was not performed, and the same operation was repeated for the number of batches shown in Table 4 with the operation of the polymerization and the washing in the polymerization vessel as one batch. For each experiment,
After the end of the final batch, the amount of polymer scale attached to the liquid phase in the polymerization vessel and the amount of polymer scale attached near the interface between the gas phase and the liquid phase were measured by the following methods. The results are shown in Table 4. -Measurement of amount of adhered polymer scale The scale adhered to a predetermined area of 10 x 10 cm on the inner wall of the polymerization vessel was scraped off with a stainless steel spatula as completely as possible with the naked eye and weighed with a balance. The measured value was multiplied by 100 to obtain the scale adhesion amount per 1 m ² .

Further, the number of fish eyes when the polymer obtained in each experiment was molded into a sheet was measured by the following method. The results are shown in Table 4.・Fish eye measurement 100 parts by weight of the obtained polymer, dioctyl phthalate (DO
P) A mixture prepared by mixing 50 parts by weight, 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 is kneaded at 150 ° C. for 7 minutes using a 6 inch roll. After that, the sheet 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, in order to evaluate the initial colorability when the polymer obtained in each experiment was molded into a sheet, a lightness index was used.
(L value) was measured by the following method. The results are shown in Table 4. -Measurement of lightness index (L value) 100 parts by weight of the obtained polymer, 1 part by weight of tin laurate-based stabilizer (TS-101 manufactured by Akishima Chemical Co., Ltd.), cadmium-based stabilizer (C-Katsuda Kako Co., Ltd. 100 J) 0.5 part 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 a sheet having a thickness of 1 mm is formed. Next, the molded sheet is put in a 4 × 4 × 1.5 cm frame and heated and pressure molded at 160 ° C. and 65 to 70 kgf / cm ² for 0.2 hours to prepare a measurement sample. JIS for this sample
The lightness index L in the Hunter color difference formula described in Z 8730 (1980) was determined, and the larger the L value, the higher the whiteness, that is, the better the initial colorability. The L value is obtained as follows. Standard light C, photoelectric colorimeter (Nippon Denshoku Industries Co., Ltd., Z-1001DP colorimetric color difference meter) according to JIS Z 8722
Using the stimulus value direct reading method, the stimulus value Y in the XYZ color system
Ask for. The geometric conditions for illumination and light reception are JIS
The condition d described in Section 4.3.1 of Z 8722 was adopted. From the obtained stimulation value Y, the formula described in JIS Z 8730 (1980): L = 10
The L value is calculated from Y ^1/2 .

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

Example 2 (Experiment Nos. 201 to 210) In each experiment, a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 20 liters was used as the polymerization vessel. In each experiment,
Conditions shown in Table 7 (solvent composition, condensation product (A) + (B) + (C) +
(D) + (E) total concentration, (A) :( B) :( C) :( D) :( E) weight ratio and p
H) becomes the condensation product (A), aromatic amine compound (B), water-soluble polymer compound (C), inorganic colloid (D), and alkali metal silicate (E) shown in Table 6. ), And
Coating solutions were prepared using the solvents and alkaline compounds shown in Table 7. The coating liquid is applied to the inner wall of the polymerization vessel and the stirring shaft,
Apply to the stirring blade and other parts where the monomer contacts during polymerization,
After heating at 40 ° C. for 15 minutes and drying to form a coating film, the inside of the polymerization vessel was washed with water.

Next, in each experiment, polymerization was carried out as follows. Into the polymerization vessel where the coating film was formed by coating as described above, 9 kg of water, 225 g of sodium dodecylbenzenesulfonate, 12 g of t-dodecyl mercaptan and 13 g of potassium peroxodisulfate were charged, and the inside of the polymerization vessel was filled with nitrogen gas. After replacement, 1.3 kg of styrene and 3.8 of butadiene
After charging kg, 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 coating operation was not carried out, and the above-mentioned polymerization and washing in the polymerization vessel were regarded as one batch, and the same operation was repeated for the number of batches shown in Table 8. For each experiment,
After the end of the final batch, the amount of polymer scale attached to the liquid phase in the polymerization vessel and the amount of polymer scale attached near the interface between the gas phase and the liquid phase were measured in the same manner as in Example 1. The results are shown in Table 8. Further, in order to evaluate the initial colorability when the polymer obtained in each experiment is formed into a sheet, the lightness index (L
The value) was measured by the following method. The results are shown in Table 8.

Measurement of lightness index (L value) To 1 kg of the obtained polymer latex, 1 kg of a 2% magnesium sulfate solution was added to carry out coagulation precipitation, and then the precipitate was separated by filtration. The precipitate separated by filtration was washed with hot water at 80 to 90 ° C. for 2 to 3 times and then dried at 40 ° C. for 25 hours using a vacuum dryer to obtain a resin. The obtained resin is put in a mold of 9 × 9 cm, depth of 0.1 cm, heated at 195 ° C. at 50-60 kgf / cm ² for 0.2 hours, and pressure-molded at a final pressure of 80 kgf / cm ² to obtain a measurement sample. It was made.
The lightness index L of this sample was determined in the same manner as in Example 1.

[0086]

[Table 6]

[0087]

[Table 7]

[0088]

[Table 8]

Example 3 A polymerization vessel made of stainless steel and equipped with a stirrer and having an internal volume of 20 liters was used as the polymerization vessel. The coating solution used in Experiment No. 201 of Example 2 was applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade and other portions where the monomer comes into contact during the polymerization, and heated at 50 ° C. for 15 minutes and dried to form a coating film. After forming, the inside of the polymerization vessel was washed with water.

Then, 4.0 kg of water and 6 g of sodium dodecylbenzenesulfonate were charged into the polymerization vessel having the coating film formed by the coating treatment as described above, and the temperature was raised to 60 ° C. with stirring. Next, after replacing the gas phase in the polymerization vessel with nitrogen gas,
94 g of n-butyl acrylate, 220 g of methyl methacrylate, 5 g of acrylic acid and 5 g of methacrylic acid were charged, subsequently 1 g of ammonium persulfate and 1 g of sodium hydrosulfite were charged, and the mixture was stirred at 60 ° C. for 20 minutes. In addition, mixed monomer (n-butyl acrylate 2.1 kg, methyl methacrylate) was added to the polymerization vessel.
4.8 kg, a mixture of 100 g of acrylic acid and 100 g of methacrylic acid) 500 g of 1 wt% ammonium persulfate aqueous solution, 1
500% by weight sodium hydrosulfite aqueous solution and 25% by weight
Polyoxyethylene nonyl phenyl ether aqueous solution 2.0k
g was added in a constant amount over 3 hours. After the addition was completed, the temperature of the polymerization vessel was raised to 70 ° C. and polymerization was carried out for 2 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 from the formation of the above-mentioned coating film to the washing of the inside of the polymerization vessel through the polymerization is regarded as one batch.
After repeating 90 batches, the amount of polymer scale attached to the liquid phase portion in the polymerization vessel at the 90th batch and the amount of polymer scale attached near the interface between the gas phase and the liquid phase were determined in the same manner as in Example 1. As a result, the amount of polymer scale attached to the liquid phase portion was 0 g / m ² , and the amount of polymer scale attached near the interface between the gas phase and the liquid phase was 15 g / m ² .

[0092]

According to the present invention, it is possible to effectively prevent the adhesion of polymer scale not only in the liquid phase portion in the polymerization vessel but also in the vicinity of the interface between the gas phase and the liquid phase. Therefore,
When the polymerization is carried out by applying the present invention, it is not necessary to carry out the polymer scale removal work for each polymerization, thereby improving the productivity. When a polymer obtained by applying the present invention for polymerization is molded into a sheet or the like, a molded product having extremely few fish eyes can be obtained. Furthermore, the molded product has good initial colorability. Specifically, the lightness index (L value) in the Hunter color difference formula described in JIS Z 8730 (1980) is, for example, 70 or more for vinyl chloride polymers and 80 or more for SBR.

Claims (3)

[Claims] 1. A monomer having an ethylenically unsaturated double bond, which comprises (A) a condensation product having a molecular weight of 400 to 50000 obtained by condensing a quinone compound, and (B) an aromatic amine compound. Polymer scale anti-sticking agent for body polymerization. 2. The polymer scale adhesion preventive agent according to claim 1, further comprising (C) a water-soluble polymer compound, (D) an inorganic colloid, and (E) an alkali metal silicate. Those containing at least one selected from the group. 3. A method for producing a polymer by polymerizing a monomer having an ethylenically unsaturated double bond in a polymerization vessel, wherein a molecular weight obtained by condensing (A) a quinone compound on the inner wall surface.
It has a step of applying a liquid containing 400 to 50000 condensation products and (B) an aromatic amine compound, and performing the polymerization in a polymerization vessel having a coating film formed by drying. A manufacturing method in which adhesion of polymer scale in a polymerization vessel is prevented.