JPH0782303A - Polymer scale inhibitor and production of polymer by using the inhibitor - Google Patents

Abstract

PURPOSE:To produce a polymer scale inhibitor comprising an alkaline solution containing a condensate of specified diphenyl and quinone compounds to prevent deposition of polymer scale in the polymerization reactor in which monomers containing an ethylenically unsaturated double bond are polymerized. CONSTITUTION:The inhibitor comprises an alkaline solution (for example: a solution consisting of NaOH, water and methanol) which contains a condensate of a diphenyl compound and a quinone compound (for example: alpha- naphthoquinone), the diphenyl compound containing at least two amino groups and represented by the formula [wherein R' represents H, OH, COOH, SO3H, NH2, Cl, NO2, COCH3, OCH3, N(CH3)2, or 1-3C alkyl: X represents 1-5C alkylene, -N(CH3)2-, -C(CH3)2-, -CONH-, -P(=O)H-, -SO2-, -O-, -S-, or -Si(R)2- (R representing 1-10C alkyl); and n is 1 or 2].

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 particularly unfavorable industrially, when the water-soluble catalyst is used in the polymerization.

[0006] In order to overcome this disadvantage, for example, JP-A-53
No. -13689 discloses a method of applying a polymer scale anti-adhesion agent containing a condensation product of an aromatic amine compound as an active ingredient to the inner wall of a polymerization vessel or the like. Such a polymer scale anti-adhesion agent is applied to a portion such as the inner wall of the polymerization vessel where the monomer comes into contact, and a coating film is formed. No polymer scale deposition occurs. 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. There is. When the polymer scale is mixed in the polymer in this way, when the polymer is processed into a molded article such as a sheet, many fish eyes are generated in the molded article obtained,
The quality of the molded product will be significantly reduced.

When a polymer obtained by polymerization is molded into a sheet or the like, the molded product obtained 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 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 article may be lowered, that is, the initial colorability may be lowered.

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) the following general formula (1):

[Chemical 3] [In the formula, plural R ^{1 s} may be the same or different, and
_{-OH, -COOH, -SO 3 H,} -NH 2, -Cl, -NO 2, -COC
H _3, -OCH _3, an alkyl group of -N (CH _{3) 2} or -C 1 to 3, X is an alkylene group having 1 to 5 carbon _{atoms, -N (CH 3) -,} - C (CH ₃ ) ₂ −, −CONH−, −P (=
_{O) H -, - SO 2} -, - O -, - S- , or -Si (R) ₂ -
(Here, R is an alkyl group having 1 to 10 carbon atoms.). n is an integer of 1-2. ] For the polymerization of a monomer having an ethylenically unsaturated double bond, which is composed of an alkaline liquid containing a condensation product of a diphenyl compound having at least two amino groups represented by the following formula (B) and a quinone compound. To provide a polymer scale anti-adhesion agent.

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) the following general formula (1) :

[Chemical 4] [In the formula, plural R ^{1 s} may be the same or different, and
_{-OH, -COOH, -SO 3 H,} -NH 2, -Cl, -NO 2, -COC
H _3, -OCH _3, an alkyl group of -N (CH _{3) 2} or -C 1 to 3, X is an alkylene group having 1 to 5 carbon _{atoms, -N (CH 3) -,} - C (CH ₃ ) ₂ −, −CONH−, −P (=
_{O) H -, - SO 2} -, - O -, - S- , or -Si (R) ₂ -
(Here, R is an alkyl group having 1 to 10 carbon atoms.). n is an integer of 1-2. ] A diphenyl compound having at least two amino groups represented by the following, and an alkaline liquid containing a condensation product of (B) a quinone compound are applied and dried in a polymerization vessel having a coating film formed. There is provided a production method which comprises the step of carrying out the above-mentioned polymerization, thereby preventing adhesion of polymer scale in a polymerization vessel.

Component (A) The component (A) is composed of the amino group (-
It is a diphenyl compound having at least two NH ₂ ).

Specific examples of the component (A) include 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ether, 4,4 'diaminodiphenylpropane and 4,4'.
-Diaminodiphenyl sulfone, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) phosphine oxide, bis (4-aminophenyl) -N-methylamine, 4,4'-diaminobenzanilide, 4,4 Examples include'-diaminodiphenylmethane and the like.

Of these, preferred are 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylmethane.

The above-mentioned component (A) can be used alone or in combination of two or more kinds.

Examples of the quinone compound (B) as the component (B) include compounds represented by the following general formula (2)
A benzoquinone compound represented by (3), and the following general formula
Examples thereof include naphthoquinone compounds represented by (4) to (5).

[0017]

[Chemical 5]

[0018]

[Chemical 6]

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

Specific examples of the benzoquinone compounds represented by the above general formulas (2) and (3) include o- and p-benzoquinone, hydroxy-p-benzoquinone, chloro-p-benzoquinone and bromine-p-. Examples thereof include benzoquinone, juroquinone, chloranil and the like.

[0021]

[Chemical 7]

[0022]

[Chemical 8]

(In each formula, a plurality of R ² may be the same or different and are as described above. Also, a plurality of R ³ may be the same or different, and --H, --Cl, --Br,-. OH, -COCH
_3, -OCH _3, -CH _3, a -COOH or -SO ₃ H. )
The naphthoquinone compound represented by the general formula (3) and (4), specifically, 6-methyl-1,4-naphthoquinone,
Examples include 2-methyl-1,4-naphthoquinone, lawson, juglone, plumbagin, α-naphthoquinone, β-naphthoquinone.

Among the above quinone compounds, preferred are o- and p-benzoquinone, α-naphthoquinone, β-naphthoquinone and lawson.

The above quinone compound (B) may be used alone or in a mixture of 2
It is also possible to use a combination of two or more species.

Condensation Reaction A condensation product of the above-mentioned component (A) and the above-mentioned component (B), which are the essential components of the polymer scale adhesion preventive agent of the present invention, is obtained by using the components (A) and (B) as a suitable solvent. In the presence of a catalyst, if necessary, the reaction is usually carried out at room temperature to 200 ° C. for 0.5 to 100 hours, preferably at room temperature to 150 ° C. for 3 to 30 hours.

Since the component (B) also acts as a condensation catalyst, it is not usually necessary to add any other condensation catalyst, but as the condensation catalyst which can be used when another condensation catalyst is added, iodine or bromine can be used. Elemental or molecular elemental halogen such as chlorine, fluorine and fluorine; oxyacids and oxyacid salts of halogens such as iodic acid, periodate, potassium periodate and sodium perchlorate; Inorganic peroxides such as sodium oxide, potassium persulfate and ammonium persulfate; for example, peracetic acid, benzoyl peroxide,
Organic peroxides such as cumene hydroperoxide, perbenzoic acid and p-menthane hydroperoxide; selected from iron and copper such as ferrous chloride, ferric chloride, copper sulfate and cuprous chloride Metal chlorides and sulfates; eg, α, α'-azobisisobutyronitrile, α, α '
-Azo compounds such as azobis-2,4-dimethylvaleronitrile; for example, nitrobenzene, o-, m- and p-oxynitrobenzene, o-, m- and p-nitroanisole, o-, m- and p-chloro Examples thereof include aromatic nitro compounds such as nitrobenzene, o-, m- and p-nitrobenzoic acid, o-, m- and p-nitrobenzenesulfonic acid.

As the solvent for the condensation reaction, for example, organic solvents such as alcohols, ketones and esters are used.
Among them, it is preferable to use an organic solvent miscible with water. 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; and dimethylformamide, for example. Aprotic solvents such as dimethyl sulfoxide and acetonitrile are exemplified, and among them, alcohols are particularly preferable. Also,
It is also possible to use a mixed solvent of an organic solvent miscible with water and water.

The pH of the medium for conducting the condensation reaction is usually 1 to 13
Therefore, the pH adjuster can be used without particular limitation.

When carrying out the condensation reaction, the ratio of the component (A) and the component (B) depends on the components (A), (B) and the type of solvent used.
Although it is affected by the reaction temperature, the reaction time, etc., it is generally preferable that the amount of the component (B) is 0.01 to 10 parts by weight, and further 0.1 to 5 parts by weight, per 1 part by weight of the component (A). preferable.
If the amount of the component (B) is too large or too small, the effect of preventing polymer scale adhesion of the condensation product obtained will decrease. The total concentration of the component (A) and the component (B) in the solvent in the condensation reaction is preferably 0.5 to 30% by weight, more preferably 1 to 15% by weight.

Containing a condensation product of the component (A) and the component (B)
Polymer scale anti-adhesive agent consisting of an alkaline liquid polymer scale anti-adhesive agent of the present invention, the above (A) component and
It consists of an alkaline liquid containing a condensation product with the component (B). The polymer scale adhesion preventive agent is applied to the inner wall surface of the polymerization vessel and the like, and dried to form a coating film, whereby the adhesion of the polymer scale to the inner wall surface of the polymerization vessel can be prevented.

The polymer scale anti-adhesion agent is prepared, for example, by adding the following solvent to the liquid containing the condensation product obtained by the above condensation reaction, if necessary, and adjusting the pH to be alkaline. Further, the polymer scale adhesion preventive agent is
After the condensation product-containing liquid was poured into cold water to precipitate the condensation product, the precipitate was filtered off, and the dried product was added with the following solvent to adjust the pH to alkaline. Good.

By making the polymer scale anti-adhesion agent of the present invention alkaline, the solubility of the condensation products of the components (A) and (B) in the solvent is improved. Therefore, since the polymer scale adhesion preventing agent becomes a uniform solution, the polymer scale adhesion preventing effect can be improved when applied on the inner wall surface of the polymerization vessel or the like. The polymer scale anti-adhesion agent of the present invention preferably has a pH of 7.5 to 13.5, and particularly preferably pH 8.0 to 12.5. As the alkaline compound used for pH adjustment, for example, LiOH,
Alkali metal compounds such as NaOH, KOH, Na ₂ CO ₃ , and Na ₂ HPO ₄ ; ammonium compounds such as NH ₄ OH; organic amine compounds such as ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, etc. To be done.

The solvent used for preparing the polymer scale anti-adhesive agent is, for example, water; for example, methanol, ethanol, propanol, butanol, 2-butanol,
Alcohol solvents such as 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 2-pentanol; for example, acetone, methyl ethyl ketone, methyl isobutyl Ketone-based solvents such as ketones; for example, methyl formate, ethyl formate,
Ester solvents such as methyl acetate, ethyl acetate and methyl acetoacetate; for example, ether solvents such as 4-methyldioxolane and ethylene glycol diethyl ether; furans; aprotic solvents such as dimethylformamide, dimethylsulfoxide and acetonitrile. Etc. are illustrated. 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, water-miscible organic solvents include, for example, alcohol solvents such as methanol, ethanol and propanol; ketone solvents such as acetone and methyl ethyl ketone; methyl acetate, ethyl acetate and the like. The ester-based solvent and the like are listed. 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 content is preferably 50% by weight or less, more preferably 30% by weight or less.

Other Components Further , in order to further improve the polymer scale adhesion preventing effect, the above-mentioned inhibitor is added to (C) a water-soluble polymer compound, (D) an inorganic colloid and (E) an alkali metal silicate. 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,
Amphoteric polymer compounds such as casein; for example, anionic polymer compounds such as polyacrylic acid, polystyrene sulfonic acid, carboxymethyl cellulose, alginic acid; and cationic nitrogen-containing polymer compounds such as polyvinylpyrrolidone, chitosan, polyacrylamide; Examples thereof include hydroxyl group-containing polymer compounds such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, and pectin. Of the above water-soluble polymer compounds, preferred are gelatin, casein,
Polyacrylic acid, carboxymethylcellulose, polyvinylpyrrolidone and pectin.

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

(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 inorganic colloids (D) are
Colloids of oxides and hydroxides of aluminum, titanium, zirconium, tin and iron, and colloidal silica. The inorganic colloid (D) can be used either individually or in combination of two or more. The amount of component (D) added is usually 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, per 100 parts by weight of the condensation product.

(E) Alkali Metal Silicates Examples of the alkali metal silicates (E) include, for example, alkali metal metasilicates (M ₂ SiO ₃ ) such as lithium, sodium and potassium, and orthosilicate ( 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 the component (E) is usually 1-1000 parts by weight, preferably 5-500 parts by weight, per 100 parts by weight of the condensation product.

When the component (D) and the component (E) are used in combination, the total amount of the component (D) and the component (E) is the above-mentioned condensation product.
The amount is preferably 1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, per 100 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 concentration of the condensation product in the alkaline solution is not particularly limited as long as the total coating amount described below can be obtained, but is usually about 0.001 to 5% by weight, preferably 0.01 to 1%.
It is about% by weight. Further, the total concentration of the condensation product and (C)-(E) components when the components (C)-(E) are added is
It is preferably about 0.05 to 5% by weight, and further 0.1 to
It is preferably about 2% by weight.

Formation of coating film A polymer scale anti-adhesive agent comprising an alkaline liquid containing a condensation product of the component (A) and the component (B) prepared as described above was used to coat the inner wall surface of the polymerization vessel. To form a coating film, first, the inhibitor is applied to the inner wall surface of the polymerization vessel, and then,
For example, after being sufficiently dried in a temperature range from room temperature to 100 ° C., it is further washed with water if necessary.

Further, the polymer scale adhesion preventive agent is
It is preferable to apply 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, a stirring blade,
Examples include stirring shafts, baffles, condensers, headers, search coils, bolts and nuts.

More preferably, the polymer scale anti-adhesion agent is a site other than the site where the monomer contacts during the polymerization, but a site where the polymer scale may adhere, for example, recovery of unreacted monomer. On the inside of the system equipment and piping,
It is better to form the coating film. Specific examples include inner surfaces of a monomer distillation column, a condenser, a monomer storage tank, a valve, and the like.

The method for applying the polymer scale anti-adhesion agent 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 polymer scale anti-adhesion agent. In addition, JP-A-57-61001, JP-A-55-36288 and JP-A-56-
The automatic coating methods described in JP-A-501116, JP-A-56-501117 and JP-A-59-11303 can also be used.

There is no limitation on the method of drying the wet surface due to the application of the polymer scale anti-adhesion agent, and the following method can be used, for example. That is, after the application of the polymer scale anti-adhesive agent, a method of applying an appropriately heated hot air to the application surface, or the inner wall surface of the polymerization vessel and the other surface to which the polymer scale anti-adhesion agent is applied are preliminarily set to, for example, 30 It is possible to use a method in which the polymer scale adhesion preventive agent is directly applied to the heated surface by heating to -80 ° C. 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, and a suspending agent, a solid dispersant, a nonionic or 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.

The general polymerization method will be specifically described below by taking the cases of suspension polymerization and emulsion polymerization as examples. First,
Charge water and dispersant into the polymerizer. Next, the inside of the polymerization vessel was evacuated and the pressure was reduced to 0.1 to 760 mmHg, and then monomers were 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 irrespective of the material of the inner wall surface of the polymerization vessel. For example, a glass lined polymerization vessel or the like can be used. 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 substances 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, whereby the scale prevention effect is improved. 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.

[0060]

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

Production Example 1 Production of Condensation Product No. 1 In a reactor having an internal volume of 2 liter equipped with a reflux condenser, 800 g of methanol and 100 g of dimethylformamide (DMF).
And (4) -diaminodiphenyl sulfone as component (A)
40 g were charged and stirred at room temperature to dissolve 4,4'-diaminodiphenyl sulfone in methanol / DMF. The methanol / DMF solution thus obtained was mixed with α-as the component (B).
Add 60 g of naphthoquinone, raise to 65 ℃,
Reacted for hours. Next, the obtained reaction mixture was cooled and added dropwise to water, and the deposited precipitate was separated by filtration and dried. Thus, condensation product No. 1 was obtained.

Production of Condensation Products Nos. 2 to 7 In each production, (A) component (diphenyl compound having at least two amino groups) and (B) component (quinone compound) shown in Table 1 and Table 2 A condensation product was produced in the same manner as the production of the condensation product No. 1 using the indicated solvent. Table 2 shows (A) + (B) total concentration, (A) :( B) weight ratio, reaction temperature and reaction time.

[0063]

[Table 1]

[0064]

[Table 2]

Example 1 (Experiment Nos. 101 to 108) In each experiment, a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 1000 liters was used as the polymerization vessel. In each experiment,
Conditions shown in Table 4 (solvent composition, condensation product (F) + (C) + (D) +
(E) total concentration, (F) :( C) :( D) :( E) weight ratio and pH) so that the condensation product (F) and water-soluble polymer compound (C ), An inorganic colloid (D), an alkali metal silicate (E), an alkaline compound and a solvent shown in Table 4, and a polymer scale anti-adhesive agent was prepared. The inorganic colloids (a) to (g) in Table 3 and Table 7 used in this example and in Example 2 below are as shown in Table 6.

In each experiment, the polymer scale anti-adhesive agent prepared as described above was applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blades and other parts where the monomers come in contact with each other during the polymerization.
After heating and drying at 15 ° C for 15 minutes to form a coating film, the inside of the polymerization vessel was washed with water.

Then, in each experiment, polymerization was carried out as follows. Water 400 kg, vinyl chloride 200 kg, partially saponified polyvinyl alcohol 250 g, hydroxypropyl methylcellulose 25 g and 3,5,5-trimethylhexanoyl peroxide 70 g were placed in the polymerization vessel where the coating film was formed by the above coating treatment. Was charged and polymerized at 66 ° C. for 6 hours with 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 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 5. 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 5.

Measurement of polymer scale The scale attached to a predetermined area of 10 × 10 cm on the inner wall of the polymerization vessel was scraped off as completely as possible with a stainless steel spatula 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) 50 parts by weight, dibutyltin dilaurate 1 part by weight, cetyl alcohol 1 part by weight, titanium oxide 0.25 parts by weight, carbon black 0.05 parts by weight A mixture prepared at a mixing ratio 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, the lightness index (L value) was measured by the following method in order to evaluate the initial colorability when the polymer obtained in each experiment was molded into a sheet. 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.

According to JIS Z 8722, standard light C, photoelectric colorimeter (Nippon Denshoku Industries Co., Ltd., Z-1001DP type colorimetric color difference meter) was used, and the XYZ color system stimulus was obtained by the stimulus value direct reading method. Calculate the value Y. 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 according to the formula: L = 10Y ^1/2 described in JIS Z 8730 (1980).

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

[Table 5]

[0076]

[Table 6]

Example 2 (Experiment Nos. 201 to 207) In each experiment, a stainless steel polymerization vessel having an internal volume of 20 liter and equipped with a stirrer was used as the polymerization vessel. In each experiment,
Conditions shown in Table 8 (solvent composition, condensation product (F) + (C) + (D) +
(E) total concentration, (F) :( C) :( D) :( E) weight ratio and pH) so that the condensation product (F) and water-soluble polymer compound (C ), An inorganic colloid (D), an alkali metal silicate (E), and an alkaline compound and a solvent shown in Table 8 were used to prepare a polymer scale adhesion preventive agent. These polymer scale anti-adhesion agents are 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 performed, 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 9. 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 9. 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 9.

Measurement of lightness index (L value) To 1 kg of the obtained polymer latex was added 1 kg of a 2% magnesium sulfate solution, coagulation and precipitation were carried out, 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.

[0081]

[Table 7]

[0082]

[Table 8]

[0083]

[Table 9]

Example 3 A polymerization vessel made of stainless steel with an internal volume of 20 liter and equipped with a stirrer was used as the polymerization vessel. The polymer scale anti-adhesion agent 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 monomers come into contact with each other during the polymerization, and the mixture was heated to 50 ° C.
After heating for 15 minutes and drying to form a coating film, it 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 operations from the formation of the above-mentioned coating film to the washing of the inside of the polymerization vessel through the polymerization are regarded as one batch.
After repeating 80 batches, the amount of polymer scale attached to the liquid phase portion in the polymerization vessel of the 80th 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 20 g / m ² .

[0087]

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 portion and the liquid phase portion. Therefore, when the present invention is applied to carry out the polymerization, it is not necessary to carry out the work of removing the polymer scale 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) The following general formula (1): [In the formula, plural R ^{1 s} may be the same or different, and
_{-OH, -COOH, -SO 3 H,} -NH 2, -Cl, -NO 2, -COC
H _3, -OCH _3, an alkyl group of -N (CH _{3) 2} or -C 1 to 3, X is an alkylene group having 1 to 5 carbon _{atoms, -N (CH 3) -,} - C (CH ₃ ) ₂ −, −CONH−, −P (=
_{O) H -, - SO 2} -, - O -, - S- , or -Si (R) ₂ -
(Here, R is an alkyl group having 1 to 10 carbon atoms.). n is an integer of 1-2. ] For the polymerization of a monomer having an ethylenically unsaturated double bond, which is composed of an alkaline liquid containing a condensation product of a diphenyl compound having at least two amino groups represented by the following formula (B) and a quinone compound. Polymer scale anti-sticking agent. 2. The polymer scale adhesion preventing 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. 3. A process for producing a polymer by polymerizing a monomer having an ethylenically unsaturated double bond in a polymerization vessel, wherein (A) the following general formula (1): ] [In the formula, plural R ^{1 s} may be the same or different, and
_{-OH, -COOH, -SO 3 H,} -NH 2, -Cl, -NO 2, -COC
H _3, -OCH _3, an alkyl group of -N (CH _{3) 2} or -C 1 to 3, X is an alkylene group having 1 to 5 carbon _{atoms, -N (CH 3) -,} - C (CH ₃ ) ₂ −, −CONH−, −P (=
_{O) H -, - SO 2} -, - O -, - S- , or -Si (R) ₂ -
(Here, R is an alkyl group having 1 to 10 carbon atoms.). n is an integer of 1-2. ] A diphenyl compound having at least two amino groups represented by the following, and an alkaline liquid containing a condensation product of (B) a quinone compound are applied and dried in a polymerization vessel having a coating film formed. A production method comprising the step of carrying out the above-mentioned polymerization, whereby adhesion of polymer scale in a polymerization vessel is prevented.