JPH0725912A - Agent for preventing adhesion of polymer scale and production of polymer using the same - Google Patents

Abstract

PURPOSE:To obtain a preventing agent consisting of an alkaline solution containing an anthraquinone-based pigment, a reducing agent, a water-soluble high polymer and an inorganic colloid, capable of preventing occurrence of scale in polymerization of a substance having an ethylenic unsaturated double bond and providing a high-quality product and being environmentally safe. CONSTITUTION:This preventing agent consists of an alkaline solution containing (A) an anthraquinone-based pigment, (B) a reducing agent, (C) a water-soluble high polymer compound and (D) an inorganic colloid. The preventing agent is applied to the inner wall of a polymerizer for polymerizing a monomer having ethylenic unsaturated double bond and dried and then, polymerization of the monomer is carried out. The component B is preferably sodium hydrosulfite. The component A is preferably 'C.I. Vat. Yellow 26(R)'. The component C is preferably gelatin, casein, etc. The component D is preferably aluminum, titanium, etc.

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, the polymer scale is likely to adhere to the inner wall of the polymerization vessel, the agitator, and the like where the monomer contacts.

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, and is obtained by molding the polymer. The disadvantage is that the quality of the molded product is reduced. Moreover, not only excessive labor and time are required to remove the adhered polymer scale,
Since the unreacted monomer is contained in this polymer scale, there is a risk of human injury due to the monomer, which has become a very serious problem in recent years.

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 comprising an organic compound,
Also, a method of adding these compounds to an aqueous medium is known (Japanese Patent Publication No. 45-30343).

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). In this respect, the use of a water-soluble catalyst has a particularly great effect and is not industrially satisfactory.

In order to overcome this disadvantage, JP-A-53-13689
It is proposed in the publication to use a condensation product of an aromatic amine compound as a polymer scale anti-adhesion agent. When a coating film containing the condensation product of this aromatic amine compound is formed on the inner wall of the polymerization vessel where the monomer contacts, even if the polymerization is repeated about 100 to 200 batches, the liquid phase portion in the polymerization vessel No polymer scale deposition occurs. Also, when a water-soluble catalyst is used, polymer scale adhesion in the liquid phase portion is similarly prevented.

[0007]

However, there is a drawback that polymer scale adheres to the vicinity of the interface between the gas phase portion and the liquid phase portion located in the upper layer portion in the polymerization vessel.

Once the polymer scale adheres to the vicinity of the interface between the gas phase portion and the liquid phase portion, the adhered polymer scale gradually grows as the polymerization is repeated, and finally, the polymer scale adheres to the surface and peels off. May be mixed during coalescence. When the polymer scale is mixed in 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 resulting molded product, and the quality of the molded product is significantly deteriorated. Will end up.

When forming a coating film of the condensation product of the aromatic amine compound, the condensation product is an organic solvent or a mixed solvent of water and an organic solvent containing an organic solvent as a main component (generally,
Since it is used as a coating solution in which an organic solvent is dissolved in 60% by weight or more), there is a risk of ignition and explosion of the organic solvent, and there is also a problem in handling safety such as toxicity.

Therefore, an object of the present invention is to polymerize a monomer having an ethylenically unsaturated double bond, not only in the liquid phase part in the polymerization vessel but also in the vicinity of the interface between the gas phase part and the liquid phase part. Also effectively prevents the adhesion of polymer scale, can produce a polymer with very few fish eyes when processed into molded products such as sheets, and also ignites the organic solvent when forming a coating film. Another object of the present invention is to provide a polymer scale adhesion preventive agent having a low risk of explosion and having no problem in handling safety such as toxicity, and a method for producing a polymer using the preventive agent.

[0011]

The present invention comprises an alkaline solution containing (A) anthraquinone dye, (B) a reducing agent, and (C) a water-soluble polymer compound and / or (D) an inorganic colloid. Provided is a polymer scale adhesion inhibitor for polymerization of a monomer having an ethylenically unsaturated double bond.

Further, the present invention is a method for producing a polymer by polymerizing a monomer having an ethylenically unsaturated double bond in a polymerization vessel, wherein (A) anthraquinone dye, B) a step of applying an alkaline solution containing a reducing agent and (C) a water-soluble polymer compound and / or (D) an inorganic colloid, and performing the polymerization in a polymerization vessel having a coating film formed by drying And thereby to prevent the adhesion of polymer scale.

(A) Anthraquinone dye Anthraquinone dye (A), for example, 1,4-dibenzamide anthraquinone, CI Vat Yellow 26, C.
I. Bat Yellow 12, CI Bat Yellow 10, CI Bat Die (CI 66000), CI Bat Violet 17, etc. Acylaminoanthraquinone compounds; for example, CI Bat Orange 20, di-α-anthraquinoyl-2,6-dianthraquinone Anthraimide compounds, such as CI Vat Yellow 2, CI vat Blue 30, and other anthraquinone thiazole compounds; For example, CI Vat Red 13, such as anthrapyrazolone compounds; For example, CI Vat Yellow
29, CI Vat Yellow 31 and other anthrapyrimidine compounds; for example, violantrone, isoviolantrone, C.I.
I. Vat Blue 22, CI Vat Blue 19, CI Vat Violet 10, CI Vat Violet 9,6,15-Dimethoxyisoviolanthrone, CI Vat Green 3 and other dibenzanthrone compounds; for example, Anzantron, C.I.
I. Bant Orange 19, CI Bat Orange 3 and other Anzantron compounds; for example, 2,1-anthraquinone acridone, 1,2-anthraquinone acridone, CI vat blue 33, CI vat red 38, CI vat violet 1
3, CI bat orange 13, CI bat green 12, C.
I. Anthraquinone acridone compounds such as Bat Brown 55; for example, pyrantrone, CI Vat Orange 9, C.
Pyrantron compounds such as I. Vat Orange 2;
CI Bat Yellow 28, CI Bat Orange 15, CI Bat Brown 3, CI Bat Black 27, CI Bat Green 3, CI Bat Brown 1, CI Bat Brown
3, CI Bat Brown 44, CI Bat Orange 11, C.
Examples include anthraquinonecarbazole compounds such as I. Bat Brown 8 and CI Bat Green 8.

Among the above-mentioned anthraquinone dyes, preferred are CI Vat Yellow 26 and CI Vat Orange.
11, CI Bat Red 13, CI Bat Yellow 28, Anthraquinone Carbazole, CI Bat Blue 22, CI
Bat Blue 30, CI Bat Blue 33, CI Bat Brown 1, CI Bat Orange 13, and Anthraquinone Acridone.

The above-mentioned anthraquinone dyes can be used alone or in combination of two or more.

(B) Reducing agent Examples of the reducing agent (B) include hydrogen, hydrogen iodide, hydrogen bromide, hydrogen sulfide, lithium aluminum hydride, sodium borohydride, calcium borohydride, zinc borohydride. , Tetraalkylammonium borohydride,
Hydrogenated trichlorosilane, triethylsilane, etc .; for example, carbon monoxide, sulfur dioxide, sodium thiosulfate, sodium thiosulfite, sodium sulfite, potassium sulfite, sodium bisulfite, sodium hydrosulfite, and other lower oxides and lower oxyacid salts. Sulfur compounds such as Rongalit, sodium sulfide, sodium polysulfide, ammonium sulfide; alkali metals such as sodium and lithium; electropositive large metals such as magnesium, calcium, aluminum, zinc and amalgams thereof; ; For example, iron (II) sulfate, tin chloride
(II), Titanium (III) trichloride, and other low-valent metal salts; for example, phosphorus trichloride, phosphorus triiodide, trimethylphosphine, triphenylphosphine, trimethylphosphite, hexamethylphosphorus triamide, etc. Phosphorus compounds of, for example, hydrazine, diborane, ethane-1,2
Examples include diborane such as diaminoborane, dimethylamine-borane and pyridineborane, and substituted borane. Preferred among these are sodium hydrosulfite,
Rongalit, sodium thiosulfate and sodium sulfite.

(C) Water-soluble polymer compound Examples of the water-soluble polymer compound include amphoteric polymer compounds such as gelatin and casein, and anionic polymer compounds such as polyacrylic acid, polystyrene sulfonic acid, carboxymethyl cellulose and alginic acid. Examples thereof include cationic nitrogen-containing polymer compounds such as polyvinylpyrrolidone and polyacrylamide; and hydroxyl group-containing polymer compounds such as polyvinyl alcohol, hydroxyethyl cellulose, 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 may be used alone or in combination of two or more.

(D) Inorganic colloid Inorganic colloid is, for example, a dispersion method using water as a dispersion medium,
It is a particle colloid produced by the condensation method, and the size of the colloid particles is 1 to 500 mμ. As the inorganic colloid, specifically, aluminum, thorium, titanium,
Colloids of oxides and hydroxides of metals selected from zirconium, antimony, tin, iron, etc., tungstic acid, vanadium pentoxide, colloids of gold and silver, silver iodide sol, colloids of selenium, sulfur, silica, etc. Is exemplified.

Preferred among the above inorganic colloids are colloids of oxides and hydroxides of metals selected from aluminum, titanium, zirconium, tin and iron,
And colloidal silica. The above inorganic colloids can be used alone or in combination of two or more.

The polymer scale adhesion preventive agent of the present invention is
In addition to the components (A) and (B), the components (C) and //
Alternatively, the component (D) is contained, but it is preferable to use the component (C) and the component (D) together in order to further improve the polymer scale adhesion preventing effect.

(A) component, (B) component, and (C) component and
/ Or Polymerization consisting of alkaline solution containing component (D)
Body scale anti-adhesive agent The polymer scale anti-adhesive agent of the present invention comprises the component (A),
It is composed of an alkaline solution containing the component (B) and the component (C) and / or the component (D). The polymer scale adhesion preventing agent is applied to the inner wall surface of the polymerization vessel or the like and dried to form a coating film, whereby the polymer scale can be prevented from adhering to the inner wall surface of the polymerization vessel or the like.

The polymer scale adhesion preventive agent of the present invention is prepared, for example, by mixing and dispersing the above-mentioned components (A) and (B) in an appropriate medium, and then further adding the component (C) and / or the component (D). Is added and mixed to adjust the pH of the resulting mixed solution to be alkaline.

The polymeric scale anti-sticking agent of the present invention is alkaline. Therefore, the solubility of the component (A) in the medium is improved, and the polymer scale deposition inhibitor can be obtained as a uniform solution. Therefore, when the polymer scale adhesion preventive agent of the present invention is applied to the inner wall of a polymerization vessel or the like, the polymer scale adhesion prevention effect is improved. The pH of the polymer scale anti-adhesion agent of the present invention is preferably in the range of 7.5 to 13.5, more preferably in the range of 8.0 to 12.0. As the alkaline compound used as the pH adjuster, for example, Li
OH, KOH, NaOH, Na ₂ CO ₃ , Na ₂ SiO ₃ , Na ₂ HPO ₄ ,
Examples thereof include alkali metal compounds and ammonium compounds such as NH ₄ OH, and organic amine compounds such as ethylenediamine, monoethanolamine and triethanolamine. It is also possible to adjust the polymer scale anti-adhesion agent to be a uniform solution by adjusting it to be alkaline, and then to adjust the polymer scale anti-adhesion agent to be acidic in a range in which heterogeneity such as precipitation does not occur. The acidic compound used as the pH adjuster in this case can be used without particular limitation.

The medium used for preparing the polymer scale anti-adhesion agent is preferably water or a mixed solvent of water and an organic solvent miscible with water. When using a mixed solvent of water and a water-miscible organic solvent, the content of the organic solvent is not risk of ignition, explosion, etc.
The amount is preferably such that toxicity or the like does not pose a safety problem in handling, and specifically, the organic solvent content is preferably 50% by weight or less, more preferably 20% by weight or less.
Examples of the water-miscible organic solvent include alcohols such as methanol, ethanol, propanol, and isobutyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate. Of these, alcohols are preferred.

The mixing ratios of the component (A), the component (B), the component (C) and the component (D) differ depending on the kinds of those components. The amount of component (B) added is 100 parts by weight of component (A),
It is usually 0.1 to 1000 parts by weight, preferably 1 to 300 parts by weight. If component (C) is used, the amount added is
The amount is usually 5 to 300 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the component (A). When the component (D) is used, its addition amount is usually 10 to 1000 parts by weight, preferably 50 to 300 parts by weight, per 100 parts by weight of the component (A).

When component (C) and component (D) are used in combination, the total amount of addition of component (C) and component (D) is 100 parts of component (A).
It is usually 5 to 3000 parts by weight per part by weight, preferably
50 to 1000 parts by weight. Also, in such a case, component (C) 1
The component (D) is preferably 10 to 5000 parts by weight, more preferably 50 to 1000 parts by weight, per 00 parts by weight.

The component (A) in the polymer scale deposition inhibitor,
The total concentration of the component (B) and the component (C) and / or the component (D) is not particularly limited as long as the total coating amount described below can be obtained, but is usually 0.05 to 5% by weight, preferably 0.1 to 1% by weight. %.

Formation of coating film The polymer scale adhesion preventive agent of the present invention is formed as a coating film on the inner wall surface of a polymerization vessel or the like to prevent adhesion of the polymer scale to the inner wall surface of the polymerization vessel or the like. You can To form a coating film on the inner wall surface of the polymerization vessel using the polymer scale anti-adhesion agent prepared as described above,
First, a polymer scale anti-adhesion agent is applied to the inner wall surface of the polymerization vessel, and then sufficiently dried in a temperature range from room temperature to 100 ° C., and then 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 the site where the polymer scale may adhere, for example, the unreacted monomer is recovered. 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 of applying the polymer scale anti-adhesion agent to the inner wall surface of the polymerization vessel is not particularly limited, and for example, brush coating, spray coating, a method of withdrawing after filling the polymerization vessel with the polymer scale anti-adhesion agent, etc. 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 for drying the wet surface due to the application of the polymer scale anti-adhesion agent. For example, the following method can be used. 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 particularly preferably 0.
It is preferably from 05 to ² g / m ² .

Since the formed coating film has high durability and the action of preventing polymer scale from adhering continues, the above coating operation is not necessarily required to be carried out for each batch of polymerization.
Therefore, 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,
Water and a dispersant are charged into a polymerization vessel, and then a polymerization initiator is charged. 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), and then 30 ~
Polymerize at reaction temperature of 150 ° C. During the polymerization, one or more kinds of water, a dispersant and a polymerization initiator are added, if necessary. Further, the reaction temperature at the time of polymerization varies depending on the type of the monomer to be polymerized, for example, in the case of vinyl chloride polymerization, the polymerization is carried out at 30 to 80 ° C., and in the case of styrene polymerization,
Polymerize at 50-150 ° C. For polymerization, the internal pressure of the polymerization vessel is 0-7
When it falls to kgf / cm ² · G, or when there is almost no difference between the inlet temperature and the outlet temperature of the cooling water that flows in and out of the jacket installed on the outer circumference of the polymerization vessel (that is, the heat generated by the polymerization reaction disappears). It is judged that it has been completed. Water, a dispersant, and a polymerization initiator charged during polymerization are usually 20 to 500 parts by weight of water, 0.01 to 30 parts by weight of a dispersant, and 0.01 to 5 parts by weight of a polymerization initiator with respect to 100 parts by weight of a monomer. It is a department.

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

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

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

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

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

[0045]

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. Example 1 (Experiment Nos. 101 to 126) Polymerization was carried out as follows using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 2000 liters. In each experiment,
The (A) anthraquinone dye shown in Table 1 ((A) component concentration, (B) component concentration, (C) component concentration, and (D) component concentration) under the conditions shown in Table 2 ( B) a reducing agent,
The water-soluble polymer compound (C) and the inorganic colloid (D) were dispersed in the solvents shown in Table 2. Next, each of the obtained dispersions was adjusted to the pH shown in Table 2 by using the pH adjusting agent shown in Table 2. The polymer scale anti-adhesion agent thus obtained is applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade and other portions where the monomer contacts during the polymerization, and heated at 50 ° C for 15 minutes and dried to apply. After forming the film, the inside of the polymerization vessel was washed with water.

Thereafter, in each experiment, 800 kg of water, 400 kg of vinyl chloride, and 500 parts of partially saponified polyvinyl alcohol were placed in the polymerization vessel on which the coating film was formed by the coating treatment as described above.
g, hydroxypropylmethyl cellulose 50 g and 3,
140 g of 5,5-trimethylhexanoyl peroxide 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.

The operation from the formation of the coating film through the polymerization to the washing of the inner wall of the polymerization vessel as described above is defined as one batch, and the same operation is repeated 50 batches thereafter. The amount of coal scale adhering and the amount of polymer scale adhering near the interface between the gas phase part and the liquid phase part were measured by the following methods for each experiment. However, for Experiment No. 104 *, 10
The amount of polymer scale deposited in the batch was measured. The results are shown in Table 3.

-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 spatula and weighed with a balance. The measured value
It was multiplied by 100 to determine the amount of polymer scale attached per 1 m ² .

The number of fish eyes contained per 100 cm ² when the polymer obtained in each experiment was molded into a sheet was measured by the following method. The results are shown in Table 3.

Measurement of fish eye 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.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

Example 2 (Experiment Nos. 201 to 222) Polymerization was carried out as follows using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 20 liters. In each experiment,
Under the conditions shown in Table 5 ((A) component concentration, (B) component concentration, (C) component concentration, and (D) component concentration), the (A) anthraquinone dye shown in Table 4 and ( B) a reducing agent,
The water-soluble polymer compound (C) and the inorganic colloid (D) were dispersed in the solvents shown in Table 2. Next, each of the obtained dispersions was adjusted to the pH shown in Table 5 by using the pH adjusting agent shown in Table 5. The polymer scale anti-adhesion agent thus obtained is applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade and other portions where the monomer contacts during the polymerization, and heated at 50 ° C for 15 minutes and dried to apply. After forming the film, the inside of the polymerization vessel was washed with water.

Next, in each experiment, 9 kg of water, 225 g of sodium dodecylbenzene sulfonate, 12 g of t-dodecyl mercaptan and 13 g of potassium peroxodisulfate were placed in the polymerization vessel in which the coating film was formed by the coating treatment as described above. Was charged, and the inside of the polymerization vessel was replaced with nitrogen gas.
kg and 3.8 kg of butadiene were charged and polymerized 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.

The operation from the formation of the coating film through the polymerization to the washing of the inner wall of the polymerization vessel with water is defined as one batch, and the same operation is repeated 20 batches thereafter. The combined scale deposition amount and the polymer scale deposition amount near the interface between the gas phase portion and the liquid phase portion were measured in the same manner as in Example 1 for each experiment. However, for Experiment No. 203 *, the amount of polymer scale attached in the first batch was measured. The results are shown in Table 6.

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[Table 6]

Example 3 Polymerization was carried out as follows using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 1000 liters. The polymer scale anti-adhesion agent used in Experiment No. 123 was applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade and other parts where the monomer contacts during the polymerization, and heated at 50 ° C for 10 minutes and dried to apply. After forming the film, the inside of the polymerization vessel was washed with water. Then, in a polymerization vessel in which a coating film was formed by coating in this manner, 400 kg of water, 260 kg of styrene, 140 kg of acrylonitrile, 400 g of partially saponified polyacrylamide and 1.2 k of α, α'-azobisisobutyronitrile.
Then, g was charged and polymerization was carried out at 90 ° C. for 5 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 operation from the formation of a coating film as described above to the washing in the polymerization vessel through the polymerization is repeated for 20 batches, the amount of polymer scale attached to the liquid phase part in the polymerization vessel of the 20th batch, and the gas phase. The polymer scale adhesion amount near the interface between the liquid phase part and the liquid phase part was measured in the same manner as in Example 1. As a result, the amount of polymer scale attached to the liquid phase was 0 g.
/ M ² and the amount of polymer scale attached near the interface between the gas phase portion and the liquid phase portion was 18 g / m ² .

Example 4 Polymerization was carried out as follows using a stainless steel polymerization vessel with an internal volume of 20 liter equipped with a stirrer. The polymer scale anti-adhesion agent used in Experiment No. 201 was 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 50 ° C. for 10 minutes and drying to form a coating film, the inside of the polymerization vessel was washed with water. Then, 9.5 kg of water, 240 g of sodium dodecylbenzene sulfonate, 15 g of t-dodecyl mercaptan, 2.1 kg of butadiene, 2.8 g of methyl methacrylate, styrene were placed in the polymerization vessel where the coating film was formed by the coating treatment as described above.
320 g and potassium persulfate 16 g were charged and polymerized at 60 ° C. for 10 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. After that,
The operation from the formation of the coating film as described above to the washing in the polymerization vessel through polymerization is repeated for 20 batches, the amount of polymer scale attached to the liquid phase portion in the polymerization vessel of the 20th batch, and the gas phase portion. The amount of polymer scale attached near the interface with the liquid phase part was measured 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 portion and the liquid phase portion was 12 g / m ² .

Example 5 Polymerization was carried out as follows using a stainless steel polymerization vessel with an internal volume of 100 liter equipped with a stirrer. The polymer scale anti-adhesion agent used in Experiment No. 201 was applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade, and other parts where the monomer comes into contact during the polymerization, and heated at 50 ° C for 15 minutes and dried to apply. After forming the film, the inside of the polymerization vessel was washed with water. After that, 40 kg of water and disproportionated potassium rosinate were placed in the polymerization vessel where the coating film was formed by the coating treatment as described above.
500 g, polybutadiene latex (solid content 45%) 13 kg,
Styrene monomer 9kg, acrylonitrile monomer 5kg, t
-Prepare 40 g of dodecyl mercaptan and 140 g of cumene hydroperoxide.
Charge 0 g, ferrous sulfate 2 g and sodium pyrophosphate 100 g,
Polymerization was carried out at 65 ° C. for 4 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 operation from the formation of a coating film as described above to the washing in the polymerization vessel through the polymerization is repeated for 20 batches, the amount of polymer scale attached to the liquid phase part in the polymerization vessel of the 20th batch, and the gas phase. The polymer scale adhesion amount near the interface between the liquid phase part and the liquid phase part was measured in the same manner as in Example 1. As a result, the amount of polymer scale attached to the liquid phase part was 0 g / m ² , and the amount of polymer scale attached near the interface between the gas phase part and the liquid phase part was
It was 19 g / m ² .

Example 6 Polymerization was carried out as follows using a stainless steel polymerization vessel with an internal volume of 20 liters equipped with a stirrer. The polymer scale anti-adhesion agent used in Experiment No. 120 was added 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 and drying at 50 ° C. for 15 minutes to form a coating film, 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. After replacing the gas phase in the polymerization vessel with nitrogen gas, n-butyl acrylate (94 g), methyl methacrylate (220 g), acrylic acid (5 g) and methacrylic acid (5 g) were charged, and then ammonium persulfate (1 g) and sodium hydrosulfite (1 g) were charged.
The mixture was stirred at 60 ° C for 20 minutes. Furthermore, mixed monomers (n-butyl acrylate 2.1 kg, methyl methacrylate 4.
8 kg, a mixture of 100 g of acrylic acid and 100 g of methacrylic acid) 1% by weight ammonium persulfate aqueous solution 500 g, 1% by weight sodium hydrosulfite aqueous solution 500 g and 25% by weight polyoxyethylene nonylphenyl ether aqueous solution 2.0 kg
Was added uniformly 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 coating film as described above to the washing in the polymerization vessel through the polymerization is repeated for 40 batches, the polymer scale adhesion amount of the liquid phase part in the polymerization vessel of the 40th batch, and the gas phase. The polymer scale adhesion amount near the interface between the liquid phase part and the liquid phase part was measured 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 scale attached near the interface between the gas phase portion and the liquid phase portion was 23 g / m ^2.
It was m ² .

Example 7 Polymerization was carried out as follows using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 20 liters. The polymer scale anti-adhesion agent used in Experiment No. 120 was added 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 50 ° C. for 10 minutes and drying to form a coating film, the inside of the polymerization vessel was washed with water. After that, 4.5 kg of water, 312 g of completely saponified polyvinyl alcohol and 6 g of sodium carbonate were charged into the polymerization vessel in which the coating film was formed by coating in this way, and stirred.
The temperature was raised to 65 ° C. Next, 550 g of vinyl acetate and 550 g of 1% by weight ammonium persulfate aqueous solution were charged in the polymerization vessel, and the temperature was set to 80 °
The temperature was raised to. Then, 5.0 kg of vinyl acetate in the polymerization vessel
And 1.0 kg of a 1% by weight ammonium persulfate aqueous solution were added thereto uniformly over 4 hours. After the addition of vinyl acetate and ammonium persulfate was completed, the inside of the polymerization vessel was heated to 90 ° C and polymerization was performed at 90 ° C 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 coating film as described above to the washing in the polymerization vessel through the polymerization is repeated for 40 batches, the polymer scale adhesion amount of the liquid phase part in the polymerization vessel of the 40th batch, and the gas phase. The polymer scale adhesion amount near the interface between the liquid phase part and the liquid phase part was measured in the same manner as in Example 1. As a result, the amount of polymer scale attached to the liquid phase part was 0 g / m ² , and the amount of polymer scale attached near the interface between the gas phase part and the liquid phase part was 31 g / m 2.
^{Was 2} .

Example 8 Polymerization was carried out as follows using a stainless steel polymerization vessel with an internal volume of 20 liter equipped with a stirrer. The polymer scale anti-adhesion agent used in Experiment No. 221, 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 50 ° C. for 10 minutes and drying to form a coating film, the inside of the polymerization vessel was washed with water. After that, 7.0 kg of water, 430 g of partially saponified polyvinyl alcohol, 7 g of sodium pyrophosphate, and 7 g of sodium hydrosulfite were charged into the polymerization vessel where the coating film was formed by the above coating treatment, and the temperature was raised to 50 ° C. Next, the gas phase in the polymerization vessel was replaced with nitrogen gas, the temperature was raised to 70 ° C., and ethylene was charged until the internal pressure reached 14 kg / cm ² · G. Then 6.0 kg of vinyl acetate and 2% by weight aqueous solution of ammonium persulfate
1.0 kg was added uniformly over 4 hours. After the addition of vinyl acetate and ammonium persulfate was completed, the temperature inside the polymerization vessel was raised to 80 ° C and polymerization was carried out at 80 ° C for 3 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 coating film as described above to the washing in the polymerization vessel through the polymerization is repeated for 40 batches, the polymer scale adhesion amount of the liquid phase part in the polymerization vessel of the 40th batch, and the gas phase. The polymer scale adhesion amount near the interface between the liquid phase part and the liquid phase part was measured in the same manner as in Example 1. As a result, the amount of polymer scale attached to the liquid phase part was 0 g / m ² , and the amount of polymer scale attached near the interface between the gas phase part and the liquid phase part was 18 g / m ^2.
It was m ² .

Example 9 Polymerization was carried out as follows using a stainless steel polymerization vessel with an internal volume of 20 liters equipped with a stirrer. The polymer scale adhesion inhibitor used in Experiment No. 101 was 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 60 ° C. for 10 minutes and drying to form a coating film, the inside of the polymerization vessel was washed with water. Then, an aqueous solution prepared by dissolving 1.2 kg of polyvinyl alcohol having a saponification degree of 99.4 mol% and a polymerization degree of 2250 in 15 liters of water was charged into the polymerization vessel on which the coating film was formed by the coating treatment as described above. While stirring the aqueous solution, 1 kg of 35% concentrated hydrochloric acid was added, and after 10 minutes, 800 g of butyraldehyde was added dropwise over 15 minutes. Then, the temperature inside the polymerization vessel was raised to 60 ° C. and the reaction was carried out for 3 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 coating film as described above to the washing in the polymerization vessel through the polymerization is repeated for 40 batches, the polymer scale adhesion amount of the liquid phase part in the polymerization vessel of the 40th batch, and the gas phase. The polymer scale adhesion amount near the interface between the liquid phase part and the liquid phase part was measured in the same manner as in Example 1. As a result, the amount of polymer scale attached to the liquid phase part was 0 g / m ² , and the amount of polymer scale attached near the interface between the gas phase part and the liquid phase part was 15 g / m ² .

Example 10 Prepolymer Preparation Example The prepolymer used in this Example 10 below was prepared by the following method. 6000g of styrene monomer in the polymerization vessel
, Polybutadiene rubber 720 g, mineral oil (CP-50 manufactured by Idemitsu Kosan Co., Ltd.) 480 g and n-dodecyl mercaptan 60
A prepolymer was prepared by charging 00 g and reacting at 115 ° C. for 5 hours.

Polymerization was carried out as follows using a stainless steel polymerization vessel with an internal volume of 20 liters equipped with a stirrer. Experiment No.1
Apply the polymer scale anti-adhesion agent used in 01 to the inner wall of the polymerization vessel, stirring shaft, stirring blade and other parts where the monomer contacts during polymerization, heat at 50 ° C for 15 minutes and dry to form a coating film. After that, the inside of the polymerization vessel was washed with water. Then, in the polymerization vessel in which a coating film was formed by coating in this way, water 7000 g, prepolymer 7000 g obtained in the above preparation example, hydroxyapatite 70 g, sodium dodecylbenzenesulfonate 0.14 g
, Benzoyl peroxide 17.5g and t-butyl perbenzoate 10.5g were charged and reacted at 92 ° C for 3.5 hours.
A polymer was produced by reacting at 1 ° C. for 1 hour. After completion of polymerization
The produced polymer and unreacted monomer were recovered, and the inside of the polymerization vessel was washed with water to remove the residual resin. After that, from the formation of the coating film as described above through the polymerization to washing in the polymerization vessel with water,
Forty batches were repeated, and the scale adhesion amount of the liquid phase part in the polymerization vessel of the 40th batch and the scale adhesion amount near the interface between the gas phase part and the liquid phase part were measured 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 scale attached near the interface between the gas phase portion and the liquid phase portion was 23 g / m ² .

[0069]

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 polymerization is carried out by applying the present invention, it is not necessary to carry out the polymer scale removing operation for each polymerization, and the productivity is improved. 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,
Since the polymer scale anti-adhesion agent of the present invention can suppress the use of an organic solvent at the time of forming a coating film, it is used in a range where there is little danger of ignition, explosion, etc. and there is no problem in handling safety such as toxicity. can do.

Claims (2)

[Claims] 1. An ethylenically unsaturated double bond comprising an alkaline solution containing (A) anthraquinone dye, (B) a reducing agent, and (C) a water-soluble polymer compound and / or (D) an inorganic colloid. A polymer scale anti-adhesion agent for the polymerization of a monomer having: 2. A method for producing a polymer by polymerizing a monomer having an ethylenically unsaturated double bond in a polymerization vessel, wherein (A) anthraquinone dye and (B) a reducing agent are provided on the inner wall surface. , And (C) applying a water-soluble polymer compound and / or (D) an alkaline solution containing an inorganic colloid, and performing the polymerization in a polymerization vessel having a coating film formed by drying, This is a manufacturing method in which adhesion of polymer scale is prevented.