JPH0987308A - Production of vinyl chloride polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a vinyl chloride polymer extremely reduced in initial discoloration while effectively preventing polymer scale deposition not only on polymerizer's part which is in contact with the liquid phase but on polymerizer's part around the interface between the gas and liquid phases in a process comprising repeating batchwise the polymerization of at least one vinyl monomer comprising vinyl chloride in a polymerizer. SOLUTION: The process for producing a vinyl chloride polymer comprises repeating batchwise the steps of: (A) polymerizing a monomer in an aqueous medium within a polymerizer in which a film for preventing polymer scale deposition has been formed at least on the inner surface thereof: (B) discharging the resultant polymer slurry from the polymerizer; (C) applying a polymer scale deposition inhibitor on the inner surface of the polymerizer to form a coating film; and (D) feeding the feedstock into the polymerizer. In this process, the chloride ion concentration of the reaction mixture is regulated to 50ppm or lower throughout the step (A). The steps (B) and (C) are conducted while keeping the inside of the polymerizer isolated from the surrounding air.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a vinyl chloride polymer.

[0002]

2. Description of the Related Art Conventionally, as a method for polymerizing a vinyl chloride monomer or a vinyl-based monomer mixture mainly composed of a vinyl chloride monomer, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or a gas phase polymerization method is used. The bulk polymerization method and the like are known. In any of these polymerization methods, the polymer scale is apt to adhere to the site where the monomer contacts, such as a stirring device in the polymerization vessel. When the polymer scale adheres, the yield of the polymer, the cooling capacity of the polymerization vessel, etc. are reduced, and the polymer scale peels off and mixes into the desired polymer, which is obtained by molding the polymer. This has the disadvantage of reducing the quality of the molded product. 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, so that it has become a very serious problem in recent years. There is a risk of personal injury due to the existing monomer.

As a method for preventing such adhesion of polymer scale, a method of applying a scale adhesion preventing agent to the inner wall of the polymerization vessel is known, and various scale adhesion preventing agents have been proposed. For example, a dye or a pigment is applied (Japanese Patent Publication No. 45-30835), a polyaromatic amine having a specific structure having a molecular weight of about 250 or more (Japanese Patent Publication No. 59-16561), a self-condensation product of polyhydric phenol and / or Applying a polycondensate of polyhydric phenol (JP-A-54-7487), applying a reaction product of a phenol compound and an aromatic aldehyde (Japanese Patent Publication No.
2-363), the reaction product of 1-naphthol and formaldehyde is applied (JP-A-57-1641), and further, the surface roughness of the inner wall surface of the polymerization vessel and the portion of the equipment attached to the polymerization vessel in contact with the monomer 1 μm or less, and a dye or pigment is applied to the surface thereof (Japanese Patent Publication No. 2-36602), an aromatic compound or a heterocyclic compound having 5 or more conjugated π bonds is applied, and chlorine in the reaction mixture during polymerization is applied. Control the ion concentration to 100ppm or less (Japanese Patent Publication No. 4-40405), or control the chlorine ion concentration during polymerization by coating a dye or pigment to 100ppm or less (Japanese Patent Publication No. 4-3040).
4), etc. are known. The compound having 5 or more conjugated π bonds disclosed in JP-B No. 4-30405 has a molecular weight of 1,
It is less than 000.

In order to repeatedly carry out the polymerization by using the same polymerization vessel by these methods while preventing the adhesion of polymer scale, it is usual to take out the polymer slurry from the polymerization vessel after the completion of one polymerization, and After washing with water, a polymer scale adhesion preventing agent is applied to the inner wall surface of the polymerization vessel and the like, and then raw materials such as monomers are charged again to carry out the next polymerization. At that time, the polymerization is carried out in a state in which the polymerization vessel is closed and the inside of the vessel is shut off from the atmosphere outside the vessel, but withdrawing the polymer slurry and applying the polymer scale anti-adhesive agent, the manhole of the polymerization vessel is usually opened, It is carried out with the inside of the polymerization vessel open to the outside air. Polymerization by 100-
Even if it is repeated about 200 batches, polymer scale does not occur in the portion in contact with the liquid phase during polymerization in the polymerization vessel (hereinafter referred to as the liquid phase portion).

[0005]

However, in these conventional methods, in the inner wall of the polymerization vessel, etc., the portion corresponding to the interface between the gas phase and the liquid phase during the polymerization and its vicinity (hereinafter referred to as the gas-liquid interface section) is used. Has the disadvantage that polymer scales adhere.
Once the polymer scale adheres to the gas-liquid interface, the adhered polymer scale gradually grows as the polymerization is repeated, and finally the polymer scale may peel off and enter the polymer. When the polymer scale is mixed with the polymer in this way, many fish eyes are generated in the molded product obtained when the polymer is molded into a molded product such as a sheet, and the quality of the molded product is significantly deteriorated. Become. Therefore, prevention of adhesion of the polymer scale to the gas-liquid interface has become an extremely important technical issue in the production of vinyl chloride-based polymers.

When the polymer obtained by polymerization is processed into a molded product such as a sheet, the molded product obtained is required to have high whiteness. That is, the molded product obtained by molding into a sheet or the like without adding any colorant to the polymer is colored to some extent. This coloring is called initial coloring, and it is desired that the coloring be as small as possible. However, the coating film of the scale inhibitor may be peeled off or dissolved and mixed into the polymer, but when the scale inhibitor contains, for example, an active ingredient of a dye or a pigment, the whiteness of the molded article decreases, that is, Initial coloration deteriorates. That is, although dyes and pigments have high scale adhesion preventing ability, they have a problem in initial wearing.

Therefore, an object of the present invention is to produce a vinyl chloride polymer having very little initial coloration while effectively preventing adhesion of polymer scale not only in the liquid phase part but also in the gas-liquid interface part. It is to provide a manufacturing method capable of

[0008]

The present inventors have found that the following manufacturing method is effective for achieving the above-mentioned object. That is, according to the present invention, a batch of polymerizing a vinyl chloride monomer or a vinyl-based monomer mixture mainly composed of a vinyl chloride monomer in a polymerization vessel is repeated, thereby producing a vinyl chloride-based polymer. , (A) a step of subjecting a reaction mixture containing the monomer or monomer mixture in an aqueous medium to a polymerization reaction in a polymerization vessel in which a polymer scale anti-adhesive coating film is formed on at least an inner wall surface, (B) a step of extracting the resulting polymer slurry from the polymerization vessel, (C) a step of applying a polymer scale anti-adhesion agent liquid on the inner wall surface of the polymerization vessel, and drying to form a polymer scale anti-adhesion coating film, D) a step of charging the raw materials necessary for the polymerization into a polymerization vessel, and then the steps (A) to (D) are repeated in the same manner in a method for producing a vinyl chloride polymer,

(1) controlling the chloride ion concentration in the reaction mixture to 50 ppm or less through the step (A), and

(2) A method for producing a vinyl chloride polymer, characterized in that the step (B) and the step (C) are performed in a state where the inside of the polymerization vessel is shielded from the atmosphere outside the vessel .

According to this method, the chlorine ion concentration during the polymerization is controlled, and not only the polymerization step but also (A) to (D)
Throughout the entire process, the inside of the polymerization vessel is maintained in a state of being shielded from the outside atmosphere. Moreover, in such a state, the process (A)
The polymerization batch consisting of (D) is repeated. as a result,
The resulting polymer has very little initial coloration, and it is possible to effectively and surely prevent adhesion of scale, particularly adhesion of polymer scale at the gas-liquid interface of the polymerization vessel.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention comprises the above-mentioned step (A).
Consists of repeating the polymerization batch consisting of (D) as many times as necessary.

Step (A) A vinyl chloride monomer or a vinyl-based monomer mixture containing the monomer as a main component is polymerized in a polymerization vessel in which a scale-inhibiting coating film is preformed on at least the inner wall surface. The scale adhesion preventive coating film previously formed here is formed by applying a scale preventing agent which will be described later in detail with respect to the step (C).

One of the important features of the present invention is that the concentration of chloride ion in the reaction mixture is controlled to 50 ppm or less, preferably 30 ppm or less, through this polymerization step. The chloride ion concentration in the reaction mixture during this polymerization process is 50
If it exceeds ppm, the effect of the scale adhesion preventive agent applied to the inner wall surface of the polymerization vessel is not sufficiently exerted, and the adhesion of scale cannot be effectively prevented.

In the polymerization of a vinyl chloride monomer or a monomer mixture containing it as a main component in an aqueous medium, the chloride ion concentration in the reaction mixture generally rises rapidly in the initial stage of the polymerization, and then slightly increases until the end of the polymerization. Continues to rise or level off. It is considered that various factors such as the amount of methyl chloride and hydrochloric acid contained in the vinyl chloride monomer used as a raw material and the temperature of water used for charging influence the concentration of this chlorine ion,
For vinyl chloride monomer having a level of quality usually used industrially, for example, the temperature of water to be charged is 10 to 80 ° C.
It is possible to control the chlorine ion concentration in the reaction mixture to 50 ppm or less by adjusting the interval between the two and by adjusting the degree of vacuum in the polymerization vessel after charging. In general, the higher the temperature of the charged water, the lower the chloride ion concentration. More specifically, for example, standard quality used industrially, methyl chloride content 60ppm or less,
When a vinyl chloride monomer having a hydrogen chloride content of 0.03 ppm or less is used as a raw material, generally, after the completion of polymerization, after discharging the polymer slurry from the polymerization vessel, unreacted vinyl chloride is not opened without opening the polymerization vessel. The monomer is coated in a polymerization vessel in a concentration of 100 ppm or more and 5% or less (volume basis), and the temperature of water used for charging is adjusted to 20 to 60 ° C. The degree of vacuum in the chamber is -750 to 100 mmHg (1.
3 to 113 kPa), more typically -730 to -200 mmHg (4.0
To 75 kPa), and then charging the vinyl chloride monomer described above to adjust the chloride ion concentration in the reaction mixture to 50
It can be controlled below ppm.

After completion of the polymerization in step (B), the polymer slurry formed in the polymerization vessel is withdrawn from the polymerization vessel. In the method of the present invention, this extraction step (B) needs to be performed in a state where the inside of the polymerization vessel is shielded from the outside atmosphere (that is, without opening the inside of the polymerization vessel to the atmosphere). That is, the valve of the pipe leading to the inside where the outside air may enter must be closed without opening the manhole or the like provided in the polymerization vessel.

Specifically, the polymer slurry is discharged to a blowdown tank in a state where the internal pressure is still somewhat higher than the atmospheric pressure, or a gas holder in which the internal pressure of the internal pressure is approximately atmospheric pressure is used. After being connected to make the pressure almost equal to the atmospheric pressure, the polymer slurry is discharged from the polymerizer to the blowdown tank. Such discharge operation must be performed so that air does not enter the polymerization vessel. At the end of discharging the polymer slurry, the inside of the polymerization vessel is filled with 100% vinyl chloride monomer gas.

Step (C) Next, a polymer scale adhesion preventive film is formed.
Usually, a polymer scale adhesion inhibitor is applied to at least the inner wall surface of the polymerization vessel and dried to form a coating film. In the method of the present invention, this coating film forming operation also needs to be performed after the step (B) while the inside of the polymerization vessel is shielded from the atmosphere outside the vessel (that is, without opening the polymerization vessel to the outside air).

More specifically, in order to remove the polymer remaining in the vessel in a small amount, the scale anti-adhesive agent is applied in a state where the monomer gas is filled in the vessel without opening the polymerization vessel. After washing with water, a scale anti-sticking agent is applied.
When washed with water, the gas concentration of the vinyl chloride monomer in the vessel is reduced by the partial pressure corresponding to the vapor pressure of water. Therefore, the operation of applying the polymer scale anti-adhesion agent liquid and forming the coating film is performed in a state where the monomer is filled in the polymerization vessel with 10 to 100%, preferably 50 to 100% (the balance is steam). Done in. However, it is desirable that the first application before the polymerization is performed after depressurizing the inside of the polymerization vessel, or by charging a small amount of the vinyl chloride monomer under the depressurization to make the inside of the vessel a vinyl chloride monomer atmosphere.

The polymer scale anti-adhesion agent is used not only on the inner wall surface of the polymerization vessel, but also on the portion where the scale of the equipment attached to the polymerization vessel is likely to adhere, that is, the portion where the monomers come into contact with each other during the polymerization process. It is also preferable that it is applied to (including a certain portion) to form a coating film. As the equipment in contact with the monomer in the polymerization equipment, for example, a stirring blade, a stirring shaft,
There are capacitors, headers, baffles, search coils, bolts, nuts, etc. There are no particular restrictions on the material of these auxiliary equipment, and for example, stainless steel or glass-lined equipment can be used.

The inner wall surface of the polymerization vessel and other portions where a coating film is formed in some cases have surface roughness (Rma of JIS B0106 standard).
x) is preferably 10 μm or less, further 5 μm
It is more preferred that:

The method of applying the scale adhesion preventing agent to the inner wall surface of the polymerization vessel or the like is not limited, and is described in, for example, JP-A-57-61001.
55-36288, JP-B-56-501116, JP-B-56-501117, JP-A-59-11303, and the like can be used. The jacket temperature of the polymerization vessel at the time of coating may be generally in the range of 10 to 95 ° C, preferably 40 to 80 ° C.
Drying after coating, jacket temperature 30 ~ 95 ℃, preferably
Dry at 40-80 ° C without reducing the pressure inside the container.

The polymer scale adhesion preventive agent used for coating preferably contains an organic compound having 5 or more conjugated π bonds (hereinafter referred to as a conjugated π bond compound) as an active ingredient. In the present specification, the “π bond” means a double bond and a triple bond, for example, C═C, C≡C,
Examples include N = N and C = N. “Conjugated π bond” means a π bond having a conjugate relationship with another adjacent π bond. Among these conjugated π-bond compounds, more preferable one is a compound having 5 or more π-bonds in a conjugated relationship.

Further, the conjugated π-bond compound is preferably a compound having a molecular weight of 500 or more, preferably 1000 or more, measured by gel permeation chromatography (GPC).

Examples of the conjugated π-bond compound having a molecular weight of 500 or more include the following. 1) Among reaction products obtained by condensation reaction of dihydroxybiphenyls and aldehydes described in JP-B-6-62709 in the presence of an acidic catalyst, those having a molecular weight of 1000 or more: Examples of dihydroxybiphenyls Is 2,2'-dihydroxybiphenyl, 2,2'-dihydroxy-5,
5'-dimethylbiphenyl, 2,2'-dihydroxy-
4,4 ', 5,5'-tetramethylbiphenyl, 2,
2'-dihydroxy-5,5'-dichlorobiphenyl,
2,2'-dihydroxy-5,5'-dicyclohexylbiphenyl, 2,2'-dihydroxy-5,5'-di-
Examples thereof include tert-butylbiphenyl, and among them, 2,2'-dihydroxyphenyl is industrially preferable.

Examples of aldehydes include formalin, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, crotonaldehyde, benzaldehyde, furfural, phenylacetaldehyde, 3-phenylpropionaldehyde, 2-phenylpropionaldehyde, and formalin,
Acetaldehyde is industrially and economically advantageous. Dihydroxybiphenyls and aldehydes react in the presence of acidic catalysts to form reaction products. Preferred catalysts for this reaction are strongly acidic, such as sulfuric acid, hydrochloric acid, perchloric acid, P-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc., but more preferably hydrochloric acid. And P-toluenesulfonic acid.

More preferred reaction products of dihydroxybiphenyls with aldehydes are obtained when the molar ratio of aldehydes to dihydroxybiphenyls is not greater than 1.0. The preferred range is 0.5 moles of aldehydes to 1 mole of dihydroxybiphenyls.
˜1.0 mol, more preferably 0.6 to 0.9 mol.

The reaction between dihydroxybiphenyls and aldehydes is advantageously carried out in the range of 50 to 200 ° C. for a reaction time of 5 to 30 hours, more preferably 100 to 150 ° C. The presence of common solvents may be desirable in this reaction. Examples of preferable solvents include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloroethane, trichloroethane and monochlorobenzene; ethers such as butyl methyl ether, ethylene glycol dimethyl ether and dimethyl ether; methyl ethyl ketone. And ketones such as methyl isobutyl ketone, but are not limited thereto.

2) Among the condensation reaction products obtained by the condensation reaction of 1-naphthol and formaldehyde in the presence of a catalyst described in JP-A-57-164107, those having a molecular weight of 1,000 or more: 1-naphthol is represented by the following formula: Is selected from compounds represented by.

[0030]

Embedded image [In the above formula, a is 0 or 1, m is 0, 1,
2 or 3 (preferably 0, 1 or 2); R ₁ and R ₂ may be the same or different and they are halogen (preferably Cl), hydrocarbyl (preferably having 1 carbon atom). ~ 5 alkyl), hydroxy and hydrocarbyloxy (preferably alkoxyl having 1 to 5 carbon atoms). a or m
Is 0 means that there is no substituent. ]

Examples of 1-naphthol include 1-naphthol itself, 1,3-dihydroxy-naphthalene, and 1,5-dihydroxy-naphthalene and 1,7-dihydroxy-naphthalene. Examples of the medium for carrying out the condensation reaction include organic solvents such as water, alcohols, ketones and esters, for example, alcohols such as methanol, ethanol and propanol,
Examples thereof include ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate.

As the catalyst, an acidic catalyst such as hydrochloric acid, NaOH,
Basic catalysts such as KOH and NH ₄ OH are used, and these are added in an amount of 0.5 to 0.9 mol per mol of 1-naphthols.

The ratio of 1-naphthols and formaldehyde in the condensation reaction is influenced by the type of 1-naphthols and solvent used, the reaction temperature, the reaction time, etc.
Usually, it is preferable to use formaldehyde in an amount of 0.2 to 10 moles per 1 mole of 1-naphthols, and 0.5 to 10 moles.
It is preferably 5 mol. The condensation reaction is carried out by mixing 1-naphthols and formaldehyde in a suitable medium in the presence of a catalyst, usually at 50 to 200 ° C. for 1 to 30 hours, preferably 70 to 1
The reaction may be performed at 50 ° C for 3 to 10 hours. As a medium,
Examples thereof include water, alcohols, ketones, organic solvents such as esters, and the like, for example, alcohols such as methanol, ethanol, and propanol, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate. Can be mentioned.

3) Among condensates of phenol compounds and formaldehyde or benzaldehyde described in JP-A-57-192413 and JP-B-2-363, those having a molecular weight of 1,000 or more: Phenol compounds include pyrogallol, hydroxyhydroquinone, Hydroxybenzoic acid, salicylic acid, or mixtures thereof are preferred. The condensation product of the above-mentioned phenol compound with formalin or benzaldehyde is obtained by mixing these reaction components in a suitable medium in the presence of a catalyst, usually at room temperature to 200 ° C for 2 to 100 hours, preferably at 30 to 150 ° C. It is produced by reacting for about 30 hours.

Examples of the medium for carrying out the condensation reaction include organic solvents such as water, alcohols, ketones and esters. Examples thereof include alcohols such as methanol, ethanol and propanol, acetone and methyl ethyl ketone. Examples thereof include ketones and esters such as methyl acetate and ethyl acetate. PH of medium for conducting the condensation reaction
Is usually in the range of 1 to 13, and the pH adjusting agent can be used without particular limitation.

The ratio of the phenol compound and formalin or benzaldehyde in the condensation reaction is influenced by the type of phenol compound, formalin or benzaldehyde and solvent used, the reaction temperature, the reaction time, etc. Formaldehyde or benzaldehyde is preferably 0.5 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.

4) Polyaromatic amines described in JP-B-59-16561 having a molecular weight of 1,000 or more: The polyaromatic amine is a condensation reaction of any one of the following compounds, or two or more of them are combined together. It is obtained by reacting with. (a) expression

[0038]

Embedded image Wherein R ₁ and R ₂ are —H, halogen, —NH ₂ , —OH or an alkyl group having 1 to 8 carbon atoms and may be the same or different, such as ortho -, Meta- and para-phenylenediamine; diaminotoluene, diaminoxylene, diaminophenol, triaminobenzene, toluene and xylene; ethyl, propyl, butyl and pentyldi-
And triaminobenzene and the like, most preferred compounds are those in which R ₁ is —H and R ₂ is —H, a methyl group, or an ethyl group;

[0039]

Embedded image (In the formula, R ₃ and R ₄ are —H, halogen, —NH ₂ , —OH,
Or an alkyl group containing 1 to 8 carbon atoms and may be the same or different), for example, catechol, resorcinol, chlororesorcinol, hydroquinone, phloroglucinol, pyrogallol, etc .; dihydroxytoluene and Xylene; trihydroxytoluene and xylene; ethyl, propyl, butyl and pentyldi- and trihydroxybenzene and the like, most preferred compounds are those in which R ₃ is --H and R ₄ is --H or --OH. Yes; (c) expression

[0040]

Embedded image Wherein R ₅ and R ₆ are —H, halogen, —NH ₂ , —OH or an alkyl group having 1 to 8 carbon atoms, and may be the same or different, and Alkyl-substituted aminophenols such as ortho, meta, and para-aminophenols; diamino- and triamino-phenols; methyl, ethyl, propyl, butyl and pentylamino and diaminophenols; most preferred compounds are those in which R ₅ is is H, are those wherein R ₆ is -H or -NH _2; and
(d) diphenylamine, alkyl-substituted diphenylamine and formula

[0041]

Embedded image (In the formula, R is

[0042]

[Chemical 6] Or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ₁ , R ₂ , R ₃ and R ₄ are each —H,
-NH _2, -OH, an alkyl group having 1-8 halogen or carbon atom, and at least two -NH _2,
--OH or one of each)), such as bisphenol A, and the most preferred compounds are R ₁ and R ₄ are --OH or --NH ₂ , and R ₂ And R ₃ is —H.

Halogen in the above formula is chlorine, bromine,
It may be iodine or fluorine. When two or more of the above compounds are reacted together by a condensation reaction,
At least one compound must have an amino group,
And when more than two compounds are involved in the reaction, it is preferred that at least two of the compounds have amino groups. For example, useful polyaromatic amines are m-
Formed by condensing together phenylenediamine, resorcinol and p-aminophenol,
And m-phenylenediamine, resorcinol, phloroglucinol and m-aminophenol formed together by condensation.

Particularly useful polyaromatic amines are those obtained when aromatic diamines and polyhydric phenols are reacted together. Usually these compounds are reacted together in approximately equimolar ratios. However, it is also possible to use either the diamine or the phenol in excess.

As indicated above, acidic catalysts are used when any of the above compounds are self-condensed or reacted with one or more other compounds. For example, HCl, methanesulfonic acid, benzenesulfonic acid, sulfanilic acid, phosphoric acid, iodine, benzenedisulfonic acid, hydrogen bromide (HBr), hydrogen iodide (HI), aluminum chloride and the like can be used. The catalyst concentration will vary depending on the particular catalyst used. However, if the compound is allowed to self-condense, then
When one or more compounds are reacted, a catalyst concentration of about 0.005 moles to about 0.20 moles per mole of amino compound is desirable.

The reaction temperature of the compound, either alone or reacted with other compounds, will vary depending on the reaction time and the desired final product molecular weight. For example, the reaction component
It can be heated rapidly to 315 ° C. and then kept at that temperature for various times. It is also possible to heat the reaction components to various temperatures above 300 ° C. and to cool immediately. When using the latter method, reaction times are indicated as 0 hours. Thus, the reaction temperature will vary from about 250 ° C to 360 ° C and the reaction time will vary from about 0 hours to about 3 hours. The preferred reaction temperature range is 275 ° C to 330 ° C, and the reaction time is 0 hours to 1 hour.

5) A molecular weight of 1,000 among the condensation products selected from the group of self-condensation products of polyhydric phenols and self-condensation products of polyhydric naphthols described in JP-A-54-7487.
Above: Self-condensation products of polyhydric phenols are prepared by heating any one or more of resorcinol, hydroquinone, catechol or phloroglucinol, without catalyst or in the presence of a suitable catalyst. . Self-condensates of polyvalent naphthols, such as 2,7-
The same applies to self-condensates such as dihydroxynaphthalene, 3,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. Polyhydric phenol or polyhydric naphthol should be stored under an inert atmosphere such as nitrogen or argon.
Heat for 4 to 20 hours in the temperature range of 00 to 350 ° C. Various catalysts such as zinc chloride, aluminum chloride and sodium hydroxide can be used for this reaction. A catalyst concentration of about 0.05 mol to 0.50 mol per mol of one or more compounds to be condensed is sufficient.

6) Among the reaction products of a ketone resin described in JP-A-62-236804, a phenolic compound, and optionally an aldehyde compound, those having a molecular weight of 1,000 or more: The ketone resin used is generally Is a resin obtained by condensing ketones and aldehydes with a softening point of 80-
It is a solid substance at room temperature of 130 ° C. In particular, it is a product produced by using cyclohexanone or acetophenone and formaldehyde as the starting ketones.

The phenolic compound is a compound having one or more phenolic --OH groups in an aromatic compound. For example, phenol, monohydric phenol such as cresol, dihydric phenol such as resorcinol, catechol, hydroquinone and bisphenol A, trivalent phenol such as pyrogallol and hydroxyhydroquinone, or substituents such as alkyl group and carboxylic acid group on the above compounds A compound having is exemplified. Examples of the aldehyde compound include aliphatic aldehydes such as formaldehyde, paraformaldehyde and acetaldehyde, and aromatic aldehydes typified by benzaldehyde.

As a method for producing a reaction product of a ketone resin and a phenolic compound, the ketone resin and the phenolic compound are mixed with a Friedel-Craft type catalyst or an acid catalyst in a nitrogen atmosphere at 50 to 250 ° C., preferably 100 to 200 ° C. It is produced by reacting at 1 ° C. for 1 to 10 hours. Further, if desired, an aldehyde compound may be added and reacted, but as a method of adding and reacting the aldehyde compound at this time, (1) a method of simultaneously reacting a ketone resin with a phenolic compound and an aldehyde compound, (2) There is a method of reacting a ketone resin with a phenolic compound and then adding an aldehyde compound to the reaction, and (3) a method of reacting a phenolic compound with an aldehyde compound and then reacting with a ketone resin. .

As the Friedel-Crafts type catalyst or acid catalyst, usually used halides such as aluminum chloride, boron fluoride, zinc chloride and iron chloride or complex compounds thereof, inorganic acids such as hydrochloric acid and sulfuric acid, and paratoluene. Organic acids such as sulfonic acid can be used.

The ketone resin and the phenolic compound are 5 to 200 parts by weight based on 100 parts by weight of the phenolic compound.
Parts by weight, preferably 30 to 150 parts by weight, are used. The aldehyde compound is used in an amount of 0 to 2 mol, preferably 0.5 to 1.5 mol, per 1 mol of the phenolic compound.

The catalyst is used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the phenolic compound. When the amount of the catalyst is less than the above range, the reactivity is lowered, while when it is increased, the solubility in the solvent or the alkaline solution is lowered. As a medium for carrying out the condensation reaction, for example,
Examples include organic solvents such as water, alcohols, ketones and esters, and examples include alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate. . The pH of the medium for carrying out the condensation reaction is usually in the range of 1 to 13, and the pH adjuster can be used without particular limitation.

7) Among the condensates of phenothiazine and formaldehyde described in JP-A-2-500845, those having a molecular weight of 1,000 or more: In the reaction of phenothiazine and formamide, the mono-ratio of formaldehyde to phenothiazine is generally about 0.1 to less than 1. , Preferably about 0.4 to 1
Is less than. The reaction is carried out in the presence of a liquid diluent which is a solvent for phenothiazine but a non-solvent for the desired product. For example, tetrahydrofuran (THF),
Nonpolar solvents such as dimethylformamide (DMF), cyclohexanone and dimethylsulfoxide (DMSO) are used.

Either acidic or alkaline compounds can be used as catalysts for the reaction. However, acidic compounds are preferred, especially strong acids. Preferred compounds include hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Suitable caustic compounds include sodium hydroxide and other alkali metal hydroxides. The preferred reaction temperature is room temperature to the reflux temperature of the solvent having the lowest boiling point, preferably about 60 to 80 ° C.

8) Condensates of aromatic amines and aromatic nitro compounds described in JP-B-60-30681 and those based on them, having a molecular weight of 1,000 or more: (1) aromatic amine compounds and aromatics In the presence of condensation catalyst with nitro compounds 1
A condensate obtained by reacting in the temperature range of 00 to 250 ° C., and (2) a condensate obtained by forming a base with an alkali metal salt or an ammonium compound.

A condensate obtained by reacting an aromatic amine compound and an aromatic nitro compound in the presence of a mineral acid and a condensation catalyst, and / or this condensate, an alkali metal salt such as NaOH, Na ₂ CO ₃ or KOH. Some are based on ammonium compounds such as NH ₄ OH and (NH ₄ ) ₂ CO ₃ , but this condensate does not have a strict meaning, and the intermediates leading to the final condensate are naturally It is included in this condensate. The aromatic amine compound used here is a compound represented by the following general formula.

[0058]

[Chemical 7] In the above formula, R ¹ is _{-H, -NH 2, -Cl, -N} = N-C 6
_{H 5, -OH, -COCH 3,} -OCH 3, -NH-C 6 H 5, -NH-C 6 H 4
_{-NH 2, -NH-C 6 H} 4 -OCH 3, -N (CH 3) 2, -NH-C 6 H 4 -
OH, represents a -NH-CO-CH ₃ or an alkyl group having 1 to 3 carbon atoms, R ² represents -H, -NH _2, -OH, and -CH _3.

As such an aromatic amine compound,
Aniline, (ortho, meta, para) phenylenediamine, (ortho, meta, para) aminophenol, (ortho, meta, para) chloroaniline, (para) aminoazobenzene, 2,4-diaminoazobenzene, para-aminoacetanilide, (Ortho, meta, para) methylaniline, 4-aminodiphenylamine, 2-aminodiphenylamine, 4,4-diaminodiphenylamine, N,
N-dimethyl-para-phenylenediamine, 4-amino-3'-methoxydiphenylamine, 4-amino-4 '
-Hydroxydiphenylamine, 4-chloro-ortho-
Phenylenediamine, 4-methoxy-ortho-phenylenediamine, 2-amino-4-chlorophenol, 2,
3-diaminotoluene and the like are exemplified. Further, the aromatic nitro compound which is condensed with the aromatic amine compound is a compound represented by the following general formula.

[0060]

Embedded image In the above formula, R ³ is _{-H, -OH, -OCH 3, -OC} 2 H 5, -
Cl, -NH _2, -COOH, represent -SO ₃ H.

As such an aromatic nitro compound,
Nitrobenzene, (ortho, meta, para) oxynitrobenzene, (ortho, meta, para) nitroanisole,
(Ortho, meta, para) nitrophenetol, (ortho, meta, para) chloronitrobenzene, (ortho, meta, para) aminonitrobenzene, (ortho, meta, para) nitrobenzoic acid, (ortho, meta, para) nitrobenzene Sulfonic acid, (ortho, meta, para) nitroaniline, 2-nitro-para-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 4-amino-2-nitrophenol, etc. It is illustrated. For the condensation reaction of the aromatic amine compound and the aromatic nitro compound, a mineral acid and a condensation catalyst are used. Examples of the mineral acid include hydrochloric acid, nitric acid, hydrobromic acid, phosphoric acid and sulfuric acid. It is illustrated.

Suitable condensation catalysts include permanganic acid and its salts such as permanganic acid and potassium permanganate, and chromic acid-related substances such as chromium trioxide, potassium dichromate and sodium chlorochromate. Compounds, metal nitrates such as silver nitrate, lead nitrate, halogens such as iodine and bromine, hydrogen peroxide, sodium peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, peracetic acid, cumene hydroperoxide, perbenzoic acid , Peroxides such as p-menthane hydroperoxide, oxyacids or oxyacid salts such as iodic acid, potassium iodate and sodium chlorate, ferrous chloride, ferric chloride, copper sulfate, ferrous chloride Copper, cupric chloride, metal salts such as lead acetate, ozone and copper oxide, mercury oxide, cerium oxide, methane dioxide Cancer, such as oxides, such as osmium acid. It is also effective to use hydrogen peroxide in combination with ferrous chloride.

As the condensation catalyst, an oxidation catalyst such as a heavy metal salt, a peroxide or halogen and its oxygen acid is used. A condensate is obtained by heating at least one aromatic amine compound and at least one aromatic nitro compound in the presence of the above-mentioned mineral acid and condensation catalyst at 100 to 250 ° C. for 10 to 30 hours. The final product is affected by the types of aromatic amine compound, aromatic nitro compound, condensation catalyst and mineral acid, composition ratio and reaction temperature, and reaction time. The mixing ratio is preferably 0.10 mol to 0.50 mol of the aromatic nitro compound per 1 mol of the aromatic amine compound. If it is less than the lower limit of this range, the scale-inhibiting effect of the oil-soluble polymerization catalyst system is lowered, and if it exceeds the upper limit. Aromatic nitro compounds remain in the final product, reducing the scale prevention effect. Further, the condensation catalyst is preferably 0.03 mol to 0.50 mol, and the mineral acid is preferably 0.20 mol to 0.50 mol, per 1 mol of the aromatic amine compound.

The above-mentioned condensate is treated with NaOH, KOH, Na ₂ CO ₃ , NH.
Those based on alkali or ammonium compounds such as ₄ OH and (NH ₄ ) ₂ CO ₃ are also preferably used. As a method for forming the base, for example, 100 parts by weight of the target condensate is dispersed in water, 10 to 20 parts by weight of an alkali or ammonium compound is added thereto, and the mixture is heat-treated at 90 to 140 ° C. The alkali or ammonium compound may be used in an amount sufficient to neutralize the mineral acid used in the condensation.

The base compound is dissolved in chlorinated hydrocarbon which is a nonflammable solvent such as toluene or methylene chloride, trichloroethylene and perchlorethylene. Therefore, the base material has an advantage that a nonflammable solvent can be used for coating.

9) Condensate of pyrogallol and acetone described in JP-A-4-328104: The pyrogallol-acetone resin used is a condensation polymer of pyrogallol-acetone and usually has a pyrogallol / acetone molar ratio of 1 /.
It is in the range of 0.1 to 1/10 and usually has a melting point of 100 to 500 ° C. The higher the molecular weight, the higher the melting point.
A molecular weight of 1450 to 1650 corresponds to 60 to 170 ° C, and a molecular weight of 2600 to 4000 corresponds to a melting point of 200 to 220 ° C.

This pyrogallol-acetone resin is produced by dissolving pyrogallol in acetone and condensing it in the presence of a condensation catalyst. At this time, pyrogallol is usually used in an amount of 1 to 100 parts by weight per 100 parts by weight of acetone, and as the condensation catalyst, for example, oxyencarin or the like is used. The reaction may be performed at room temperature to 100 ° C.
Pyrogallol-acetone resin can also be used by obtaining a commercial product (manufactured by Fuji Chemical Industry Co., Ltd.).

10) Condensation product of aromatic amine compound, quinone compound and aromatic hydroxy compound described in JP-A-5-112603: the condensation product is (A) aromatic amine compound and (B)
It is a substance obtained by condensing a quinone compound and an aromatic hydroxy compound (C). Aromatic amine compound
(A) is a compound represented by the following general formulas (1) to (3).

[0069]

Embedded image [Here, R ¹ is —H, —NH ₂ , —Cl, —OH, —NO ₂ , —
COCH _3, -OCH _3, represents a -N (CH _{3) 2} or an alkyl group having 1 to 3 carbon atoms, R ² _{is, -H, -NH 2, -OH,} -CH 3,
-COOH, it represents the -SO ₃ H. ]

Specifically, aniline, ortho, meta or para-phenylenediamine, ortho, meta or para-aminophenol, ortho, meta or para-
Chloroaniline, ortho, meta or para-nitroaniline, ortho, meta or para-methylaniline,
N, N-dimethylparaphenylenediamine, 4-chloro-orthophenylenediamine, 4-methoxyorthophenylenediamine, 2-amino-4-chlorophenol,
Examples are 2,3-diaminotoluene, 5-nitro-2-aminophenol, 2-nitro-4-aminophenol, 4-amino-2-aminophenol, ortho, meta or para-aminosalicylic acid.

[0071]

Embedded image [Here, two R ¹ may be the same or different and is as described above, and two R ² may be the same or different,
As described above. ] Specifically, 4-aminodiphenylamine, 2-aminodiphenylamine, 4,4'-diaminodiphenylamine, 4-amino-3'-methoxydiphenylamine, 4
Examples include diphenylamines such as -amino-4'-hydroxydiphenylamine.

[0072]

Embedded image [Here, two R ¹ may be the same or different and is as described above, and R ² is also as described above. ] Specifically, α-naphthylamine, β-naphthylamine, 1,5-diaminonaphthalene, 1-amino-5-hydroxynaphthalene, 1,8-diaminonaphthalene,
2,3-diaminonaphthalene and the like are exemplified.

The quinone compound (B) is, for example, ortho, meta or para-benzoquinone, tol-para-quinone,
Ortho-xylo-para-quinone, thymoquinone, 2-methoxybenzoquinone, gentisylquinone, polyporic acid,
Benzoquinones such as ubiquinone n and their derivatives;
6-methyl-1,4-naphthoquinone, 2-methyl-1,
4 Naphthoquinone, Naphthoquinone, Juglon, Lawson,
Naphthoquinones and derivatives thereof such as blumbagin, alkannin, echinochrome A, vitamin K ₁ , vitamin K ₂ , shikonin, β, β′-dimethylacryl shikonin, β-hydroxyisowaler shikonin, and teracryl shikonin; tectoquinone, 3-hydroxy. -2-methylanthraquinone, anthraquinone, 2-hydroxyanthraquinone, alizarin, xanthobulbulin, rubiadine,
Examples thereof include anthraquinones such as mundistine, chrysophanoic acid, carminic acid, kermesic acid, and laccaic acid A and derivatives thereof; and phenanthrenequinones such as phenanthrenequinone. Among these, benzoquinones are particularly preferable. The aromatic hydroxy compound (C) is, for example, a compound represented by the general formula (4) or (5).

[0074]

[Chemical 12] [Wherein R ⁴ is —H, —Cl, —OH, —COCH ₃ , —OC
H _3, -COOH, represents -SO ₃ H or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents -H, -Cl, -OH, -OCH _3, and -OC ₂ H ₅ or -COOH . ]

Specifically, phenol, hydroquinone,
Resorcinol, catechol, hydroxyhydroquinone, pyrogallol, ortho, meta or para-chlorophenol, ortho, meta or para-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid acid,
Examples include phenol derivatives such as 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and (2,5-, 2,6-, 3,5-) dihydroxytoluene.

[0076]

Embedded image [Here, R ⁴ and R ⁵ are as described above. ] Specifically, α-naphthol, β-naphthol, (1,
3-, 1,4-, 1,5-, 2,3-, 2,6-, 2,
7-) dihydroxynaphthalene, 1-hydroxy-2-
Examples thereof include naphthol derivatives such as naphthoic acid and 3-hydroxy-2-naphthoic acid.

The condensation of the aromatic amine compound (A), quinone compound (B) and aromatic hydroxy compound (C) described above is
The reaction is performed in an organic solvent-based medium, if necessary, in the presence of a condensation catalyst. The pH of the organic solvent medium is in the range of 1 to 13, preferably 4 to 10. The pH adjuster can be used without particular limitation, examples of the acidic compound include phosphoric acid, sulfuric acid, phytic acid, acetic acid and the like, and examples of the alkaline compound include LiOH and KOH.
, An alkali metal compound such as NaOH, Na ₂ CO ₃ , Na ₂ SiO ₃ , Na ₂ HPO ₄ , NH ₄ OH, or an ammonium compound, an organic amine compound such as ethylenediamine, monoethanolamine, triethanolamine, or the like is used.

The medium for the condensation reaction is preferably an organic solvent such as alcohols, ketones, esters, etc .; a mixed solvent of water and an organic solvent miscible with water. Examples of the medium miscible with water include alcohols such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone; and esters such as methyl acetate and ethyl acetate.

If necessary, a condensation catalyst may be used. Examples of the condensation catalyst include α, α′-azobisisobutyronitrile, α, α′-azobis-2,4-dimethylvaleronitrile and the like. Azo catalysts, elemental or molecular simple halogens such as iodine, bromine, chlorine, hydrogen peroxide, sodium peroxide, benzoyl peroxide, potassium persulfate,
Peroxides such as ammonium persulfate, peracetic acid, cumene hydroperoxide, perbenzoic acid, p-menthane hydroperoxide, oxyacids such as iodic acid, periodate, potassium periodate, sodium perchlorate, etc. A salt is illustrated. Since the quinone compound acts as a condensation catalyst, the condensation reaction is performed without using a condensation catalyst.

At least one or more of the aromatic amine compound (A), at least one or more of the quinone compound (B) and at least one or more of the aromatic hydroxy compound (C) are added in the above-mentioned organic solvent medium. If necessary, a condensation product is obtained by reacting at room temperature to 200 ° C. for 0.5 to 100 hours under a condensation catalyst. The condensation product is an aromatic amine compound,
Although it is affected by the kind of quinone compound and aromatic hydroxy compound, composition ratio and reaction temperature, reaction time, in the present invention, 0.03 to 1.0 mol of quinone compound (B) is added per 1 mol of aromatic amine compound (A). It is preferable that

11) Condensation product of aromatic amine compound (A) and quinone compound (B) described in JP-A-6-56911: The aromatic amine compound (A) comprises a hydroxyl group, a carboxyl group and a sulfone group. The aromatic amine compound (A-1) has at least one selected from the group, and the aromatic amine compound (A-2) has neither a hydroxyl group, a carboxyl group nor a sulfone group.

[(A-1) Aromatic amine compound having at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and a sulfone group] The compound (A-1) is, for example, a compound represented by the following general formula ( It is a compound represented by 6) to (8).

[0083]

Embedded image (Where m is an integer of 1 to 5 and R ¹ is —OH, —CO
OH, and at least one selected from the group consisting of -SO ₃ H
R ² is —H, —NH ₂ , —Cl, —NO ₂ , —COCH
_3, - OCH _3, at least one selected from the group consisting of alkyl groups of -N (CH _{3) 2} and 1 to 3 carbon atoms. When a plurality of R ¹ are present, they may be the same or different, and when a plurality of R ² exist, they may be the same or different. )

Specifically, o-, m- or p-aminophenol, 2-amino-4-chlorophenol, 5-nitro-2-
Aminophenol, 2-nitro-4-aminophenol, 4-
Nitro-2-aminophenol, o-, m- or p-aminobenzoic acid, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 4 , 6-Diaminobenzoic acid, 3- or 4-aminophthalic acid, 2-, 4- or 5-aminoisophthalic acid, 4,6-diaminoisophthalic acid, 2,5- or 2,6-diaminoterephthalic acid, 3- , 4- or 5-aminosalicylic acid, 4-oxyanthranilic acid, o-, m- or p-aminobenzenesulfonic acid, 2,3-, 2,4-, 2,5-, 2,6-, 3, 4- or 3,5-diaminobenzenesulfonic acid, 2-amino-1-phenol-4-sulfonic acid, 6-amino-4-nitro-1-phenol-2-sulfonic acid, 6-amino-4-chloro- Examples thereof include 1-phenol-2-sulfonic acid.

[0085]

[Chemical 15] (Here, m, R ¹ and R ² are as defined in the general formula (6), n is an integer of 0 to 5, and when plural R ¹ are present, they may be the same or different. Well, when there are a plurality of R ² , they may be the same or different.) Specifically, 4-hydroxydiphenylamine, 4-amino
-4'-hydroxydiphenylamine, 4-carboxydiphenylamine, 4-amino-4'-carboxydiphenylamine, 4-sulfodiphenylamine, 4-amino-4'-sulfodiphenylamine and the like are exemplified.

[0086]

Embedded image (Here, p is an integer of 0 to 4, q is an integer of 0 to 3, and p and q are not 0 at the same time. Further, R ² is as defined in the general formula (6). , R ³ is -OH, -COO
H, —CH ₂ COOH, —CH ₂ CH ₂ COOH, and —SO ₃ H, and at least one selected from the group consisting of ^two or more R ² may be the same or different. ³
When there are two or more, they may be the same or different. ) Specifically, 4-amino-1-naphthol, 1-amino-5-naphthol, 1,2-naphthylenediamine-7-carboxylic acid, 1,
5-naphthylenediamine-2-carboxylic acid, 1,5-naphthylenediamine-4-carboxylic acid, 1,6-naphthylenediamine-4-
Carboxylic acid, 1,8-naphthylenediamine-4-carboxylic acid,
1,2-naphthylenediamine-3-sulfonic acid, 1,2-naphthylenediamine-4-sulfonic acid, 1,2-naphthylenediamine-5
-Sulfonic acid, 1,2-naphthylenediamine-6-sulfonic acid, 1,2-naphthylenediamine-7-sulfonic acid, 1,3-naphthylenediamine-5-sulfonic acid, 1,3-naphthylenediamine -6-sulfonic acid, 1,4-naphthylenediamine-2-sulfonic acid, 1,4-naphthylenediamine-7-sulfonic acid, 1,5-naphthylenediamine-2-sulfonic acid, 1,5-naphthyl Diamine-4-sulfonic acid, 1,5-naphthylenediamine-7-sulfonic acid, 1,6-naphthylenediamine-2-sulfonic acid, 1,6-
Naphthylenediamine-4-sulfonic acid, 1,6-naphthylenediamine-7-sulfonic acid, 1,8-naphthylenediamine-4-sulfonic acid, 1,8-naphthylenediamine-3,6-disulfonic acid, 1,8-naphthylenediamine-4,5-disulfonic acid, α-
Amino-β-naphthalenepropionic acid, α-amino-β
-Naphthalenecarboxylic acid, 2-naphthylamine-1-sulfonic acid, 8-naphthylamine-1-sulfonic acid, 5-naphthylamine-1-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-8 -Naphthol-6-sulfonic acid (γ
Acid), 2-amino-5-naphthol-7-sulfonic acid (J
Acid), 1-amino-8-naphthol-3,6-disulfonic acid (H
Acid) and the like.

Preferred compounds (A-1) are o-,
m- or p-aminophenol, 2,4- or 2,5-diaminobenzenesulfonic acid, 2,3-, 2,4-, 2,5-, 3,4- or 3,5-diaminobenzoic acid, 4,6-diaminoisophthalic acid, 2,5- or 2,6-diaminoterephthalic acid, 2,5- or 2,6-diaminoterephthalic acid, 1,2-naphthylenediamine-7-sulfonic acid, 1,5 -Or 1,6-naphthylenediamine-4-sulfonic acid and 1,5- or 1,6-naphthylenediamine-4-carboxylic acid.

[(A-2) Aromatic Amine Compound Having No Hydroxyl Group, Carboxyl Group, or Sulfone Group] The compound (A-2) can be produced, for example, by the following general formula (9)
To (11).

[0089]

Embedded image (Here, plural R ^{2 s} may be the same or different and are as defined in the general formula (6).)

Specifically, aniline, o-, m- or p-
Phenylenediamine, o-, m- or p-chloroaniline, o-, m- or p-nitroaniline, o-, m- or
p-methylaniline, N, N-dimethyl-p-phenylenediamine, 4-chloro-o-phenylenediamine, 4-methoxy-o-
Examples thereof include phenylenediamine and 2,3-diaminotoluene.

[0091]

Embedded image (Here, plural R ^{2 s} may be the same or different and are as defined in the general formula (6).) Specifically, 4-aminodiphenylamine, 2-aminodiphenylamine, 4,4′-diamino Diphenylamine, 4-
Amino-3'-methoxydiphenylamine and the like are exemplified.

[0092]

Embedded image (Here, a plurality of R ² may be the same or different and are as defined in the general formula (6).) Specifically, α-naphthylamine, β-naphthylamine, 1,5-diaminonaphthalene, 1 Examples include 2,8-diaminonaphthalene and 2,3-diaminonaphthalene. Compound (A
-2) are preferably o-, m- or p-phenylenediamine, 2- or 4-aminodiphenylamine,
4,4'-diaminodiphenylamine and 1,5- or 1,8
-It is diaminonaphthalene.

The aromatic amine compound (A) can be used alone or in combination of two or more. As the aromatic amine compound (A), the above compound (A-1) and the compound
At least one of (A-2) is used, preferably a compound
(A-1) is used, and more preferably, compound (A-1) and compound (A-2) are used in combination.

The quinone compound (B) is, for example, a compound represented by the following general formulas (12) to (15).

[0095]

Embedded image

[0096]

[Chemical 21] (Here, R ⁴ is -H, -NH ₂ , -Cl, -Br, -OH, -NO ₂
, -COCH ₃ , -OCH ₃ , -N (CH ₃ ) ₂ or 1 to 3 carbon atoms
Wherein R ⁵ is -H, -NH ₂ , -OH, -CH ₃ ,-
COOH or an -SO ₃ H. )

Specific examples include o-, m- or p-benzoquinone, oxy-p-benzoquinone, chloro-p-benzoquinone, bromo-p-benzoquinone, duroquinone, chloranil and the like.

[0098]

Embedded image

[0099]

Embedded image (Here, R ⁴ and R ⁵ are as defined in the general formula (12), and R ⁶ is -H, -OH, -CH ₃ , -Cl, -Br, -COCH ₃ , -OC.
Represents H ₃ , -COOH or -SO ₃ H. ) Specifically, 6-methyl-1,4-naphthoquinone, 2-methyl-
Examples include 1,4-naphthoquinone, lawson, juglone, plumbagin, α-naphthoquinone, β-naphthoquinone and the like.

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

The condensation product of the aromatic amine compound (A) and the quinone compound (B) is prepared by mixing the component (A) and the component (B) in a suitable medium, if necessary, in the presence of a catalyst, ordinarily. Room temperature ~ 20
0.5 to 100 hours at 0 ℃, preferably 3 to room temperature to 150 ℃
It is produced by reacting for 30 hours.

Since the quinone compound (B) also acts as a condensation catalyst, it is not necessary to add another condensation catalyst in particular, but examples of the condensation catalyst usable when adding another condensation catalyst include: Azo compounds such as α, α'-azobisisobutyronitrile and α, α'-azobis-2,4-dimethylvaleronitrile, elemental elements such as iodine, bromine, chlorine and fluorine, or elemental halogens in molecular form, peroxidation Inorganic peroxides such as hydrogen, sodium peroxide, potassium persulfate and ammonium persulfate, organic peroxides such as peracetic acid, benzoyl peroxide, cumene hydroperoxide, perbenzoic acid and p-menthane hydroperoxide, iodic acid ,
Periodic acid, potassium periodate, oxyacids such as sodium perchlorate or oxyacid salts, ferrous chloride, ferric chloride, copper sulfate, metal salts such as cuprous chloride, nitrobenzene,
o-, m- or p-oxynitrobenzene, o-, m- or p-nitroanisole, o-, m- or p-chloronitrobenzene, o-, m- or p-nitrobenzoic acid, o-, m- Alternatively, aromatic nitro compounds such as p-nitrobenzenesulfonic acid and the like can be mentioned.

Examples of the medium for carrying out the above condensation reaction include organic solvents such as alcohols, ketones and esters. For example, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone. And esters such as methyl acetate and ethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, toluene and xylene.

The pH of the medium for carrying out the condensation reaction is usually 1 to
The pH is in the range of 13, and the pH adjuster can be used without any particular limitation.

Aromatic amine compound for carrying out condensation reaction
The ratio of (A) and the quinone compound (B) is affected by the type of the aromatic amine compound, the quinone compound and the solvent used, the reaction temperature, the reaction time, and the like.
(A) The quinone compound (B) is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 1 part by weight. If the amount of the quinone compound (B) is too large or too small, the effect of the obtained condensation product on preventing the adhesion of the polymer scale decreases.

In order to further improve the polymer scale adhesion preventing effect, it is preferable to use (A-1) as the component (A) as described above, and further to use (A-1) and (A-2 ) Is preferably used in combination. When (A-1) and (A-2) are used in combination as the component (A), the compound (A-1) and the compound (A
-2) and because when the condensation product of the quinone compound (B) is applied to the inner wall surface of the polymerization vessel as an alkaline solution described below, the adhesion of the condensation product to the inner wall surface of the polymerization vessel is improved. It is estimated that there is. The above two kinds of aromatic amine compounds
When (A-1) and (A-2) are used in combination, it is preferable to use 0.01 to 10 parts by weight of compound (A-2) per 1 part by weight of compound (A-1), and further 0.1 to 5 parts by weight. It is preferred to use parts by weight.

If the condensation degree of the condensation product of the above components (A) and (B) is too high, precipitation of the condensation product occurs when the condensation product is an alkaline solution described below, and the coating solution is It may become non-uniform and the effect of preventing polymer scale adhesion may decrease. Therefore, it is preferable to add a reaction terminator (C) at an appropriate time during the condensation reaction between the components (A) and (B) to control the degree of condensation of the condensation product. Also, a reaction terminator
If (C) is added, the condensation product can be stored for a long period of time.

Examples of the reaction terminator (C) include, for example,
The following inorganic reducing agent (C-1), aromatic hydroxy compound (C-2) and aromatic hydroxy compound-based condensation product (C-
3).

[(C-1) Inorganic reducing agent] Specific examples of the inorganic reducing agent (C-1) include hydrogen, hydrogen iodide, hydrogen bromide, hydrogen sulfide, lithium aluminum hydride and borohydride. Sodium, calcium borohydride, zinc borohydride, tetraalkylammonium borohydride, trichlorosilane, hydrides such as triethylsilane, carbon monoxide, sulfur dioxide, sodium thiosulfate, sodium thiosulfite, sodium sulfite, potassium sulfite, Lower oxides or lower oxyacid salts such as sodium bisulfite and sodium hydrosulfite, sulfur compounds such as Rongalit, sodium sulfide, sodium polysulfide, ammonium sulfide, alkali metals such as sodium and lithium, magnesium, calcium, aluminum, zinc, etc. Large electropositive metals or their Salts of low-valence metals such as malgam, iron (II) sulfate, tin (II) chloride, titanium (III) trichloride, phosphorus trichloride, phosphorus triiodide, trimethylphosphine, triphenylphosphine, trimethylphosphine Examples thereof include phosphorus compounds such as fit and hexamethylphosphorus triamide, hydrazine, diborane, ethane-1,2-diaminoborane, dimethylamine-borane, diborane such as pyridineborane, and substituted boranes. Among these, preferred are hydrogen iodide, hydrogen bromide, sodium borohydride, sulfur dioxide, sodium thiosulfate, sodium thiosulfite, sodium sulfite, potassium sulfite, sodium bisulfite, sodium hydrosulfite and Rongalit.

[(C-2) Aromatic Hydroxy Compound] The aromatic hydroxy compound (C-2) is, for example, a compound represented by the following general formula:
It is a compound represented by (16) to (18).

[0111]

Embedded image (Where R ⁷ is —H, —Cl, —OH, —COCH ₃ , —O
Represents CH ₃ , —COOH, —SO ₃ H or an alkyl group having 1 to 3 carbon atoms, and R ⁸ represents —H, —Cl, —OH, —OCH ₃ , —OC ₂
Representing the H ₅ or -COOH. )

Specifically, phenol, hydroquinone,
Resorcinol, catechol, hydroxyhydroquinone, pyrogallol, o-, m- or p-chlorophenol, o-, m- or p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2, Examples include 6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,5-, 2,6- or 3,5-dihydroxytoluene. Preferred among these are hydroquinone, resorcinol, catechol, hydroxyhydroquinone, o-, m- or p-hydroxybenzoic acid and pyrogallol.

[0113]

Embedded image (Here, two R ⁷ may be the same or different and are as described above, and R ⁸ is also as described above.) Specifically, α-naphthol, β-naphthol, 1,3-,
1,4-, 1,5-, 2,3-, 2,6- or 2,7-dihydroxynaphthalene, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2
-Examples include naphthoic acid. Preferred among these are α-naphthol, β-naphthol and 1,3- or 2,7-dihydroxynaphthalene.

[0114]

[Chemical formula 26] (Here, two R ⁷ may be the same or different and are as described above, and R ⁸ is also as described above.) Specifically, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxy Biphenyl, 2,2'-dihydroxybiphenyl, 5,5'-dihydroxybiphenyl, 4,4'-
Dihydroxybiphenyl etc. are mentioned.

[(C-3) Aromatic Hydroxy Compound Condensate] The aromatic hydroxy compound condensate is a condensate containing the above aromatic hydroxy compound (C-2) as an essential condensation component, and An aromatic hydroxy compound (C-2) alone condensate, the compound (C-2) and another compound, for example, acetone,
Examples thereof include condensation products with aldehydes and aromatic amine compounds, aromatic hydroxyl group-containing natural organic compounds, and flavonoid hydroxyl group-containing natural organic compounds.

[(C-3-1) Condensate of Aromatic Hydroxy Compound Alone] Any of the aromatic hydroxy compounds exemplified above.
Condensates of (C-2) can also be obtained by a condensation reaction, and typical examples thereof include respective condensates of pyrogallol, resorcinol, catechol, 2,7-dihydroxynaphthalene, 2-hydroxynaphthoquinone and the like. This condensate is obtained by mixing an aromatic hydroxy compound in water, an organic solvent such as alcohols, ketones, and esters, or a mixed solvent of water and the organic solvent, with a peroxide, an azo compound, a nitro compound, a halogen compound. It can be obtained by reacting at room temperature to about 100 ° C. in the presence of a catalyst such as a compound, quinone or metal salt. Specific examples of the catalyst include peroxides such as periodic acid, potassium periodate, and hydrogen peroxide; α, α ′
Examples include azo compounds such as azobisisobutyronitrile; metal salts such as ferric chloride; aromatic nitro compounds such as nitrobenzene; aromatic quinone compounds such as p-benzoquinone.

[(C-3-2) Aromatic Hydroxy Compound-Acetone Condensate] Aromatic Hydroxy Compound (C-2) Exemplified above
Any of the condensates of acetone and acetone can be used. Representative examples are pyrogallol-acetone condensate, resorcinol-acetone condensate, 2,7-dihydroxynaphthalene-acetone condensate, 1,5-dihydroxynaphthalene-acetone condensate, 2,6-dihydroxynaphthalene-acetone condensate. Body, 2,3-dihydroxynaphthalene-acetone condensate, 2-hydroxynaphthoquinone-acetone condensate, alizarin-acetone condensate and the like. The condensate can be obtained by dissolving an aromatic hydroxy compound in acetone and reacting at room temperature to about 100 ° C. in the presence of a catalyst. Examples of the catalyst include phosphorus oxychloride.

[(C-3-3) Aromatic Hydroxy Compound-Aldehyde Condensate] Examples of the aldehyde which is the other component of the condensate include formaldehyde, acetaldehyde, glyoxal, glutaraldehyde and bendaldehyde. Any of the above-described condensates of an aromatic hydroxy compound and an aldehyde can be used. Typical examples are phenol, hydroquinone, catechol, pyrogallol, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, alizarin, anthraflavic acid, or
Condensates of 1,4,5,8-tetrahydroxynaphthalene and formaldehyde, pyrogallol-benzaldehyde condensates, phenol-benzaldehyde condensates, 2,3-dihydroxynaphthalene-benzaldehyde condensates, catechol-benzaldehyde condensates, anthraflavin Acid-benzaldehyde condensate, 2,7-dihydroxynaphthalene-
Examples thereof include a benzaldehyde condensate, a 1,4,5,8-tetrahydroxynaphthalene-benzaldehyde condensate, and a 1,5-dihydroxynaphthalene-benzaldehyde condensate.
This condensate is obtained by mixing an aromatic hydroxy compound and an aldehyde in an aqueous or alcoholic solvent in the presence of a catalyst at room temperature to
Obtained by reacting at about 200 ° C. Examples of the catalyst include acidic compounds such as phosphoric acid and hydrochloric acid, alkaline compounds such as sodium hydroxide, potassium hydroxide and ammonia.

[(C-3-4) Aromatic Hydroxy Compound-Aromatic Amine Compound Condensate] The aromatic amine compound which is the other condensation component of this condensate is the same as that of the polymer scale adhesion preventive agent of the present invention. Examples of the component (A) include those already described. The combination of the aromatic hydroxy compound and the aromatic amine compound is not particularly limited. As a typical example, pyrogallol-p-phenylenediamine condensate,
Resorcinol-m-phenylenediamine condensate, pyrogallol-1,8-diaminonaphthalene condensate, catechol
-1,8-diaminonaphthalene condensate, 2,7-dihydroxynaphthalene-p-aminophenol condensate, 4-aminodiphenylamine-pyrogallol condensate, 2,3-dihydroxynaphthalene-1,5-diaminonaphthalene condensate, etc. Can be mentioned. This condensate contains an aromatic hydroxy compound and an aromatic amine compound in water, in an organic solvent such as alcohols, ketones and esters, or in a mixed solvent of water and the organic solvent in the presence of a catalyst at room temperature to Obtained by reacting at about 200 ° C. Examples of the catalyst include peroxides such as periodic acid, potassium periodate, and hydrogen peroxide; α, α ′
Examples include azo compounds such as azobisisobutyronitrile; metal salts such as ferric chloride; aromatic nitro compounds such as nitrobenzene; aromatic quinone compounds such as p-benzoquinone.

[(C-3-5) Aromatic Hydroxyl Group-Containing Natural Organic Compound] Examples of the aromatic hydroxyl group-containing natural organic compound include quintuple tannin, smack tannin, tara tannin, baronia tannin, chestnut tannin, and miro Balan tannins, oak tannins, dividi bit tannins, argalovia tannins, gambier tannins, quebracho tannins, wattle tannins, mimosa tannins, mangrove tannins, hemlock tannins,
Examples thereof include spruce stannin, burmacatitanin, oak bark tannin, oyster astringent tannin, curcumin, urushiol, lignin, ligninsulfonic acid sodium salt, and alkali lignin.

[(C-3-6) Flavonoid Hydroxyl Group-Containing Natural Organic Compound] Specific examples of the flavonoid hydroxyl group-containing natural organic compound include perilla pigment, grape juice pigment, grape skin pigment, and red cabbage pigment. , Corn pigment, chollian pigment, safflower pigment, cocoa pigment and the like.

The aromatic hydroxy compound condensate (C
-3-1) to (C-3-6), preferred are pyrogallol-acetone condensate, 2,7-dihydroxynaphthalene-acetone condensate, 2,3-dihydroxynaphthalene-acetone condensate, resorcinol- Acetone condensate, 2,7-dihydroxynaphthalene-benzaldehyde condensate, 2,3-dihydroxynaphthalene-formaldehyde condensate, 1,4,5,8-
Tetrahydroxynaphthalene-benzaldehyde condensate, pyrogallol-formaldehyde condensate, 2,7-dihydroxynaphthalene condensate, pyrogallol condensate, 2,7-
Dihydroxynaphthalene-p-aminophenol condensate, catechol-4-aminodiphenylamine condensate, pyrogallol-1,8-diaminonaphthalene condensate, quintuple tannin, wattle tannin, mimosa tannin, oak tannin, hemlock tannin, quebracho tannin, Chestnut tannin, oyster astringent tannin and mangrove tannin.

The reaction terminator may be added as it is or after being dissolved in an appropriate solvent such as the solvent used in the above condensation reaction. The reaction terminator (C) may be added after initiating the condensation reaction between the components (A) and (B), and is preferably performed immediately before the precipitation of a condensation product of the components (A) and (B). ,
That is, although it varies depending on the types of the components (A) and (B), the reaction rate, etc., the conversion of the condensation reaction between the components (A) and (B) is 50%.
Add when ~ 99 wt% is reached. The condensation reaction conversion rate is determined by the following formula. Conversion rate of condensation reaction (% by weight) = {(ab) / a} × 100

The amount of the reaction terminator (C) added is the same as that of the component (A).
It is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 1 part by weight of the component (B). 12) The reaction product of polyvinyl alcohol and aminobenzoic acid as described in WO 88/05055:

[0125]

Embedded image [In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each is a hydrogen atom or an amino group (NH ₂ ), provided that at least one of these substituents is an amino group. m, n
And p are integers of m> 2, n ≧ 0 and p ≧ 0, respectively. ] Aminobenzoic acid ester of partially saponified polyvinyl acetate represented by

This ester is obtained as follows. First, partially saponified polyvinyl acetate and formula (i)

[0127]

Embedded image [In the formula, R ′, R ″ and R ′ ″ may be the same or different and each is a hydrogen atom or a nitro group (—NO ₂ ), provided that at least one of these substituents is a nitro group. ]
With an acid halide represented by the formula (ii): in a suitable medium, in the presence of a catalyst, at room temperature to 200 ° C. for 1 to 50 hours.

[0128]

[Chemical 29] [Wherein R ′, R ″ and R ′ ″ are as described above,
m, n and p are integers of m> 2, n ≧ 0 and p ≧ 0, respectively. ] The compound represented by this is obtained. Next, this compound is reduced with triethanolammonium monoformic acid in the presence of a palladium catalyst to obtain the required aminobenzoic acid ester.

Among these conjugated π-bond compounds, preferred are the condensates of aromatic amine compounds and quinone compounds, the condensates of aromatic amine compounds and aromatic nitro compounds, and the aromatic amine compounds and quinone compounds. And an aromatic hydroxy compound.

The concentration of the conjugated π-bond compound in the coating liquid when the scale anti-adhesion agent is applied is preferably 0.01 to 5.0, more preferably 0.05 to 2.0.

The above-mentioned polymer scale anti-adhesion agent preferably contains at least one selected from the group consisting of inorganic colloids and alkali metal silicates in order to further improve the scale anti-adhesion effect. The additive probably interacts with the conjugated π-bonding compound to enhance the hydrophilicity of the surface of the coating film composed of the obtained scale anti-adhesion agent or enhance the adhesion of the polymer scale anti-adhesion agent to the inner wall of the polymerization vessel. It is presumed that there is an effect.

Examples of the inorganic colloid include aluminum, thorium, titanium, zirconium, antimony,
Examples thereof include colloids of oxides and hydroxides of metals selected from tin, iron, etc., tungstic acid, vanadium pentoxide, colloids of gold and silver, colloids of silver iodide sol, selenium, sulfur, silica and the like. Preferred among these are colloids of oxides and hydroxides of metals selected from aluminum, titanium, zirconium, tin and iron, and colloidal silica. The inorganic colloid may be obtained by any production method, and the production method is not particularly limited. For example, a dispersion method using water as a dispersion medium,
It may be a particle colloid produced by the agglomeration method. The size of the colloid particles is preferably from 1 to 500 mμ.

Examples of alkali metal silicates include alkali metal metasilicates (M ₂ SiO ₃ ) and orthosilicates (M ₄ S) such as lithium, sodium and potassium.
iO ₄ ), disilicate (M ₂ Si ₂ O ₃ ), trisilicate (M ₃ Si
₃ O 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 inorganic colloid and the alkali metal silicate can be used alone or in combination of two or more.

The amount of the component selected from the inorganic colloid and the alkali metal silicate is the conjugated π-bond compound 1
It is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight per part by weight.

Further, the above-mentioned polymer scale adhesion preventing agent preferably contains a water-soluble polymer compound in order to further improve the polymer scale adhesion preventing effect. This is also presumably due to an effect of increasing the hydrophilicity of the coating film surface by interacting with the conjugated π-bonded compound.

Examples of the water-soluble polymer compound include amphoteric polymer compounds such as gelatin and casein; anionic polymer compounds such as polyacrylic acid, polystyrenesulfonic acid, carboxymethylcellulose and alginic acid; and polyvinylpyrrolidone, for example. Cationic nitrogen-containing polymer compounds such as polyacrylamide; examples thereof include hydroxyl group-containing polymer compounds such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, and pectin. Further, the above-mentioned polymer scale anti-adhesion agent may contain a dye and / or a pigment to such an extent that the initial coloration of the resulting polymer product is not deteriorated.

Step (D) Raw materials for the subsequent polymerization are charged into the polymerization vessel thus formed with the polymer scale-inhibiting coating as usual. Then, the steps (A) to (D) are repeated as many times as necessary. INDUSTRIAL APPLICABILITY The method of the present invention is applied to homopolymerization of vinyl chloride monomer in an aqueous medium and copolymerization of a vinyl-based monomer mixture containing vinyl chloride monomer (usually containing 50% by weight or more of vinyl chloride). be able to. The type of polymerization may be suspension polymerization or emulsion polymerization. Examples of vinyl-based monomers that can be subjected to copolymerization with a vinyl chloride monomer include, for example,
Vinyl acetate, vinyl esters such as vinyl propionate, acrylic acid, methacrylic acid or their esters or salts, maleic acid or fumaric acid, and their esters or anhydrides, butadiene, chloroprene,
Diene monomer such as isoprene, styrene,
Examples thereof include acrylonitrile, vinylidene halide, vinyl ether and the like.

Other conditions for carrying out the method of the present invention are those commonly used in suspension polymerization or emulsion polymerization of vinyl chloride monomer or a vinyl-based monomer mixture mainly containing it in an aqueous medium. It is good under the conditions. As the polymerization catalyst, for example, t
-Butylperoxy neodecanoate, di-2-ethylhexyl peroxydicarbonate, 3,5,5-trimethylhexanoel peroxide, α-cumylperoxy neodecanoate, cumene hydroperoxide,
Cyclohexanone peroxide, t-butyl peroxypivalate, di-2-ethoxyethyl peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate and acetylcyclohexyl peroxide Organic peroxides such as oxides, α, α′-azobisisobutyronitrile, α,
Azo catalysts such as α'-azobis-2,4-dimethylvaleronitrile, water-soluble peroxides such as potassium persulfate and ammonium persulfate, and the like can be used. Also,
Examples of the dispersant include partial oxides of polyvinyl acetate, polyacrylic acid, copolymers of vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropylmethyl cellulose, and natural and synthetic polymer compounds such as gelatin. Suspending agents, sorbitan monolaurate, nonionic emulsifiers such as sorbitan trioleate, sodium lauryl sulfonate, anionic emulsifiers such as anionic emulsifiers such as sodium alkylbenzene sulfonate, calcium carbonate as other additives,
Fillers such as titanium oxide, tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, stabilizers such as dioctyltin mercaptide, lubricants such as rice wax, stearic acid and cetyl alcohol, DOP, DBP
A plasticizer such as, a chain transfer agent such as trichlorethylene or mercaptans, and a pH adjusting agent are added to the polymerization system.
According to the method of the present invention, the adhesion of polymer scale can be effectively prevented regardless of the types of the catalyst, dispersant, and additive.

[0140]

[Function] It is unclear how performing steps (B) and (C) in a state where the inside of the polymerization vessel is shielded from the atmosphere outside the vessel contributes to the prevention of scale adhesion. Considering the fact that the scale anti-sticking agent liquid is usually applied to the inside of the vessel in a state where the vessel is open to the outside air, considering the fact that the inside of the vessel is replaced with air, the method of the present invention probably indicates that the polymerization vessel is That the oxygen and minute dust adsorbed on the inner wall surface of the
It is presumed that controlling the chloride ion concentration in the reaction mixture to 50 ppm or less has some synergistic effect, resulting in a decrease in the initial coloration of the polymer and a marked decrease in the amount of scale deposits.

[0141]

The present invention will be described in detail below with reference to examples and comparative examples. In addition, "part" means "part by weight".

Production of Condensation Product In the production examples below, the molecular weight of the obtained condensation product was measured as follows.

Measurement of molecular weight The weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) under the following measurement conditions. Column: Guard column Product name slim-pack GPC-800DP, manufactured by Shimadzu Corporation Analysis column Product name slim-pack GPC-803D, 802D, manufactured by Shimadzu Corporation Mobile phase: 10mM LiBr / DMF Flow rate: 1.0ml / min Detector: RI temperature: 60 ℃

Production Example 1 Production of Condensation Product No. 1 In a pressure resistant reactor, methanol 30,000 mol (960 kg), 1,8-
100 mol (15.8 kg) of diaminonaphthalene, 50 mol (5.4 kg) of parabenzoquinone and 250 mol (31.5 kg) of pyrogallol were charged, and the temperature was raised to 80 ° C while stirring. After reaction at 80 ° C. for 5 hours, the mixture was cooled to obtain a methanol solution of a condensation product. In this way, a solution of the condensation product No. 1 was obtained. The condensation product No. 1 had a weight average molecular weight of 2,000.

Production Example 2 Production of Condensation Product No. 2 Referring to Production Example 3 of Japanese Patent Publication No. 6-62709, a scale adhesion preventive agent was produced. In a pressure-resistant reactor, 2,2'-dihydroxybiphenyl 30 mol (5.59 kg), paraformaldehyde with a purity of 95% 22.5 mol (0.711 kg), paratoluenesulfonic acid
0.19 kg and 10 ethylene glycol dimethyl ether
L was charged and the temperature was raised to 130 ° C. with stirring. At 130 ° C
After reacting for 17 hours, it was cooled to 50 ° C, and the reaction mixture was mixed with water 50
It was put into L. The resin deposited by pouring into water was filtered, washed with water and dried to obtain 5.1 kg of 2,2'-dihydroxybiphenyl-formalin condensation resin (condensation product No.
2) was obtained. Weight average molecular weight of condensation product No. 2 is 4300
Met.

Production Example 3 Production of Condensation Product No. 3 With reference to Production Example 1 of JP-A-57-164107, a scale anti-sticking agent was produced. 250 mol of 1-naphthol (36.0 kg) and 1N NaOH aqueous solution (180 mol of NaOH, 7.2 kg) in a pressure resistant reactor.
(Containing) 180 L was charged and the temperature was raised to 70 ° C. with stirring. Next, formaldehyde (38 w / v% aqueous solution 19.75 L, 250 mol) was added dropwise to the reaction mixture over 1.5 hours. During this time, the internal temperature of the reactor was controlled not to exceed 80 ° C.
The reaction mixture was then cooled to 60 ° C. over 3 hours with continued stirring. The reaction mixture was then warmed to 98 ° C and at 98 ° C for 0.
Allowed to react for 5 hours. Then, the reaction mixture was cooled to obtain an alkaline solution of a condensation product (condensation product No. 3). The condensation product No. 3 had a weight average molecular weight of 700.

Production Example 4 Production of Condensation Product No. 4 A scale anti-sticking agent was produced with reference to Synthesis 2 of coating compound of JP-A-57-192413. Pyrogallol for pressure-resistant reactor
100 mol (12.6 kg) and 100 L of water were charged, and pyrogallol was dissolved in water. Next, 200 mol (21.2 kg) of benzaldehyde and 300 mol (29.4 kg) of phosphoric acid were added to the resulting solution, and the mixture was reacted at 100 ° C for 6 hours. As a result, a reddish brown product insoluble in water was obtained. Was obtained. After washing the water-insoluble product with ether, a methanol-soluble component was extracted from the water-insoluble product with methanol, and then methanol was removed by drying from the extract to obtain a condensation product No. 4 (pyrogallol- Benzaldehyde condensate)
I got The weight average molecular weight was 4000.

Production Example 5 Production of Condensation Product No. 5 Referring to Production Example I of JP-B-59-16561, a scale anti-sticking agent was produced. M-phenylenediamine for pressure-resistant reactor
100 mol (10.8 kg), resorcinol 200 mol (22.0 kg) and 1.04 kg of 35% hydrochloric acid as a catalyst (10 mol as HCl) were charged, and the temperature was raised to 305 ° C. As soon as the mixture in the reaction vessel reached 305 ° C, it was cooled. The steam generated during the temperature rise and reaction was removed, and the internal pressure was kept at 150 kPa or less. After cooling, the obtained m-phenylenediamine-resorcinol condensate was pulverized to obtain a condensation product No. 5. The weight average molecular weight was 3,000.

Production Example 6 Production of Condensation Product No. 6 Referring to Production Example VI of JP-B-59-16561, a scale anti-sticking agent was produced. P-Aminophenol 10 in pressure resistant reactor
0 mol (10.9 kg) and 30% hydrochloric acid 0.99 kg (9.5 mol as HCl) were charged, and the temperature was raised to 169 ° C. When it reaches 169 ℃,
18 L of xylene was gradually added. The purpose of adding xylene is to remove water produced during the condensation reaction as an azeotropic mixture. Next, the reaction mixture was heated to 222 ° C and heated to 222 ° C.
And reacted for 3 hours. The mixed vapor of xylene and water generated during the reaction was removed, and the internal pressure was kept at 150 KPa or less. After 3 hours of reaction, the reaction mixture was cooled. The obtained reaction product was solid. Next, the reaction product was pulverized into fine particles, washed with water, filtered and dried to obtain a condensation product No. 6. The weight average molecular weight was 2500.

Production Example 7 Production of Condensation Product No. 7 A scale anti-sticking agent was produced with reference to Example 1 of JP-A-54-7487. Resorcinol 200 mol (22.
(0 kg) was charged and heated under a nitrogen atmosphere. Resorcinol was heated to 300 ° C., reacted at 300 ° C. for 8 hours, and cooled. The obtained solid self-condensation resorcinol was pulverized to obtain a condensation product No. 7. The weight average molecular weight was 1700.

Example 1 The following experiment was conducted using the polymerization apparatus shown in FIG. FIG.
In the above, the stainless steel polymerization vessel 1 having an internal volume of 130 M ³ is equipped with a stirring means 2, a heating / cooling jacket 3, a manhole 4, and other auxiliary equipment (not shown) usually provided in the polymerization vessel for vinyl chloride polymerization. There is. The line 5 connected to the upper part of the polymerization vessel 1 is a raw material charging line,
As shown, vinyl chloride monomer (VCM) charging line 5
a, catalyst solution charging line 5b, suspension agent solution charging line 5
c, branch lines such as pure water charging line 5d are connected. This charging line has valves V1 and V at the positions shown.
2, V3, V4 and V5 are provided. Further, the line 6 connected to the upper part of the polymerization vessel 1 is an exhaust gas inside the polymerization vessel 1,
It is provided for collecting monomers and the like, and is guided to a vacuum pump 12 and a gas holder 13 by a branched line 7. A monomer recovery line 8 is led out from the gas holder 13, and a line 9 branched from the line is connected to the line 6 and used for a pressure equalizing operation described later. These lines 6, 7, 8
And 9 have valves V6, V7, V8, V in the positions shown.
9, V10 and V18 are provided. Furthermore, the polymerization vessel 1
A line 10 is connected to the upper part of the reactor via a device 11 for washing the inside of the polymerization vessel and applying the scale anti-adhesion agent. The line 10 includes a pure water supply line 10a and a scale anti-adhesion agent supply line 10b. Connected as shown. These lines have valves V14 and V1 at the positions shown.
5, V16 and V17 are provided. A line 14 is connected to the bottom of the polymerization vessel 1 and is divided into a line 14a for introducing the polymer slurry to the blowdown tank and a line 14b for discharging the scale adhesion preventing agent liquid and washing water to the waste water tank. The composition of the polymer scale anti-adhesive coating solution used in each experiment is shown in Table 1. In each experiment, polymerization of vinyl chloride monomer was repeated as follows. However, the experiment numbers marked with * in Tables 1 to 3 are comparative examples,
Some did not follow the procedure below. That is, in the experiments of Nos. 101 to 106, after completion of the polymerization, the polymerization vessel was opened to the atmosphere and the scale anti-adhesion agent liquid was applied. First, all valves and manholes of the polymerizer are closed.

(1) Pretreatment in the vessel The valves V6, V8 and V9 were opened and the vacuum pump was started to reduce the pressure in the polymerization vessel to -700 mmHg. Valve V6
And the valves V14, V15, and V17 are opened to apply the scale anti-sticking agent coating liquid to the inner wall of the polymerization vessel, the stirring means, and the entire surface in contact with the monomer. After coating, valves V14 and V
15, V17 is closed, valve V6 is opened, the vacuum pump is operated, the jacket temperature is reduced to -650 mmHg at 60 ° C, and the coating solution is dried. The vacuum pump is stopped, and valves V6, V8,
V9 was closed. Open the valves V14, V15 and V16
Wash with water of 10 kg / cm ² (gauge pressure), valves V11, V13
Open and send the wash water to the waste water tank, then open the valve V14,
Close V15, V16, V11 and V13.

(2) Charging Valves V1, V2, V3, V4 and V5 were opened, 100 parts of vinyl chloride monomer, 200 parts of pure water, 0.022 part of partially saponified polyvinyl alcohol, 0.028 of hydroxymethyl cellulose.
Part, 0.03 part of t-butyl peroxyneodecanate are charged, and valves V1, V2, V3, V4 and V5 are closed.

(3) Polymerization When the charged raw materials are polymerized for 7 hours while stirring at an internal temperature of 52 ° C., the pressure inside the vessel is reduced to 5 kg / cm ² . At this point, the polymerization is completed.

(4) Exhaust gas The valves V6, V8 and V9 are opened, and exhaust gas is discharged to the gas holder until the internal pressure of the device becomes almost atmospheric pressure. After that, the valves V8 and V9 are closed.

(5) Pressure equalization The valves V7 and V10 are opened to equalize the pressure.

(6) Slurry withdrawal The valves V11 and V12 are opened, and the polymer slurry is withdrawn into the blowdown tank.

(7) First water washing valve inside the vessel Open the valves V14, V15 and V16 to wash the inside of the vessel and send the washing water to the blowdown tank. After that, the valves V12 and V16 are closed.

(8) Coating The valves V17 and V13 are opened, and the scale adhesion preventing agent coating liquid is coated.

(9) Drying The valves V14, V15, V17, V11, V13, V7 and V10 are closed, the valves V8 and V9 are opened, the vacuum pump is started, the jacket temperature is reduced to -700 mmHg and the coating liquid is applied. To dry. Then, the vacuum pump is stopped and the valves V6, V
8. Close V9.

(10) Second water washing valve inside the vessel Open the valves V14, V15, V16, V11 and V13 to wash the inside of the vessel and discharge the washing water to the west water tank.
The valves V14, V15, V16, V11 and V13 are closed. The operation from the charging (2) to the second washing with water (10) after the polymerization was set as one batch, and was repeated up to 800 batches.

The chlorine ion concentration during the polymerization in each experiment was determined by the contents of methyl chloride and hydrochloric acid contained in the vinyl chloride monomer as a raw material, the temperature of the ion-exchanged water (10-80%).
Temperature range) and so on. In addition, as in the present application, the chlorine ion concentration decreases when shut off from the outside air.

The raw material vinyl chloride monomer used in each experiment had a methyl chloride content of 50 ppm or less and a hydrogen chloride content of 0.03 ppm or less.
What was adjusted to ° C was used. However, Experiment No. 101 ~ 12
No. 1 uses a polymerization vessel of which inner wall material is SUS404, and Experiment Nos. 122 to 130 use a polymerization vessel of SUS316L. In each experiment, 50th, 100th, 200th, 300th,
After the completion of each batch of 400, 500, 600, 700 and 800 batches, the scale adhesion state in the liquid phase part and the gas-liquid interface part of the inner wall of the polymerization vessel was visually evaluated according to the following criteria (a).
Further, after the final batch was completed, the amount of scale adhered to the liquid phase portion and the gas-liquid interface portion was determined by the following method (b). The results are shown in Table 2. In addition, the fish eye when the polymer obtained in each experiment was molded into a sheet, the following method
Measured in (c). Table 3 shows the results. Further, the brightness index (L value) when the polymer obtained in each experiment was molded into a sheet was measured by the following method. Table 3 shows the results.

(A) Evaluation scale of polymer scale adhesion A: No scale adhesion B: Sandy scale adhesion of several% C: Partial thin scale adhesion (adhesion rate of about 10%) D: Partial Thick scale adheres (approx. 10%) E: Partially thin scale adheres (approx. 50%) F: Partially thick scale adheres (approx. 50%) G: Thin scale on the entire surface Is attached H: Thick scale is attached to the entire surface

(B) Method for measuring the amount of polymer scale adhered The scale adhered to a 10 cm square area at a predetermined location on the inner wall of the polymerization vessel was scraped off with a spatula and weighed with a balance. The measured value was multiplied by 100 to determine the scale adhesion amount per 1 m ² .

(C) Measurement of Fish Eye 100 parts by weight of polymer, 50 parts by weight of dioctyl phthalate (DOP), 1 part by weight of dibutyltin dilaurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of titanium oxide and 0.05 part by weight of carbon black. The mixture prepared in the mixing ratio was kneaded with a 6-inch roll at 150 ° C for 7 minutes, and then formed into a sheet with a thickness of 0.2 mm. The number of fish eyes contained in 100 cm ^{2 of the} obtained sheet was measured by the light transmission method. Investigated by.

(D) Measurement of lightness index (L value) 100 parts by weight of the obtained polymer, a stabilizer (TS, manufactured by Akishima Chemical Co., Ltd., TS
-101) 1 part by weight, stabilizer (C-100J, manufactured by Katsuta Kako Co., Ltd.) 0.5
Parts by weight and 50 parts by weight of DOP as a plasticizer are kneaded using a two-roll mill at 160 ° C. for 5 minutes and then formed into a sheet having a thickness of 1 mm. 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. For this sample,
The brightness index L in the color difference formula of the hunter described in JIS Z 8730 (1930) is calculated, and the larger the L value, the higher the whiteness, that is,
It was evaluated that the initial coloring was low. The L value is obtained as follows. Standard light C, photoelectric colorimeter (manufactured by Sanbon Denshoku Industries Co., Ltd., Z-1001 DP colorimetric color difference meter) according to JIS Z 8722
Using the stimulus value direct reading method, the stimulus value Y in the XYZ color system
Ask for. The geometric conditions for illumination and light reception are JIS
The condition c described in Section 4.3.1 of Z 8722 was adopted. From the obtained stimulation value Y, the formula described in JIS Z 8730 (1980): L = 10
The L value is calculated from Y ^1/2 .

[0168]

[Table 1]

[0169]

[Table 2]

[0170]

[Table 3]

[0171]

EFFECTS OF THE INVENTION According to the production method of the present invention, it is possible to effectively prevent the adhesion of polymer scale not only in the liquid phase part in the polymerization vessel but also in the gas-liquid interface part, and to obtain high quality with very little initial coloring The vinyl chloride polymer can be produced. Also,
As a result of effectively preventing the adhesion of polymer scale, the cooling capacity of the polymerization vessel can be maintained satisfactorily and stably, there is no risk that the scale will be mixed into the product, and the occurrence of fisheye is small, so the product polymer Quality is improved.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a polymerization apparatus used in Examples for carrying out the method of the present invention.

[Description of sign]

 1 Polymerizer 5 Raw Material Preparation Line 6 Exhaust and Monomer Recovery Line 10 Vacuum Pump 11 Gas Holder

Claims (3)

[Claims] 1. A method for producing a vinyl chloride-based polymer, which comprises repeating a batch of polymerizing a vinyl chloride monomer or a vinyl-based monomer mixture containing a vinyl chloride monomer as a main component in a polymerization vessel, comprising: ) A step of subjecting the reaction mixture containing the monomer or the monomer mixture in an aqueous medium to a polymerization reaction in a polymerization vessel in which a polymer scale anti-adhesive coating film is formed on at least the inner wall surface, (B) occurs. A step of extracting the polymer slurry from the polymerization vessel, (C) a step of applying a polymer scale anti-adhesion agent liquid on the inner wall surface of the polymerization vessel, and drying to form a polymer scale anti-adhesion coating film, (D) In the method for producing a vinyl chloride polymer, which comprises the steps of charging raw materials necessary for polymerization in a polymerization vessel, and then repeating the above steps (A) to (D) in the same manner, (1) Through the step (A) Control the chloride ion concentration in the reaction mixture below 50 ppm. And (2) the above process
A method for producing a vinyl chloride polymer, wherein (B) and step (C) are performed in a state where the inside of the polymerization vessel is shielded from the atmosphere outside the vessel. 2. The method according to claim 1, wherein the polymer scale anti-adhesion agent contains a compound having 5 or more conjugated π bonds and having a molecular weight of 500 or more. 3. The polymer scale adhesion preventing agent further contains at least one selected from the group consisting of inorganic colloids and alkali metal silicates.
The method described in.