JP2001040003A - Method for producing polymer of monomer having ethylenic double bond - Google Patents

Abstract

(57) [Problem] To improve the polymerization method of a monomer having an ethylenic double bond, shorten the time for forming a coating film such as a scale inhibitor, improve productivity, and prevent adhesion of polymer scale. Improves effectiveness and enhances the quality of the resulting polymer product. A monomer having an ethylenic double bond is polymerized in a polymerization vessel having a coating film for preventing adhesion of polymer scale on an inner wall surface or other surfaces. The coating film is applied using steam as a carrier with a coating solution containing a nitrogen-containing polymer compound and a tannin-based compound, or a first coating solution containing a nitrogen-containing polymer compound and a tannin-based compound. It is formed by applying the two coating solutions using steam as a carrier. Thus, a method for producing a polymer from a monomer having an ethylenic double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a polymer by polymerizing a monomer having an ethylenic double bond in a polymerization vessel. The present invention relates to a method for producing a polymer which can prevent the production of a polymer having good quality.

[0002]

2. Description of the Related Art In a method for producing a polymer by polymerizing a monomer in a polymerization vessel, it is known that the polymer adheres as a scale to the inner wall surface of the polymerization vessel. When the polymer scale adheres to the inner wall of the polymerization vessel, the yield of the polymer decreases, the cooling capacity in the polymerization vessel decreases, and the adhered polymer scale peels off and mixes into the polymer product, resulting in product quality. This leads to disadvantages such as a large amount of labor and time required for removing the polymer scale. Moreover,
Because the polymer scale contains unreacted monomers, workers may be exposed to it and cause physical injury.

[0003] Therefore, in the polymerization of a monomer having an ethylenic double bond, for example, the polymer is attached to the inner wall of the polymerization vessel and a stirrer in order to prevent adhesion of the polymer scale to the inner wall of the polymerization vessel. Various methods are known for forming a coating film by applying a scale adhesion inhibitor (hereinafter referred to as a scale inhibitor) in a one-step coating operation (hereinafter referred to as a one-component coating method). Specifically, for example, polar organic compounds such as amine compounds, quinone compounds and aldehyde compounds, or dyes and pigments
45-30343, JP-B-45-30835); a polar organic compound or dye treated with a metal salt (JP-B-52-24953);
Mixture of electron donating compound and electron accepting compound (JP-B-53-28347); condensation reaction product of 1-naphthol with formaldehyde (JP-A-57-164107); condensation reaction product of phenol compound and formaldehyde (Japanese Patent 57
−192413); polyaromatic amines (JP-B-59-16561);
Self-condensation product of polyhydric phenol or self-condensation product of polyhydric naphthol (JP-A-54-7487); condensation reaction product of ketone resin and phenol compound (JP-A-62-236804);
Condensation reaction product of aromatic amine and aromatic nitro compound and its base (JP-B-60-30681); Condensation reaction product of aromatic amine compound and quinone compound 7309).

[0004] In the polymerization scale adhesion-preventing coating film obtained by this one-component coating method, scale easily adheres to the vicinity of the gas-liquid interface in the polymerization vessel during polymerization, or depending on the composition of the polymerization reaction solution, the scale may be formed on the entire wall surface. To prevent this, the coating solution of the scale inhibitor to prevent this,
Water-soluble polymer compounds such as anionic polymer compounds, amphoteric polymer compounds, cationic polymer compounds, and hydroxyl group-containing polymer compounds; inorganic colloids; and monomers such as inorganic salts such as alkali metal salts. It is also known to mix a substance having no affinity (hereinafter referred to as an anti-scale agent). These one-part coating methods involve the polymerization of a monomer having an ethylenic double bond in a polymerization vessel,
Effective for preventing polymer scale adhesion.

[0005] In the one-component coating method, when the effect of preventing adhesion of the polymer scale cannot be sufficiently obtained, (a) a coating solution containing the above-described scale inhibitor is applied to form a first layer; Furthermore, two types of coating liquids are applied in two steps of forming a second layer by applying a coating liquid containing the above-mentioned polymer scale adhesion preventing aid (b) to form a coating film thereon. (Hereinafter referred to as a two-liquid two-stage coating method)
03-74404, JP-A-02-80403, JP-A-02-80402, JP-A-02-80401, and JP-A-02-47102) have been proposed.

[0006] The above-described method for preventing adhesion of polymer scale by one-liquid coating and the method for preventing adhesion of polymer scale by two-liquid two-step coating are applied from the viewpoint of productivity such as workability. Spray coating methods are commonly used.

[0007] The formation of the coating film in the one-part coating method of the scale inhibitor by the spray coating method is as follows: Step 1: drying the coated surface to form a dry coating film; Step 3: washing the formed coating surface to remove excess coating liquid; 3 is provided.

[0008] The two-liquid two-stage coating method comprising the application of a scale inhibitor and the application of a scale-preventing auxiliary agent by the spray coating method also comprises the same steps 1 to 3 in the second-stage coating. A film forming operation is performed.

When the above-mentioned spray coating method is used, the surface of the baffle and the stirring blade facing the inner wall surface of the polymerization vessel has a blind spot when viewed from the spray nozzle. Since the coating liquid hardly reaches the surface of the shaded or hidden portion when viewed from such a spray nozzle, the scale inhibitor cannot be applied similarly to other non-shaded surfaces. Therefore, it is difficult to form a uniform coating film on the shaded surface and the non-shaded surface. Further, in order to prevent the scale from adhering to the surface to be shaded, if an effective amount of a coating film is to be formed, a coating solution containing a larger amount of a scale inhibitor than other surfaces must be used. Unnecessary excess scale inhibitor will be applied to non-shading surfaces. Therefore, the coating film thus formed had coating unevenness, and the coating film was partially thicker than necessary.

Further, formation of a scale-preventive coating film by using a spray coating method has the following problems. A coating of the scale inhibitor is usually formed before each polymerization batch. Since the scale inhibitor is generally colored, if the number of repetitions of the polymerization batch increases, the scale inhibitor may be repeatedly applied, resulting in a thick portion of the coating film. Such a thick portion of the coating film is peeled and taken into the reaction mixture, or a scale inhibitor is applied on the polymer scale already formed on the inner wall of the polymerization vessel and peeled off together with a part of the scale. There is a disadvantage that it is mixed into the obtained polymer product and causes colored foreign matters or fish eyes in the molded product, and the quality of the product is deteriorated such as increasing initial coloring of the molded product. As described above, the polymer scale adhesion prevention effect on the hidden part or the shaded surface in the polymerization vessel that is blind spot from the viewpoint of the spray nozzle is considerably larger than the other surface. It is not enough to apply the inhibitor. The spray coating method requires a drying step of drying the coated surface after coating, and it takes a long time to form a coating film of the scale inhibitor. Therefore, from the viewpoint of improving productivity, it is desired to reduce the time required for forming the coating film.

As a method for solving the above drawbacks of the spray coating method, there has been proposed a method of applying a coating solution of a scale inhibitor using steam as a carrier (hereinafter referred to as steam coating) (Japanese Patent Publication No. 01-5044). . As the coating liquid in this case, a coating liquid containing a scale preventing agent alone or a coating liquid obtained by adding the above-described scale preventing auxiliary to the coating liquid is used.

This steam coating method has the following advantages. With a small amount of coating solution, the scale inhibitor necessary for effectively preventing the adhesion of scale can be formed as a thin uniform coating film. A small amount of coating solution used, a scale inhibitor required to obtain a scale adhesion prevention effect even in hidden or shaded areas in the polymerization vessel that are blind spots when viewed from the spray nozzle. Thus, the effect of preventing adhesion of the polymer scale can be obtained even in these portions. The drying step in the coating film forming step becomes unnecessary, and the time required for forming a coating film such as a scale inhibitor is reduced.

By the way, in the steam coating method, the coating solution is mixed with the steam, and the coating solution is applied to the inner wall surface of the polymerization vessel in a form carried by the steam. Therefore, the concentration of the scale inhibitor in the coating liquid is set in consideration of dilution with water vapor. Usually, the concentration of the scale inhibitor in the coating solution is 4 to 40 times that for the steam application than for the spray application. However, the amount of the scale inhibitor required for the steam application is almost the same as that for the spray application.

Although the steam coating method has the above advantages, it has the following problems. Although water vapor coating enables uniform coating in the polymerization vessel, the effect of preventing scale adhesion near the gas-liquid interface in the polymerization vessel is insufficient. Since the effect of preventing scale adhesion near the gas-liquid interface in the polymerization vessel is insufficient, polymer scale deposits grow near the gas-liquid interface when the number of repetitions of the polymerization batch increases, and the deposited scale peels off during polymerization. And it may be mixed into the polymer product to cause fish eyes. Also, as the number of repetitions of the polymerization batch increases, the scale inhibitor is repeatedly applied, and as a result, the scale inhibitor layer gradually becomes thicker, and this layer is partially peeled and mixed into the polymer product to remove colored foreign matter. This causes a problem that the anti-initial coloring property of the polymer product decreases (particularly, the brightness index decreases).

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to shorten the time required for forming a coating film such as a scale inhibitor, thereby improving productivity and improving the effect of preventing adhesion of polymer scale. Reduce the mixing of colored foreign substances into products,
An object of the present invention is to provide a method for producing a polymer by polymerizing a monomer having an ethylenic double bond, which can enhance the fisheye and anti-initial coloring properties of a molded article and improve the quality of the polymer and its processed product.

[0016]

Means for Solving the Problems The present invention provides, as a means for solving the above-mentioned problems, firstly a method for producing a polymer which comprises polymerizing a monomer having an ethylenic double bond in a polymerization vessel. Wherein the polymerization vessel has a polymer scale anti-adhesion coating on its inner wall surface and other surfaces with which the monomer contacts during polymerization; Is formed by applying a coating solution containing a nitrogen-containing polymer compound and a tannin-based compound on the surface of the substrate using steam as a carrier (hereinafter, referred to as "one-steam coating"); A method for producing a polymer from a monomer having an ethylenic double bond is provided.

The present invention also provides, as a means for solving the above problems, a second method for producing a polymer, which comprises polymerizing a monomer having an ethylenic double bond in a polymerization vessel, The polymerization vessel has a polymer scale anti-adhesion coating on its inner wall surface and other surfaces with which the monomer comes into contact during polymerization; the coating film is coated on the inner wall surface and other surfaces. A first coating solution containing a nitrogen-containing polymer compound and a second coating solution containing a tannin-based compound are simultaneously coated on top with steam as a carrier (hereinafter, referred to as “two-stage one-steam coating”). ). A method for producing a polymer from a monomer having an ethylenic double bond.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The anti-scale coating used in the method of the present invention is formed on a surface such as an inner wall of a polymerization vessel. The coating film is composed of a mixture of a nitrogen-containing polymer compound and a tannin-based compound. However, both components may at least partially react to form a reaction product. Thus, more precisely, the coating consists of a mixture of the two components and / or reaction products. It is considered that the scale prevention effect of the present invention is exerted in combination of both components, and it is difficult to determine the contribution of each. [Nitrogen-containing polymer compound] Examples of the nitrogen-containing polymer compound include proteins, nitrogen-containing nonionic polymer compounds, and water-soluble cationic polymer compounds.

The proteins include simple proteins, complex proteins, derived proteins, and alkali metal or ammonium salts such as sodium salts and potassium salts thereof.

Examples of simple proteins include albumins such as ovalbumin, milk albumin, globin and leucosine; globulins such as serum globulin, fibrinogen and glycinin; glutelins such as oryzin, glutenin and hordenine; Prolamins; collagen, elastin,
Examples include hard proteins such as keratin and fibroin; histones such as thymus histone; and protamines such as salmine and clupane.

Examples of complex proteins include nucleoproteins such as nucleohistone and nucleoprotamine, in which a nucleic acid and a simple protein are bound; glycoproteins in which a carbohydrate is bound to a simple protein, such as mucin and mucoid; casein; Phosphoproteins in which a substance containing phosphorus, such as ovoviterin, and a simple protein are bound;
Examples include lipoproteins in which a lipid (lipid) and a simple protein are bound, such as lecittoprotein and tissue fibrinogen. Examples of the derived protein include gelatin and glue.

These proteins can be used alone or in combination of two or more. Preferred among the above-mentioned proteins are gelatin, casein,
These are the alkali metal and ammonium salts of casein, gluten, ovalbumin, and collagen.

As the nitrogen-containing nonionic polymer compound,
For example, polyacrylamide, polyvinylpyrrolidone and the like can be mentioned.

Examples of the water-soluble cationic polymer compound include water-soluble aniline resin, polythiourea, polyethyleneimine, polyvinylpyridine, polyvinylamine, polyallylamine, polyaminesulfone, polyvinylcarbazole, polyvinylimidazoline, polymethylaminoethyl acrylate, Nitrogen-containing polymer electrolytes such as polydimethylaminoethyl methacrylate, N-vinyl-2-pyrrolidone-acrylamide copolymer, cyclized polymer of dimethyldiallylammonium chloride, chitosan, polygalactosamine, and water-soluble chitin. Among the nitrogen-containing polymer compounds, proteins are preferable.

[Tannin compounds] Examples of the tannin compounds include tannic acid, pentaploid tannin, gallic tannin, smack tannin, taratannin, baronia tannin, chestnut tannin, myrobaran tannin, oak tannin, dividivitannin, and Hydrolyzable tannins such as gallo-bila tannins; condensed tannins such as gambian tannins, quebracho tannins, mimosa tannins, mangrove tannins, hemlock tannins, sprutannins, burmaca tannins, oak bark tannins, oyster astringent tannins; No. Among these tannin compounds, tannic acid,
Hydrolyzable tannins such as quintuple tannin, gallic tannin and smack tannin are preferred.

[Coating Solution] In both the case of one-stage steam coating and the case of one-stage steam coating, a coating solution is prepared by dissolving the above-mentioned nitrogen-containing polymer compound and / or tannin-based compound in an appropriate solvent. Is done. As the solvent, for example, water;
Methanol, ethanol, propanol, butanol,
2-butanol, 2-methyl-1-propanol, 2-
Alcohol solvents such as methyl-2-propanol, 3-methyl-1-butanol, 2-methyl-2-butanol and 2-pentanol; acetone, methyl ethyl ketone,
Ketone solvents such as methyl isobutyl ketone; ester solvents such as methyl formate, ethyl formate, methyl acetate, ethyl acetate and methyl acetoacetate; 4-methyldioxolane;
Ether solvents such as ethylene glycol diethyl ether; furans; aprotic solvents such as dimethylformamide, dimethylsulfoxide, acetonitrile, N-methyl-2-pyrrolidone; These may be used alone or in combination of two or more.

Among the above-mentioned solvents, preferred are water and a mixed solvent of water and a hydrophilic organic solvent miscible with water. Among the above organic solvents, examples of the hydrophilic organic solvent include alcohol solvents such as methanol, ethanol, and propanol; ketone solvents such as acetone and methyl ethyl ketone; and ester solvents such as methyl acetate and ethyl acetate. Further, it is preferable to use an alcohol solvent among the above solvents. When using a mixed solvent of a hydrophilic organic solvent and water, the content of the hydrophilic organic solvent is ignited,
It is preferable that the amount is free from dangers such as volatilization and no safety problems such as toxicity. Specifically, the content of the hydrophilic organic solvent is preferably 50% by weight or less, and more preferably 30% by weight.
The following is preferred.

The pH of the coating solution is appropriately selected depending on the type of the compound used. Examples of the pH adjuster include acidic compounds such as hydrochloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, and nitric acid, or alkali metal compounds such as LiOH, NaOH, KOH, Na ₂ CO ₃ , Na ₂ HPO ₄ , and NH ₄ OH, or ammonia. Compounds: Basic compounds such as organic amine compounds such as ethylenediamine, monoethanolamine, diethanolamine and triethanolamine can be used.

[0029] In the case of one-steam coating, the total concentration of the nitrogen-containing polymer compound and the tannin compound in the coating solution is 1.0%.
To 15.0 wt%, more preferably 2.5 to 1 wt%.
0.0 wt%. If the concentration is too low, there arises a problem that an effective amount of a coating film cannot be formed even if the coating amount is increased. If the concentration is too high, the coating solution becomes unstable and precipitates during storage in the storage tank,
The coating liquid line or coating nozzle is blocked by sediment and / or sediment, making it impossible to apply the coating liquid.
This may cause a reduction in the effect of preventing scale adhesion. The mixing ratio of the nitrogen-containing polymer compound and the tannin compound in the coating solution is
Usually, the tannin compound is preferably 1 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of the nitrogen-containing polymer compound.

[0030] In the case of the two-stage steam two-liquid coating, the concentration of the nitrogen-containing polymer compound in the first coating liquid and the concentration of the tannin compound in the second coating liquid are 1.0 to 25.0 wt%, respectively.
Is more preferable, and more preferably, it is 2.5 to 15.0 wt%. In this coating method, the nitrogen-containing compound contained in the first coating liquid and the tannin-based compound contained in the second coating liquid are mixed at the time of coating and applied to the inner wall surface of the polymerization vessel or the like.
The ratio of both compounds mixed at this time is adjusted so that the tannin-based compound is 1 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, based on 100 parts by weight of the nitrogen-containing polymer compound. Is preferred. Generally, steam 2
One-stage liquid coating is more preferable than one-water vapor coating.

[Steam Carrier] The steam used as a carrier with the coating solution may be ordinary saturated steam or superheated steam, and is 2 to 35 kgf / cm ² · G (0.
Those having a pressure of 20 to 3.43 MPa · G) are more preferred.
The temperature of the steam is preferably from 120 to 260 ° C, from 130 to 200 ° C.
C is more preferred.

[Formation of Coating Film] Hereinafter, formation of a coating film by one-step application of steam and two-step application of steam will be described with reference to FIG. FIG. 1 schematically shows the configuration of the polymerization apparatus.

<Steam one-liquid coating> Step 1. (Preheating of inner wall of polymerization vessel by steam) Hot water or the like is passed through jacket 2 attached to polymerization vessel 1 to raise the temperature of the inner wall of the polymerization vessel to 50 ° C. or more (preferably, 50-95
(° C). At the top of this polymerization vessel, a downwardly directed nozzle 3a and an upwardly directed nozzle 3 are formed by an annular pipe.
An application ring 4 having b is provided. The coating ring 4 is connected to a line 5 for supplying water vapor and a coating liquid from outside the polymerization vessel 1. The line 5 is connected to a water vapor supply line 6, a first application liquid supply line 7, and a second application liquid supply line 8 via a valve. If necessary,
Steam (steam or superheated steam) is blown into the vessel from the coating nozzles 3a and 3b of the coating ring 4, and a baffle (not shown) and a stirring blade (not shown) are also heated in advance. In this device, steam is supplied from a steam supply device 9 to a flow meter 1.
It is fed to the application ring 4 via lines 6 and 5 via 0.

Step 2. (One-solution coating) Water vapor is supplied to the coating ring 4 and the first coating solution tank 11
The coating liquid containing the nitrogen-containing polymer compound and the tannin-based compound contained therein is supplied to the coating ring 4 through the lines 7 and 5 by the pump 12 or an aspirator valve (not shown). P is a pressure gauge. The coating liquid is carried by water vapor and applied in a mist state to a surface where the monomer comes into contact during polymerization, such as an inner wall surface of the polymerization vessel, a baffle surface, and a stirring blade surface, and is applied. At the same time as this coating, the coating liquid applied on these surfaces is dried (simultaneous drying) to form a coating film. Therefore, no special operation for drying is required. Mixing ratio of coating liquid (L) and water vapor (G) (L /
G) is preferably 0.005 to 0.8 in terms of weight-based flow ratio,
01-0.2 is more preferred.

Step 3. (Washing) After the supply of water vapor and the coating liquid is stopped, the inside of the polymerization vessel 1 is washed with the washing water stored in the water tank 15. Wash water is supplied by a pump 16 via a line 17 from a nozzle 18 into the polymerization vessel. However, if there is little influence on the quality, it is not necessary to wash with water. Dry coating amount of the thus coating film formed is preferably 0.001 to 5 g / m ^2, more preferably from 0.001~2g / m ^2.

<Steam Two-Liquid One-Step Coating> Step 1. The method of preheating the inner wall surface of the polymerization vessel with steam is the same as the above-described one-liquid steam coating method.

Step 2. (two-liquid one-step coating) Water vapor is supplied to the coating ring 4 and the first coating liquid tank 11
The first coating liquid contained therein is supplied to the coating ring 4 via lines 7 and 5 by a pump 12 or an aspirator valve (not shown). Almost at the same time, the second coating liquid contained in the second coating liquid 13 is similarly supplied to the coating ring 4 via the lines 8 and 5 using the pump 14. The first coating liquid and the second coating liquid are carried by water vapor and applied in a mist state to surfaces such as an inner wall surface of a polymerization vessel, a baffle surface, and a stirring blade surface, which are in contact with the monomer during polymerization, and are applied. At the same time as this coating, the mixture of the first coating liquid and the second coating liquid and / or the reaction product applied on these surfaces is dried (simultaneous drying) to form a coating film. Therefore, no special operation for drying is required. The mixing ratio (L / G) of the coating liquid (L) and water vapor (G) is represented by a weight-based flow ratio.
It is preferably from 0.005 to 0.8, more preferably from 0.01 to 0.2. This is preferably the same range for both the first coating liquid and the second coating liquid. It is preferable that the mixing ratio (L1 / L2) of the first coating liquid (L1) and the second coating liquid (L2) is appropriately adjusted according to the respective coating liquid concentrations. Depending on the concentration of both coating solutions, the flow ratio (weight / weight) of L1 / L2 is adjusted so that the weight ratio between the nitrogen-containing polymer compound in the first coating solution and the tannin-based compound in the second coating solution is in the above-mentioned range. 0.1) to 10.0
Is preferably adjusted, and more preferably 0.2 to 5.0. Step 3. (Washing) is the same as the above-described one-water-vapor application method.

[Polymerization] The method of the present invention is applied to polymerization of a monomer having an ethylenically unsaturated double bond. Examples of this monomer include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, and their esters or salts; maleic acid, fumaric acid, and the like. Esters or anhydrides; diene monomers such as butadiene, chloroprene, and isoprene; styrene; acrylonitrile; vinylidene halide; vinyl ether;

As an example in which the method of the present invention is particularly preferably carried out, suspension polymerization or emulsification of a vinyl halide such as vinyl chloride or vinylidene halide, or a monomer mixture composed mainly of these, in an aqueous medium. There is the production of these polymers by polymerization. Further, the coating film formed by the method of the present invention has a high durability even for monomers having a high solubility for conventional coating films such as α-methylstyrene, acrylate, acrylonitrile, and vinyl acetate. Therefore, the production of polymer beads such as polystyrene, polymethacrylate, polyacrylonitrile, latex, and the production of synthetic rubber such as SBR, NBR, CR, IR and IIR (these synthetic rubbers are usually produced by emulsion polymerization) )), And can be suitably carried out for the production of ABS resin.

In the polymerization of one or more of these monomers, irrespective of the type of polymerization, such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, etc., there are also emulsifiers, stabilizers, lubricants, plasticizers, The purpose of preventing scale is effectively achieved even in the presence of any additives such as a pH adjuster and a chain transfer agent. For example, in the case of suspension polymerization or emulsion polymerization of a vinyl monomer, various additives are added to the polymerization system as needed.
Examples of the additives include suspending agents such as partially saponified polyvinyl alcohol and methylcellulose; anionic emulsifiers such as sodium lauryl sulfate; nonionic emulsifiers such as sorbitan monolaurate and polyoxyethylene alkyl ether; tribasic lead sulfate; Calcium phosphate,
Stabilizers such as dibutyltin dilaurate and dioctyltin mercaptide; chain transfer agents such as trichloroethylene and mercaptans; and pH adjusters. According to the method of the present invention, even if such an additive is present in the polymerization system, the adhesion of scale is effectively prevented.

Further, the remarkable effect of preventing the adhesion of the polymer scale of the present invention is exhibited regardless of the type of the polymerization catalyst, regardless of the type of the polymerization catalyst. Specific examples of the catalyst include t-butyl peroxy neodecanoate, bis (2-ethylhexyl) peroxy dicarbonate, 3,5,5-trimethylhexanoyl peroxide, α-cumyl peroxy neodecanoate Ethate, cumene hydroperoxide, cyclohexanone peroxide, t-butylperoxypivalate, bis (2-ethoxyethyl) peroxydicarbonate, benzoyl peroxide, diisopropylbenzene hydroperoxide, lauroyl peroxide, 2,4-di Chlorbenzoyl peroxide, diisopropyl peroxydicarbonate, α, α′-azobisisobutyronitrile, α, α′-azobis-2,4-dimethylvaleronitrile, di-2-ethylhexyl diperoxyisophthalate, Sulfuric acid Potassium, ammonium persulfate, and the like.

Other conditions for the polymerization may be the same as those conventionally performed, and are not particularly limited as long as the effects of the present invention are not impaired. Hereinafter, typical polymerization conditions will be specifically described with examples of suspension polymerization, solution polymerization, and bulk polymerization as examples.
There is no limitation to this. In the case of suspension polymerization, first, water and a dispersant are charged into a polymerization vessel, and then a polymerization initiator is charged. Next, the inside of the polymerization vessel was evacuated to -759.9 ~
After reducing the pressure to 0.0 mmHg · G (-101.29 to 0.0 kPa · G), the monomer is charged (at this time, the internal pressure of the polymerization vessel is usually 0.5 to 30 k
gf / cm ² · G (0.049 to 2.942 MPa · G)], then 3
Polymerizes at a reaction temperature of 0-150 ° C. During polymerization, one or more of water, a dispersant, and a polymerization initiator are added as necessary. Further, the reaction temperature during the polymerization differs depending on the type of the monomer to be polymerized.For example, in the case of vinyl chloride polymerization, the reaction temperature is 30 to 80 ° C, and in the case of styrene polymerization, it is 50 to 80 ° C.
The polymerization is carried out at 150 ° C. For polymerization, the internal pressure of the polymerization vessel is 0 to 7 kgf / cm ²
When the temperature drops to G (0 to 0.687 MPa · G), or when the difference between the inlet temperature and the outlet temperature of the cooling water flowing into and out of the jacket provided on the outer periphery of the polymerization vessel is almost eliminated (that is, the polymerization reaction) Is determined to be completed when the heat generation due to is stopped). Water, dispersant and initiator charged during polymerization are usually 100 parts by weight of monomer, and 20 to 500 parts by weight of water, dispersant and initiator are usually 100 parts by weight of monomer. 20 to 500 parts by weight of water, 0.01 to 30 parts by weight of a dispersant, and 0.01 to 5 parts by weight of a polymerization initiator.

In the case of solution polymerization, an organic solvent such as toluene, xylene and pyridine is used as a polymerization medium instead of water. A dispersant is used as needed.
Other polymerization conditions are generally the same as the polymerization conditions for suspension polymerization.

In the case of bulk polymerization, about -759.9
After evacuating to a pressure of about 0.0 mmHg (-101.29 to 0.0 kPa · G), a monomer and a polymerization initiator are charged into the polymerization vessel, and −
Polymerizes at a reaction temperature of 10-250 ° C. For example, in the case of vinyl chloride polymerization, the polymerization is carried out at 30 to 80 ° C, and in the case of styrene polymerization, the polymerization is carried out at 50 to 150 ° C.

[0045]

(Preparation of coating liquid)

<Preparation of coating liquid No. 101 to 115 for one-liquid coating> Conditions shown in Table 1 [Nitrogen-containing polymer compound (A), tannin compound (B) pH adjuster, weight of (A) / (B)] Ratio, (A) +
(B), a coating solution was prepared using the nitrogen-containing polymer compound, the tannin-based compound, the pH adjuster, and the solvent shown in Table 1. However, the coating liquid No. 102 is a coating liquid prepared at a low concentration for spray coating. The water-soluble polymer compound which is hardly dissolved at room temperature was dissolved by heating the solvent to about 70 ° C.

<First coating liquid for two-liquid one-step coating No. 116 to 13>
Preparation of 2> Conditions shown in Table 2 [Nitrogen-containing polymer compound (A), pH adjuster, concentration of (A), solvent composition, and p
H] the nitrogen-containing polymer compound shown in Table 2 so that
A first coating solution was prepared using a pH adjuster and a solvent. In addition, the nitrogen-containing high molecular compound which is hardly dissolved at room temperature was dissolved by heating the solvent to about 70 ° C.

<Second coating solution for two-stage one-step coating No. 201 to 21>
Preparation of 9> Conditions shown in Table 3 [tannin-based compound (B), pH adjuster, concentration of (B), solvent composition, and p
H], tannin compounds shown in Table 3 and pH
A second coating solution was prepared using a modifier and a solvent. However,
Coating liquid No. 218 is a coating liquid prepared at a low concentration for spray coating.

[0048]

[Table 1] (Note) *: Comparative example

[0049]

[Table 2]

[0050]

[Table 3] (Note) *: Comparative example

Example 1 FIG. 2 schematically shows the structure of a polymerization apparatus. Regarding the polymerization vessel, the same elements as those in FIG. 1 are indicated by the same reference numerals. The following experiment was performed using the polymerization apparatus shown in FIG. In FIG. 2, a SUS 316 L stainless steel polymerization vessel 1 having an internal volume of 2 m ³ is provided with a stirring device 21 having stirring blades 20.
A drive motor (not shown), a heating / cooling jacket 2, a manhole 22, a baffle 23, and other accessory equipment (not shown) normally provided in a polymerization vessel for vinyl chloride polymerization are provided. A line 24 connected to the upper part of the polymerization vessel 1 is a raw material charging line, and as shown in FIG. Line 24c,
A branch line such as the pure water charging line 24d is connected. Valves V1, V2, V3, V4 and V5 are provided at the positions shown in the supply lines 24 and 24a to 24d. A line 2 connected to the upper part of the polymerization vessel 1
Numeral 5 is provided for exhausting the inside of the polymerization vessel 1, collecting monomers, and the like, and is led to a gas holder 27 via a line 26 branched from a line 25. A monomer recovery line 28 is led out of the gas holder 27, and a line 29 led out of the gas holder 27 is connected to a line 25 and used for a pressure equalizing operation described later. These lines 25, 26, 28 and 29 have valves V6, V7, V8, V
9, V10, V11, V12 and V13 are provided. The line 26 branches again into a line 26a provided with a vacuum pump 30 used for exhausting the polymerizer 1, collecting monomers, and the like, and a line 26b not provided with such a pump, and then again. One line is connected to the gas holder 27. Further, a line 31 is connected to an upper portion of the polymerization vessel 1 in order to wash the inside of the polymerization vessel with water. The line 31 is provided with a valve V14 at a position shown in the figure, and a nozzle 32 is provided at a tip guided into the vessel. Further, above the polymerization vessel 1, a first coating liquid supply line 34 and a second coating liquid supply line 35 are connected to the coating liquid supply line 33 as shown in the figures, respectively.
Connected through. Further, a steam supply line 36 is connected to the line 33 via a valve V19.
The coating nozzles 3a, 3
An application ring 4 provided with b is provided. The line 33 is provided with valves V15 and V16 at the positions shown. A line 37 is connected to the bottom of the polymerization vessel 1,
This is divided into a line 38a for guiding a polymer slurry to a blowdown tank and a line 38b for discharging a coating liquid or the like and washing water to a wastewater tank. These lines 38, 3
8a and 38b at the positions shown in the figures respectively.
V21 and V22 are provided. In each experiment, a coating solution was previously applied to the surface of the inner wall of the polymerization vessel or the like by the method described below, and dried if necessary in a polymerization vessel in which a coating film was formed by drying as follows. The polymerization was repeated.

(1) Coating and drying The following a), on the inner wall of the polymerization vessel of the polymerization apparatus shown in FIG.
A coating film is formed by the method of b), c) or d). In addition,
The methods a) and b) are comparative example methods. In the description of each method, it is assumed that all valves are initially closed.

A). One-spray coating and drying Hot water is passed through the jacket 2 to heat the inner wall of the polymerization vessel 1 to a temperature of 70 ° C. (Preheating time in jacket; 10
Minutes) Open valves V17, V16, V15, V20, and V22, and apply 5 L of a coating solution containing a scale inhibitor (shown as “first coating solution” in Table 4) from first coating solution line 34.
Apply for 1.5 minutes at a flow rate of (liter) / min. Valve V17,
V16, V15, V20, V22 are closed and valves V6, V
8, open V13, V9, start the vacuum pump 30, and
The pressure is reduced to mmHg · G (-93.3 kPa · G), and the wet coating film is dried (necessary drying; drying time: 25 minutes) to form a coating film.
Thereafter, the vacuum pump is stopped, and valves V8, V13, V9
Close. Next, the valves V7 and V10 are opened, and the polymerization reactor 1 is opened.
Is made the same as the internal pressure of the gas holder 27. Then, the valves V6, V7, and V10 are closed. Jacket 2
Stop the hot water flow to the system.

B). Two-stage spray two-solution coating and drying In advance, hot water is passed through the jacket 2 to heat the inner wall surface of the polymerization vessel 1 to 70 ° C. (preheating time in the jacket: 10 minutes) ). Valves V17, V16, V15, V20,
V22 is opened and the first coating solution (undercoat) is applied at a flow rate of 5 L / min for 1.5 minutes. Valves V17, V16, V15,
V20, V22 are closed and valves V6, V8, V13, V
9 and start the vacuum pump 30 to -700 mmHg · G (-9
Reduce the pressure to 3.3 kPa · G) and dry the coating solution (needs drying;
Drying time: 25 minutes) to form the first layer. Thereafter, the vacuum pump is stopped, and the valves V8, V13, and V9 are closed. Next, the valves V7 and V10 are opened to make the internal pressure of the polymerization reactor 1 the same as the internal pressure of the gas holder 27. After that, V6, V
7. Close V10. Next, valves V18, V16, V
15, V20 and V22 are opened, and the second coating solution (overcoat) is applied on the first layer at a flow rate of 5 L / min for 1.5 minutes. Close the valves V18, V16, V15, V22, V20, open the valves V6, V8, V13, V9, start the vacuum pump 30, and reduce the pressure to -700 mmHg · G (-93.3 kPa · G),
The coating solution is dried (necessary drying; drying time: 25 minutes) to form a second layer. Thereafter, the vacuum pump is stopped, and the valve V8,
Close V13 and V9. Next, V7 and V10 are opened to make the internal pressure of the polymerization vessel 1 the same as the internal pressure of the gas holder 27. Then, V6, V7, and V10 are closed. The flow of the hot water to the jacket 2 is stopped.

C). One-solution steam application (and simultaneous drying) Hot water is passed through the jacket 2 to heat the inner wall of the polymerization vessel 1 to 70 ° C. (preheating time in the jacket: 10).
Minutes). Open the valves V19, V22, V20, V15 and V16 and apply steam of 4 kgf / cm ^{2 ·} G (0.392 MPa · G) [143 ° C] to 240
After blowing into the polymerization vessel at a flow rate of kg / Hr for 3 minutes and preheating the inside of the vessel, the valve V17 was opened, and the first coating solution containing a scale inhibitor was sprayed with the steam at a flow rate of 0.2 L / min for 2 minutes. Is used as a carrier to apply and simultaneously dry. After that, valves V19, V22, V20, V15, V16,
Close V17. The flow of the hot water to the jacket 2 is stopped.

D). One-step coating of two liquid steam (and simultaneous drying) (1) Coating and drying Hot water is passed through the jacket 2 to heat the inner wall surface of the polymerization vessel 1 to 70 ° C. (Preheating time in the jacket: 10 minutes). Valves V19, V22, V20, V15,
V16 is opened, and steam of 4 kgf / cm ² · G (0.392 MPa · G) [143 ° C] is blown into the polymerization vessel 1 at a flow rate of 240 kg / Hr for 3 minutes. After preheating the inside of the vessel, the valve V17 is opened. , The first coating solution
The valve 18 is opened at a flow rate of 0.2 L / min for 2 minutes, and almost simultaneously with the opening of the valve V17, and the second coating solution is applied at a flow rate of 0.1 L / min for 2 minutes using the steam as a carrier and simultaneously dried. Form a coating. Thereafter, the valves V17 and V18 are closed. After that, the valves V19, V2
2. Close V20, V15 and V16. The flow of the hot water to the jacket 2 is stopped.

(2) First Rinsing in Vessels Valves V14, V20, V22, V6, V7, V10 are opened to rinse the interior of the vessel, and the flushed water is discharged to a waste water tank. The valves V14, V20, V22 are closed. A) above
Alternatively, when the method of b) is used, the washing time is 4 minutes. When the above method c) or d) is used, the washing time is 1 minute.

(3) Charging The valves V1, V2, and V3 are opened, and 200 parts by weight of pure water, 0.022 parts by weight of partially saponified polyvinyl alcohol, and 0.028 parts by weight of hydroxymethyl cellulose are charged into the polymerization vessel 1.
The valves V1, V2, V3, V6, V7, V10 are closed. Next, the valves V1 and V5 are opened, 100 parts by weight of vinyl chloride monomer (VCM) are charged, and the valve V5 is closed.
Next, while stirring the charged raw materials, the valve V4 is opened, 0.03 parts by weight of t-butyl peroxyneodecanate is charged, and the valves V1 and V4 are closed.

(4) Polymerization While stirring the charged raw materials, hot water was passed through the jacket 2 to raise the temperature. When the internal temperature reached 52 ° C., cooling water was passed through the jacket 2 to reduce the internal temperature to 52 ° C. And polymerization was carried out. The polymerization was terminated when the pressure in the vessel dropped to 5 kgf / cm ² · G (0.49 MPa · G). (5) Exhaust gas The valves V6, V8, V12, and V9 are opened, and the exhaust gas is exhausted to the gas holder 27 until the internal pressure becomes substantially atmospheric pressure.
Thereafter, the valves V12, V8, and V9 are closed. Valve V1
1. Open V10 and send the monomer recovered in the gas holder 27 to the VCM recovery process via the line 28, and then close the valves V11 and V10.

(6) Equalization The valves V7 and V10 are opened to make the internal pressure of the polymerization vessel 1 and the internal pressure of the gas holder 27 equal (equalization). (7) Slurry extraction Valves V20 and V21 are opened, and the polymer slurry is extracted from the vessel into a blowdown tank (not shown). The polymer slurry discharged to the blowdown tank is then dehydrated and dried to obtain a vinyl chloride polymer product. (8) Second Vessel Rinsing In the vessel, the valve V14 is opened to rinse the inside of the polymerization vessel 1, and the cleaning water is sent to the blowdown tank. Then the valves V14, V20,
V21, V6, V7 and V10 are closed. During the water washing in this vessel, the temperature of the polymerization vessel wall was passed by passing hot water through the jacket 2.
Keep at 70 ° C.

Table 4 shows the coating solutions used in each experiment and the method of forming the coating film. In each experiment, the operations from the coating and drying (1) to the second washing (8) after the completion of polymerization were regarded as one batch, and the same operation was repeated as many batches as shown in Table 6.

[0062]

[Table 4] (Note) *: Comparative example

<Evaluation> The following items were measured and evaluated in each experiment. The results are shown in Tables 5 to 9. - Table 5 the required time required for formation of the coating film coating film forming time required Examples and Comparative Examples
Shown in ・ Measurement of polymer scale adhesion amount In each experiment, after the final batch, the polymer scale adhesion amount in the liquid phase part in the polymerization vessel, the polymer scale near the interface between the stirring blade and baffle surface and the interface between the gas phase part and the liquid phase part The amount of adhesion was determined by the following method. The scale attached to an area of 10 cm × 10 cm on the surface of the object was scraped off with a spatula as far as the naked eye could confirm, and weighed with a balance. By multiplying the weighed value by 100, the amount of scale attached per 1 m ² was obtained. Tables 6 and 7 show the results.
Shown in

Measurement of Fish Eye In each experiment , the fish eye obtained when the polymer obtained after the final batch was formed into a sheet was measured by the following method. 100 parts by weight of polymer, dioctyl phthalate 50
Parts by weight, 1 part by weight of dibutyltin dilaurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of titanium oxide, and 0.05 part by weight of carbon black at 150 ° C. using a 6-inch roll.
After kneading for 7 minutes, a sheet having a thickness of 0.2 mm was formed.
The number of fish eyes contained per 100 cm ^{2 of the} obtained sheet was examined by a light transmission method. Tables 8 and 9 show the results.
Shown in Measurement of lightness index (L value) In order to evaluate the initial coloring when the polymer was molded into a sheet, the lightness index (L value) was measured by the following method. Tables 8 and 9 show the results. 100 parts by weight of the obtained polymer, 1 part by weight of a dibutyltin laurate-based stabilizer (TS-101, manufactured by Akishima Chemical Co., Ltd.) and a cadmium organic complex-based stabilizer (C-100, manufactured by Katsuta Kako Co., Ltd.)
J) 0.5 parts by weight and dioctyl phthalate as a plasticizer
The mixture of 50 parts by weight was heated to 160 ° C. using a two-roll mill.
After kneading for 5 minutes, a sheet having a thickness of 1 mm was formed. The sheet obtained was placed in a 4 × 4 × 1.5 cm formwork,
A sample for measurement was prepared by applying a pressure of 65 to 70 kgf / cm ² at a temperature of 0 ° C. The lightness index L of this sample was determined as follows.

First, in accordance with JIS Z 8722, using standard light C and a photoelectric colorimeter (Z-1001 DP type colorimetric colorimeter manufactured by Nippon Denshoku Industries Co., Ltd.), XYZ colorimetry was performed by a stimulus value direct reading method. The stimulus value Y of the system was determined. Here, as the geometrical condition of illumination and light reception, condition d described in JIS Z 8722, section 4.3.1 was adopted. Next, the obtained stimulus value Y was substituted into the Hunter's color difference formula: L = 10Y1 ^{/ 2} described in JIS Z 8730 (1980) to calculate the L value. The larger the L value, the higher the whiteness, that is, the better the initial coloring.

Measurement of Colored Particles In each experiment, 100 parts by weight of a polymer obtained after the end of the final batch was used, and as a stabilizer [TVS N-2000, manufactured by Nitto Kasei Co., Ltd.]
E] 2 parts by weight, and dioctyl phthalate 2 as a plasticizer
0 parts by weight of the mixture, after sufficiently kneading, 160mm × 130mm
× 3mm formwork, temperature of 175 ℃, 35kgf / cm ²・ G (3.43MP
A sample for measurement was prepared by press-molding under the pressure of a · G). This sample was visually examined for the number of colored particles. Tables 8 and 9 show the results.

[0067]

[Table 5] (Note) ^{* The} first and second liquids were applied simultaneously.

[0068]

[Table 6] (Note) *: Comparative example

[0069]

[Table 7] (Note) *: Comparative example

[0070]

[Table 8] (Note) *: Comparative example

[0071]

[Table 9]

[0072]

According to the polymerization method of the present invention, the time required for forming a coating film such as a scale inhibitor is shortened to improve the productivity, and when the vinyl chloride monomer is polymerized, the polymerization time in the polymerization vessel is reduced. The adhesion of the polymer scale can be effectively prevented not only on the liquid phase wall surface, but also on the stirring device, the baffle surface facing the wall surface, near the interface between the gas phase and the liquid phase, and the like. For this reason, the quality of the obtained polymer product is improved,
The number of colored particles in the polymer can be significantly reduced as compared with the related art, and a molded product obtained by molding the polymer into a sheet or the like has very few fish eyes and very little initial coloring.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a polymerization apparatus for performing the method of the present invention.

FIG. 2 is a schematic diagram of another polymerization apparatus for performing the method of the present invention.

[Explanation of symbols]

 1. Polymerizer 4. Application ring 6. 6. Steam supply line 7. First coating liquid supply line Second coating liquid supply line 17. Cleaning water supply line 20. Stirrer blade 23. Baffle 24. Raw material supply line 27. Gas holder 31． Cleaning water supply line 34. First coating liquid supply line 35. Second coating liquid supply line 36. Steam supply line

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tatsuya Fujimoto 1 Towada, Kazu-gun, Kashima-gun, Ibaraki Pref. Shin-Etsu Chemical Co., Ltd. No. 1 Towada Shin-Etsu Chemical Co., Ltd. PVC Research Laboratory F-term (reference) 4J011 EB04 EB08 EB09 EB10 EB12 4J100 AB02P AC03P AC04P AE02P AG02P AG04P AJ02P AL01P AL03P AL04P AL34P AM02P AS02P AS03P AS07 FA47

Claims (3)

[Claims] 1. A method for producing a polymer, comprising polymerizing a monomer having an ethylenic double bond in a polymerization vessel, wherein said polymerization vessel has an inner wall surface and said monomer is polymerized during polymerization. A polymer scale adhesion-preventing coating film on the other surface to be contacted; the coating film contains a nitrogen-containing polymer compound and a tannin-based compound on the inner wall surface and other surfaces. A method for producing a polymer from a monomer having an ethylenic double bond, which is formed by applying a coating liquid using steam as a carrier. 2. A method for producing a polymer, comprising polymerizing a monomer having an ethylenic double bond in a polymerization vessel, wherein said polymerization vessel has an inner wall surface and said monomer is polymerized during polymerization. A coating film having a polymer scale anti-adhesion coating on the other surface to be contacted; the coating film comprising a first coating liquid containing a nitrogen-containing polymer compound on the inner wall surface and the other surface. A polymer formed from a monomer having an ethylenic double bond, which is formed by simultaneously applying a second coating solution containing a tannin-based compound and water vapor as a carrier; How to make. 3. The method according to claim 1 or 2, wherein
A method characterized in that the nitrogen-containing polymer compound is a protein.