JPH09235304A - Polymerization of vinyl chloride-based monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To extremely effectively prevent the adherence of a polymer in a polymerization tank and carry out polymerization enabling closed polymerization by using a reaction product obtained by carrying out oxidation polymerization of a phenolic monomer as a coating liquid. SOLUTION: A coating solution containing a reaction product obtained by subjecting a phenolic monomer (e.g. bisphenol A) of the formula [U, V, X and Y are each H, an alkyl, an alkoxy, an aryl or phenylalkyl; Z is CO or (R<1> )C(R<2> ) [R<1> and R<2> are each H or a 1-5C alkyl] to oxidation polymerization, preferably oxidation polymerization by enzyme is applied to the surface of inner wall of a polymerization apparatus to form a coating film, and then, polymerization of vinyl chloride monomer or copolymerization of the monomer with a monomer capable of copolymerizing with the monomer is carried out.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved homopolymerization or copolymerization method of vinyl chloride, and more specifically, at the time of polymerization, a method for preventing adhesion of a polymer to an inner wall surface of a polymerization tank or the like which is a polymerization apparatus and a polymer used therefor. Regarding anti-adhesion agent.

[0002]

2. Description of the Related Art When performing vinyl chloride homopolymerization, copolymerization with a monomer copolymerizable therewith or graft polymerization of vinyl chloride (hereinafter simply referred to as "polymerization"), an inner wall of a polymerization tank, a reflux condenser, The polymer adheres to the parts of the equipment that come into contact with the monomer during the polymerization operation, such as stirring blades, baffles and various attached piping connections, so the cooling capacity of the polymerization tank is reduced, or the polymer that once adhered and peeled off is chlorided. There are problems such as mixing in a vinyl homopolymer or copolymer (hereinafter referred to as "product") to lower the quality of the product.

[0003] Therefore, it is customary to clean the inside of the polymerization tank each time after the polymerization is completed, and then polymerize again. However, this requires a great deal of labor and time, and reduces the operation rate of the polymerization tank and increases the product cost. Has brought.

In order to avoid this, a method has been conventionally proposed in which a chemical is applied to the inner wall of the polymerization tank and other parts to prevent the adhesion of the polymer.

[0005] However, although these methods are effective in preventing polymer adhesion, they have various disadvantages such as, for example, slowing down the polymerization rate and deteriorating various physical properties of products, and all of them are satisfactory as industrially used methods. I couldn't do it. In addition, a method which does not adversely affect the polymerization rate and various physical properties of the product has been proposed, but such a method does not have a large effect of preventing polymer adhesion and a long-lasting effect.

For example, a method of applying a self-condensation product of a dihydric or trihydric polyhydric phenol (JP-A-54-7487).
Publication: Corresponding US Patent U.S. Pat. S. P. 4,080,17
3), a method of applying a reaction product of a polycondensation product of a polyhydric phenol and a bleaching agent (JP-A-55-500823), a method of applying a reaction product of thiodiphenol and a bleaching agent (special Table 56-500417: Corresponding U.S. Pat. No. 4,297,320), a method of applying a cocondensate of resorcinol and an aldehyde (Table 57-5).
No. 02169 and No. 57-502170:
Corresponding US Patent U.S. Pat. S. P. 579, 758), but the effect of preventing polymer adhesion is not yet sufficiently effective.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have found that in the polymerization of vinyl chloride monomers, the adhesion of the polymer in a polymerization tank or the like can be extremely reduced without affecting the polymerization rate or various physical properties of the product. An object of the present invention is to make it possible to effectively prevent such a situation, eliminate the need to carry out an operation of removing the adhered polymer every time the polymerization is completed, and achieve a closed polymerization without opening a manhole every polymerization.

In the present invention, the vinyl chloride type monomer means vinyl chloride monomer alone, or a mixture of vinyl chloride and at least one monomer copolymerizable with vinyl chloride or graft-copolymerizable with the polymer.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and have reached the present invention.

That is, according to the present invention, when a vinyl chloride monomer alone or a monomer copolymerizable with the vinyl chloride monomer is (co) polymerized, the inner wall of the polymerization apparatus with which the monomer comes into contact is A method of polymerizing a vinyl chloride monomer by a method of applying a coating liquid in advance to prevent the scale from adhering to the inner wall, and a phenolic monomer represented by the following general formula (1) Reaction product of oxidative polymerization of

[0011]

Embedded image (However, in the above general formula (1), U, V, X, and Y are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a phenylalkyl group, and Z is -CO-,-.
^{(R 1) C (R 2} ) -, - O -, - OR 3 -, - R 4 O-,
-R ⁵ -, or -C (R ⁶⁾ - is represented by. R ¹ , R
² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be linear or branched. R ³ and R ⁴ are
It represents an alkylene group having 1 to 5 carbon atoms which may be linear or branched. R ⁵ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R
⁶ represents a saturated aliphatic ring group having 3 to 6 carbon atoms. The present invention provides a method for polymerizing a vinyl chloride-based monomer, which comprises applying a coating solution containing a) to the inner wall surface to form a coating film.

Another object of the present invention is to provide a method for polymerizing the vinyl chloride-based monomer, which uses a reaction product obtained by using enzymatic oxidative polymerization in the oxidative polymerization.

Another object of the present invention is to provide a polymer anti-adhesion agent containing as an active ingredient a reaction product obtained by oxidatively polymerizing a phenolic monomer represented by the general formula (1) (formula 4).

[0014]

Embedded image (However, in the above general formula (1), U, V, X, and Y are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a phenylalkyl group, and Z is -CO-,-.
^{(R 1) C (R 2} ) -, - O -, - OR 3 -, - R 4 O-,
-R ⁵ -, or -C (R ⁶⁾ - is represented by. R ¹ , R
² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be linear or branched. R ³ and R ⁴ are
It represents an alkylene group having 1 to 5 carbon atoms which may be linear or branched. R ⁵ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R
⁶ represents a saturated aliphatic ring group having 3 to 6 carbon atoms. In the present invention, the coating liquid is an aqueous solution of an alkali metal or alkaline earth metal hydroxide of the reaction product, and the reaction product in the aqueous solution of the alkali metal or alkaline earth metal hydroxide. Concentration is 0.1-1
0.0 wt% and the concentration of alkali metal hydroxide or alkaline earth metal hydroxide is 0.05 to 5.0 wt%
To provide the above method using.

The present invention also provides the above method, wherein the coating liquid is a solution of the reaction product in an organic solvent.

The present invention also provides the above method, wherein the concentration of the reaction product in the organic solvent solution is 0.03 to 3.0 wt%.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention is a method of applying a coating solution in advance to prevent the produced vinyl chloride-based polymer from adhering to the surface. A reaction product obtained by oxidatively polymerizing the phenolic monomer shown.

[0018]

Embedded image (However, in the above general formula (1), U, V, X, and Y are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a phenylalkyl group, and Z is -CO-,-.
^{(R 1) C (R 2} ) -, - O -, - OR 3 -, - R 4 O-,
-R ⁵ -, or -C (R ⁶⁾ - is represented by. R ¹ , R
² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be linear or branched. R ³ and R ⁴ are
It represents an alkylene group having 1 to 5 carbon atoms which may be linear or branched. R ⁵ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R
⁶ represents a saturated aliphatic ring group having 3 to 6 carbon atoms. Is applied to the surface to form a coating film, which is a method for polymerizing a vinyl chloride-based monomer.

The coating agent used in the method of the present invention is obtained by oxidatively polymerizing a phenolic monomer. In this oxidative polymerization, a phenolic monomer is produced by a dehydration reaction between oxygen and hydrogen in the phenolic monomer. There is no particular limitation as long as the monomer can be polymerized.

A preferred method for producing the reaction product used in the present invention is BIOTECHNOLOGY AND BIOENGINEERIN.
As described in G, Vol. 26, 599 to 603 (1984) and Japanese Patent Publication No. 63-502079, a phenolic monomer is used in a water-organic solvent or in an organic solvent under a peroxidase enzyme catalyst. The method obtained by enzymatic oxidative polymerization by adding peroxide is applied. Oxidative polymerization by the enzyme described above is suitable for obtaining the reaction product of the present invention. In addition, Furukawa: Polymer Synthesis (February 1987,
Also, oxidative coupling polymerization using a copper-based catalyst can be used as described on pages 213 to 215 by Kagaku Dojin.

The method of enzymatic oxidative polymerization will be described below.

The enzymatic oxidative polymerization reaction of the present invention is carried out in water-organic solvent or in an organic solvent. As the organic solvent, a solvent compatible with water is preferable, but a solvent not compatible with water may be used. As the organic solvent compatible with water, methanol, ethanol, dioxane, tetrahydrofuran (T
HF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, acetone and the like. As a solvent that is incompatible with water,
Examples thereof include hexane, chloroform, methyl ethyl ketone, ethyl acetate, butanol, toluene, etc., but are not limited thereto.

The water may be distilled water or a buffer solution. When using a buffer solution, a phosphate buffer solution, an acetate buffer solution, a succinate buffer solution, and the like are preferable in the range of pH 4 to 12, but not limited to these.

The mixing ratio (volume ratio) of water and organic solvent is water:
The organic solvent is preferably 1: 9 to 9: 1, but is not limited thereto.

The enzyme catalyst used in the reaction is a peroxidase enzyme. The most preferable peroxidase enzyme is horseradish peroxidase or soybean peroxidase, but chloroperoxidase, lactoperoxidase or the like may be used.

The amount of the enzyme catalyst used is the phenolic monomer 1
It is 10 mg to 10 g per 00 g.

It is recommended to use a peroxide as an oxidant for the above reaction, and the peroxide is generally, but not limited to, hydrogen peroxide which is inexpensive and easy to handle. The amount of peroxide used is, for example, 0.1 to 2.0 mol per mol of the phenolic monomer in the case of hydrogen peroxide.

As the reaction method, an organic solvent or a solution in which an organic solvent and water are mixed is prepared, and a phenolic monomer and a peroxidase enzyme are dissolved in this solution and stirred. Alternatively, the phenolic monomer is dissolved in an organic solvent, the peroxidase enzyme is dissolved in water, and both solutions are mixed and stirred. The reaction is carried out between 10 and 40 ° C, preferably at room temperature (20 ° C). In addition, a phenolic monomer as a raw material can be added during the reaction.

After completion of the reaction, the reaction product is obtained by filtering the reaction solution. When the reaction product is dissolved in the solvent due to the polarity of the reaction solvent, the reaction product can be easily removed by removing the organic solvent under reduced pressure or adding a poor solvent for the reaction product such as water. Can be precipitated and collected by filtration.

The phenolic monomer used in the reaction may be only one kind or a mixture of two or more kinds.

The phenolic monomer that can be used is not particularly limited as long as it is a compound represented by the general formula (1). For example, bisphenol A (4,4'-dihydroxydiphenyl-2,2-propane), bisphenol F
(2,2'-dihydroxydiphenylmethane, 2,4'-
Dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylmethane), 4,4′-dihydroxydiphenylketone and the like.

In the method of the present invention, a part of the phenolic monomer represented by the general formula (1) is replaced with another phenolic monomer represented by the general formula (2) (formula 6) (less than 50 mol%). It can be used as a mixture with.

[0033]

[Chemical 6] (However, in the general formula (2), P and Q are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
An alkoxy group having a hydrocarbon residue having 1 to 10 carbon atoms,
It is represented by an aryl group having 6 to 20 carbon atoms, a phenylalkyl group having 6 to 20 carbon atoms, a hydroxyl group, and -COOR (R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). ).

The phenolic monomer is not particularly limited as long as it is a compound represented by the general formula (2). For example, phenol: o-cresol, m-cresol, p
Examples thereof include alkylphenols such as ethylphenol and 3,4-xylenol; arylphenols such as p-phenylphenol; polyhydric phenols such as catechol, hydroquinone, resorcin, and pyrogallol.

The molecular weight of the reaction product is 400 to 35,000 in terms of weight average molecular weight, preferably 600 to 1
It is 0,000. The molecular weight can be measured by using GPC. For example, 1 wt% acetic acid-added polymer solution having a polymer concentration of 0.2 wt% THF is used at 40 ° C. to measure phenol, bisphenol A, and Irganox 1076.
(Ciba-Geigy: trade name) and Irganox 10
A phenol compound such as 10 (manufactured by Ciba-Geigy: trade name) can be measured as a standard.

The theoretical basis for preventing polymer adhesion by applying the above-mentioned reaction product to the inner wall of the polymerization tank of vinyl chloride, etc. is not clear, but it is probably located in the side chain of this reaction product. Since the hydroxyl groups are hydrophilic, the wall surface is oil repellent and does not impede the vinyl chloride monomer, and the hydroxyl group has a high radical scavenging effect. It is believed that this is to prevent the polymerization of Further, since the reaction product is considered to be partially three-dimensional, it is difficult to elute in the vinyl chloride polymerization reaction solution, and the polymerization rate does not slow down.

Although the structure of the reaction product obtained by enzymatic oxidative polymerization is not clear, for example, when the phenolic monomer is simple phenol, its structure is represented by the following formula (3) (formula 3) (the structural formula is It is presumed that two kinds of bonds, A and B, exist, and m and n in the formula indicate only the average number of constituents of both structures, which means that they are connected in a block form. It is presumed that the polyphenol structure such as the A part represented by (not shown) mainly has a polyphenylene ether structure such as the B part.

[0038]

Embedded image When the hydroxyl equivalent of the resin actually obtained by the enzymatic oxidative polymerization is measured, assuming that all the reaction products have the structure of the A portion, the calculated hydroxyl equivalent is about 92. The hydroxyl equivalent of the reaction product produced by a similar method was 180. From this, the resin obtained by enzymatic oxidative polymerization is
It is considered to be a compound having a structure in which the parts are mixed, or a mixture of only the A part and the B part. Further, in this case, the OH group in the A portion and the —O— group in the B portion are bonded at the ortho position or the para position.

The structure of the reaction product when the phenolic monomer represented by the general formula (1) of the present invention is used for the enzymatic oxidative polymerization for producing the reaction product as described above is not clear. However, it is considered that both phenol units of the general formula (1) are probably involved in the reaction.

In the present invention, an aqueous solution of alkali metal hydroxide, an aqueous solution of alkaline earth metal hydroxide or an organic solvent solution of the above reaction product is applied to the inner wall of the polymerization tank or the like.

In the case of an aqueous solution of alkali metal hydroxide or alkaline earth metal hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide or the like is used as the alkali metal hydroxide, preferably sodium hydroxide, It is potassium hydroxide and the alkaline earth metal hydroxide is preferably calcium hydroxide. In this case, the coating solution has an alkali metal hydroxide or alkaline earth metal hydroxide concentration of 0.05 to 5.0 wt%, preferably 0.1.
1 to 3.0 wt%, reaction product concentration is 0.1 to 10.0
It is prepared in an alkaline aqueous solution so as to have a wt%, preferably 0.2 to 6.0 wt%. The reaction product has a concentration of 0.
When it is 1 wt% or more, the amount of liquid for application is appropriate and good workability is maintained, and the polymer adhesion preventing effect is good. If the content is 10.0 wt% or less, it can be easily and evenly applied to the wall surface, and the amount of application is appropriate and economical.
Furthermore, since the coating composition is applied at an appropriate concentration, there is no disadvantage that the coating film components are eluted into the reaction system and the product is colored.

When an aqueous solution of the alkali metal hydroxide or the alkaline earth metal hydroxide of the reaction product is used, a water-soluble aqueous solution is added in order to increase the adhesion efficiency of the scale inhibitor to the wall surface of the polymerization tank. You may add an additive. Examples of the additive include humic acid or a derivative thereof described in JP-A-54-85291,
No. 162782, cellulose or cellulose derivatives, alginic acid described in JP-A-55-13708, hemicellulose described in JP-A-55-231235, JP-A-54-3
No. 8844 discloses starch or starch derivatives, or water-soluble compounds such as polyvinyl alcohol and polyvinylpyrrolidone.

When an organic solvent solution of the reaction product is used, any organic solvent may be used as long as it dissolves the reaction product and does not affect the polymerization reaction and the physical properties of the polymer.
For example, tetrahydrofuran, dioxane, methanol, ethanol, acetone, chloroform and mixtures thereof can be preferably used. The reaction product concentration in the organic solvent is preferably 0.03 to 3.0 wt%, more preferably 0.06 to 1.5 wt%. 0.03wt
When the amount is at least%, the required amount of liquid is appropriate and coating can be performed with good workability, and a good polymer adhesion preventing effect can be obtained. Also,
When the amount is 3.0 wt% or less, the coating amount of the coating liquid is appropriate and economical, and there is little possibility of causing disadvantages such as elution of coating film components into the reaction system and coloring of the product.

The method for applying the coating liquid in the present invention to the inner wall of the polymerization tank is not particularly limited, but the coating liquid can be applied by a general method such as brush coating, spraying or rinsing. After application, it is washed with water if necessary. The coating amount as the weight of the normal reaction products may range from 0.005~10g / m ^2, preferably in the range of 0.01-5 g / m ^2. 0.005g /
If it is more than m ² , the thickness of the coating film is appropriate, and a good polymer adhesion preventing effect can be obtained. If it is less than 10 g / m ² , the coating liquid is economical and may adversely affect the quality of the product. It is preferable because it is low. The application of the coating liquid may be carried out before the start of polymerization in each batch, or the polymerization may be carried out by repeating several batches or more in a single application by simply washing with water after each batch.

The method of applying the coating liquid of the present invention is not particularly limited and can be applied by a known method, but the most preferred application method is claims 1 to 3 of Japanese Patent Application No. 501,884 (Republished Patent). , And the same publication No. 9
See pages 5-29.

More specifically, the coating agent is dissolved at the temperature at which the coating liquid is applied to the wall surface of the polymerization tank, and the pH is adjusted so that the coating agent precipitates when heated on the surface of the heated polymerization tank. It is a method of applying the coating liquid. By applying in this way, the coating agent becomes a thin film uniformly and firmly adhered to the wall surface, and an excellent effect of preventing wall adhesion is obtained.

The coating agent component in the above-mentioned coating liquid is deposited when the pH is low and is deposited when the temperature is high. Therefore, the pH of the coating liquid is preferably 0.2 to more than the pH at which the coating agent component is deposited at room temperature.
It is prepared to be higher by 4.0, more preferably 0.3-3.0.

As described above, the coating agent is usually prepared as an aqueous solution of an alkali metal or alkaline earth metal hydroxide. Therefore, the pH is usually adjusted by adding an acid. Examples of acids for adjusting pH include hydrochloric acid, sulfuric acid,
Examples thereof include inorganic acids such as phosphoric acid and nitric acid, and organic acids such as ascorbic acid, acetic acid, citric acid and mercaptopropionic acid.

When the coating liquid of the present invention is applied to the inner wall of the polymerization tank, the wall surface to be applied is 40 ° C. or higher and 10
It is desirable to heat to 0 ° C. The wall temperature is more preferably 45 to 95 ° C, further preferably 50 to 90 ° C.
It is. After the coating agent is applied and deposited, it is preferably washed with water from the viewpoint of product quality.

The present invention is not limited to the homopolymerization of vinyl chloride, but also the copolymerization of vinyl chloride with at least one other radical copolymerizable monomer or the graft copolymerization of vinyl chloride into a polymer capable of being graft-polymerized. Can also be applied to.

Other polymerizable monomers used therein include vinyl acetates such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl laurate and vinyl stearate; olefins such as ethylene, propylene and isobutylene. Alkyl vinyl ethers such as isobutyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether and phenyl vinyl ether, aryl vinyl ethers; halogenated olefins such as vinylidene chloride, vinyl fluoride, propylene chloride and vinyl bromide;
Ethyl acrylate, n-butyl methacrylate, 2-
Acrylic esters and methacrylic esters such as ethylhexyl acrylate, 2-ethylhexyl methacrylate and stearyl methacrylate; acrylic derivatives such as acrylic acid, methacrylic acid and crotonic acid; and other monomers such as acrylonitrile, maleic anhydride and itaconic anhydride. Is exemplified.

As a polymer capable of graft-polymerizing vinyl chloride, an ethylene-vinyl acetate copolymer (EV
A), ethylene-ethyl acrylate copolymer, chlorinated polyethylene, polyurethane, polybutadiene, polybutadiene-styrene-methyl methacrylate (MBS),
Examples thereof include polybutadiene-acrylonitrile- (α-methyl) styrene (ABS), polybutyl acrylate, butyl rubber, polystyrene, styrene-butadiene copolymer, and crosslinked acrylic rubber.

Further, the polymerization method to which the present invention can be applied can be effectively applied to aqueous suspension polymerization of the above-mentioned monomers, aqueous emulsion polymerization and bulk polymerization of the above-mentioned monomers alone without a polymerization medium under the respective ordinary polymerization conditions. . Further, the present invention is
It is also effective under closed polymerization conditions as shown in JP-A-7-233207.

According to the method of the present invention, in the polymerization of vinyl chloride-based monomer, it is possible to very effectively prevent the adhesion of the polymer in the polymerization tank or the like without affecting the polymerization rate and various physical properties of the product. Is possible. Therefore, it is not necessary to carry out the operation of removing the adhered polymer every time the polymerization is completed, so that it is possible to achieve closed polymerization in which manholes are not opened for each polymerization which has recently been performed.

Hereinafter, the present invention will be described more specifically with reference to examples. However, this embodiment is merely illustrative, and the present invention is not limited thereto. In the examples,
Unless otherwise noted, all percentages are percentages by weight.

[0056]

【Example】

Production Example 1 240 ml of phosphate buffer (pH 7.0, phosphate concentration:
0.05M) and 160 ml of methanol in a mixed solution of 20
g (0.088 mol) of bisphenol A and 0.20
g of horseradish peroxidase was dissolved. 1 ml / of 10 ml of 31% hydrogen peroxide at room temperature (about 20 ° C)
The mixture was added dropwise at a rate of hr and stirred. After 12 hours, the reaction solution was filtered to obtain 18 g of the target resin (yield 90%) (molecular weight M
w: 1140). This resin was dissolved in a 1.0 wt% NaOH aqueous solution and adjusted to a solid content concentration of 2.0 wt% to prepare a coating liquid. (PH 12.9).

Production Example 2 The resin obtained in Production Example 1 was dissolved in methanol to adjust the resin concentration to 0.4 wt% to prepare a coating solution.

Production Example 3 240 ml of phosphate buffer (pH 7.0, phosphate concentration:
0.05M) and 160 ml of a mixture of methanol to 1
7.6 g (0.088 mol) bisphenol F and 0.20 g horseradish peroxidase were dissolved. At room temperature (about 20 ° C.), 10 ml of 31% hydrogen peroxide was added dropwise at a rate of 1 ml / hr and stirred. 12 hours later,
The reaction solution was filtered to obtain 15.8 g of the target resin (yield 90%) (molecular weight Mw: 1480). 1.0 wt% of this resin
Dissolved in 10% NaOH aqueous solution, the solid concentration is 2.0 wt%
Was adjusted so that a coating solution was prepared. (PH
13.0).

Production Example 4 The resin obtained in Production Example 3 was dissolved in methanol and adjusted to a resin concentration of 0.4% to prepare a coating solution.

Production Example 5 170 g of resorcin in a 500 ml autoclave
(1.54 mol) was charged, and the internal temperature was 300 ° C with stirring.
The temperature was raised to 1 hour, and the reaction was continued at this temperature for 8 hours. After that, the temperature was lowered, and an aqueous sodium hydroxide solution was charged. The reaction product (resin), which is a self-condensate of resorcin, was used to prepare a coating solution by adjusting to a 1.0 wt% aqueous sodium hydroxide solution containing 2.0 wt% of a resin component. (PH 12.0).

Production Example 6 89.7% by weight of deionized water, 5.0% by weight of the self-condensate of resorcinol obtained in Production Example 5, sodium hydroxide 3.
A solution of 3 wt% and 2.0 wt% of sodium hypochlorite was charged into a 1 liter autoclave and reacted at room temperature with stirring. The reaction product was diluted 100 times with deionized water to prepare a coating solution. (PH 10.0).

Production Example 7 880 g of deionized water, 4,4'-thiodiphenol 10
g and 10 g of sodium hydroxide were charged into a 2 liter autoclave, which was stirred at room temperature with 5.25 wt%.
100 g of an aqueous solution of sodium hypochlorite was slowly added dropwise to obtain a reaction product. (PH 12.0).

Example 1 A vinyl chloride monomer to be charged later such as an inner wall of a stainless steel polymerization tank having an internal volume of 15 liters provided with a stirring blade and a baffle plate, a stirring blade, a baffle plate and various attached pipe connection parts was used. The temperature of the wall surface of the polymerization tank at the time of applying the coating liquid to each contacting portion was set to 30 ° C., and the coating liquid obtained in Production Example 1 was sprayed with a sprayer so that the coating agent became 0.5 g / m ^2. After spraying, water was sprayed to rinse the coating.

4,800 g of deionized water, 1.42 g of di-2-ethylhexylperoxy-di-carbonate and 0.45 g of cumylperoxy neodecanoate were placed in the polymerization tank thus coated. Saponification degree 80m
3.2 g of partially saponified polyvinyl alcohol of ol% was charged, and the internal air was removed by a vacuum pump up to 40 mmHg. Then, charge 3,200 g of vinyl chloride, and add 58
The reaction was continued until the pressure reached 6.5 kg / cm ² -G at ℃.

After the reaction was completed, unreacted monomers were recovered, the slurry was discharged, and the inner wall of the polymerization tank was rinsed with water. Next, a second polymerization was performed in the same manner as described above except that the coating liquid was not applied. After that, the polymerization was similarly repeated up to 7 times.
Then, the weight of the polymer attached to the inner wall of the polymerization tank was examined and found to be 0.3 g / m ² . The slurry of each batch was dehydrated and dried to obtain a product, and various physical properties were measured by the test methods described below. The results are shown in Table 1.

The polymerization time and the physical properties of the resin are the average values for 7 batches. According to the method of the present invention, the amount of adhered polymer was remarkably small, and the adhered polymer could be easily washed away by simple washing with water. There is no delay in the polymerization time, and the resulting product has excellent resin physical properties.

Example 2 A vinyl chloride monomer to be charged later, such as an inner wall of a stainless steel polymerization tank having an internal volume of 15 liters provided with a stirring blade and a baffle plate, a stirring blade, a baffle plate and various attached pipe connecting portions, was used. The coating liquid obtained in Production Example 2 was sprayed onto each contacting portion with a sprayer so that the coating agent would be 0.1 g / m ² , and then methanol was distilled off under reduced pressure.

In the polymerization tank in which the coating film is formed in this way
Deionized water 4,800 g, di-2-ethylhexylpa
-Oxy-dicarbonate 1.42g and cumylpa
-Oxyneodecanoate 0.45g, saponification degree 80mo
Charge 3.2% of partially saponified polyvinyl alcohol,
The internal air was removed by a vacuum pump up to 40 mmHg. I
After curing, charge 3200 g of vinyl chloride and press at 58 ° C.
Is 6.5 kg / cm ^Two-Reaction continued until G was reached.

After completion of the reaction, unreacted monomers were recovered, the slurry was discharged, and the inner wall of the polymerization tank was rinsed with water. Next, a second polymerization was performed in the same manner as described above except that the coating liquid was not applied. Thereafter, the polymerization was similarly repeated up to 10 times continuously. Then, the weight of the polymer attached to the inner wall of the polymerization tank was checked and found to be 0.2 g / m ² . The slurry of each batch was dehydrated and dried to obtain a product, and various physical properties were measured by the test methods described below. The results are shown in Table 1. Here, the polymerization time and the resin properties are average values for 10 batches. According to the method of the present invention, the amount of adhered polymer was remarkably small, and the adhered polymer could be easily washed away by simple washing with water. No delay in polymerization time,
The resin properties of the obtained product are also excellent.

Example 3 The coating solution obtained in Production Example 1 used in Example 1 was replaced with the coating solution obtained in Production Example 3 with citric acid.
In the same manner as in Example 1 except that H was adjusted to 10.4 and the temperature of the wall of the polymerization tank at the time of applying the coating liquid was heated to 60 ° C., including the coating method, the polymerization prescription, and the number of times of polymerization. Polymerization was carried out. The results are shown in Table 1. The amount of polymer adhered was remarkably small at 0.2 g / m ^2, and the adhered polymer could be easily washed away by simple water washing. There is no delay in the reaction time, and the resin properties of the obtained product are excellent.

Example 4 Except that the coating liquid obtained in Production Example 2 used in Example 2 was changed to the coating liquid obtained in Production Example 4,
Polymerization was carried out in the same manner as in Example 2, including the coating method, polymerization recipe, and number of polymerizations. The results are shown in Table 1. The amount of adhering polymer was remarkably small at 0.1 g / m ^2, and all of the adhering polymer could be easily washed off by simple water washing. There is no delay in the reaction time, and the resin properties of the obtained product are excellent.

Comparative Example 1 Polymerization was carried out only for the first time in the same manner as in Example 1 except that the coating liquid was not applied. The results are shown in Table 1. Polymer adhesion amount is 4
It was extremely high at 0.0 g / m ² .

Comparative Example 2 A coating method was used except that the self-condensation liquid of resorcin obtained in Production Example 5 was used as the coating liquid in the method of Example 1.
Polymerization was carried out in the same manner as in Example 1 including the polymerization conditions and the number of times of polymerization. The results are shown in Table 1. According to the results shown in Table 1, the amount of attached polymer was as large as 6.5 g / m ^2, and the fisheye was also slightly increased.

Comparative Example 3 In the same manner as in Example 1, except that the coating solution was changed to a reaction product solution of the self-condensate of resorcinol obtained in Production Example 6 and sodium hypochlorite, coating method, polymerization conditions, Polymerization was carried out in the same manner as in Example 1 including the number of times of polymerization. The results are shown in Table 1. According to the results shown in Table 1, the amount of attached polymer was as large as 6.3 g / m ^2, and the fisheye was also slightly increased.

Comparative Example 4 The reaction product solution of 4,4′-thiodiphenol and sodium hypochlorite obtained in Production Example 7 was added to the coating solution in the method of Example 1 to adjust the pH to 10 Polymerization was carried out in the same manner as in Example 1, except for the coating method, the polymerization conditions, and the number of times of polymerization, except that the content was adjusted to 0.5. The results are shown in Table 1. According to the results in Table 1, the amount of polymer attached is 3
It was as high as 8.5 g / m ^2, and fisheye increased considerably.

Test Method The test and measurement methods in the above Examples and Comparative Examples were as follows. Average degree of polymerization: According to JIS K-6721. Apparent specific gravity: According to JIS.K-6721. Fish eye: A sheet prepared by kneading a mixture of a predetermined amount of PVC plasticizer, heat stabilizer and the like at 150 ° C for 5 minutes. After that, fish eyes existing in an area of 10 cm × 10 cm were measured by a conventional method. Porosity: By mercury injection method.

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[Table 1]

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The method of the present invention makes it possible to extremely effectively prevent polymer adhesion in a polymerization tank or the like without affecting the polymerization rate and various physical properties of products. Therefore, since it is not necessary to carry out the operation of removing the adhered polymer every time the polymerization is completed, it is possible to achieve closed polymerization without opening manholes each time the polymerization is performed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nao Maeda 2-1, Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemical Co., Ltd. (72) Yuzo Ono 2-chome, Tango-dori, Minami-ku, Nagoya, Aichi No. 1 Mitsui Toatsu Chemicals, Inc.

Claims (8)

[Claims] 1. When (co) polymerizing a vinyl chloride monomer alone or a monomer copolymerizable with the vinyl chloride monomer,
In the method of polymerizing a vinyl chloride-based monomer by a method of applying a coating solution in advance to the inner wall of a polymerization apparatus with which the monomer is in contact and preventing the scale from adhering to the inner wall, the following general formula (1) ( Reaction product obtained by oxidatively polymerizing the phenolic monomer shown in Chemical formula 1 (However, in the above general formula (1), U, V, X, and Y are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a phenylalkyl group, and Z is -CO-,-.
^{(R 1) C (R 2} ) -, - O -, - OR 3 -, - R 4 O-,
-R ⁵ -, or -C (R ⁶⁾ - is represented by. R ¹ , R
² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be linear or branched. R ³ and R ⁴ are
It represents an alkylene group having 1 to 5 carbon atoms which may be linear or branched. R ⁵ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R
⁶ represents a saturated aliphatic ring group having 3 to 6 carbon atoms. A method for polymerizing a vinyl chloride-based monomer, which comprises applying a coating solution containing a) to the inner wall surface to form a coating film. 2. The oxidative polymerization is enzymatic oxidative polymerization.
The described method. 3. A polymer anti-adhesive agent containing a reaction product obtained by oxidatively polymerizing a phenolic monomer represented by the general formula (1) (Chemical formula 2) as an active ingredient. Embedded image (However, in the above general formula (1), U, V, X, and Y are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a phenylalkyl group, and Z is -CO-,-.
^{(R 1) C (R 2} ) -, - O -, - OR 3 -, - R 4 O-,
-R ⁵ -, or -C (R ⁶⁾ - is represented by. R ¹ , R
² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be linear or branched. R ³ and R ⁴ are
It represents an alkylene group having 1 to 5 carbon atoms which may be linear or branched. R ⁵ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R
⁶ represents a saturated aliphatic ring group having 3 to 6 carbon atoms. ) 4. The oxidative polymerization is enzymatic oxidative polymerization.
The polymer adhesion preventive agent described. 5. The method according to claim 1, wherein the coating liquid is an aqueous solution of an alkali metal or alkaline earth metal hydroxide of the reaction product. 6. The concentration of the reaction product in the aqueous alkali metal or alkaline earth metal hydroxide solution is from 0.1 to 10.
The method according to claim 5, wherein the concentration of the alkali metal hydroxide or the alkaline earth metal hydroxide is 0 wt% and the concentration is 0.05 to 5.0 wt%. 7. The method according to claim 1, wherein the coating liquid is a solution of the reaction product in an organic solvent. 8. The method according to claim 7, wherein the concentration of the reaction product in the organic solvent solution is 0.03 to 3.0 wt%.