JPS63156802A - Production of vinyl polymer - Google Patents

Abstract

PURPOSE:To prevent the deposition of polymer scale on the inner wall of a polymerizer, etc., by polymerizing a vinyl monomer in a polymerizer having a coating film produced by applying a coating liquid containing a paint and/or a fluorescent brightener and a boron compound and drying the applied liquid. CONSTITUTION:Inner wall of a polymerizer and the other part of the polymerizer contacting with a monomer during polymerization process are coated with a coating liquid containing (A) one or more components selected from a dye (e.g. C.I. Direct Yellow 26, C.I. Acid Yellow 7, etc.) and a fluorescent brightener (e.g. C.I. Fluorescent Brightening Agent 24) and (B) a boron compound (e.g. boron oxide, metaboric acid, borax, etc.) in an amount of preferably 0.01-5wt% and the applied liquid is dried to form a coating film. A vinyl monomer is polymerized in the polymerizer having the above coating film.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing a vinyl polymer.

[Conventional technology]

Conventionally, known methods for polymerizing vinyl monomers include suspension polymerization, emulsion polymerization, solution polymerization, gas phase polymerization, and bulk polymerization. In some cases, there was also a problem in that polymer scale adhered to the inner walls of the polymerization vessel and other surfaces of the stirring device.

In other words, when vinyl monomers are polymerized using these methods, polymer scale adheres to the inner walls of the polymerization vessel and parts that come into contact with the monomers, such as the stirring device, which reduces the yield of the polymer and the cooling of the polymerization vessel. In addition to reducing capacity, this adhered scale flakes off and mixes into the product, reducing the quality of the product. In addition, in order to remove this attached scale,
Not only does it take a lot of effort and time, but unreacted monomers are adsorbed in this scale, so removing monomers (acrylonitrile, chloride, etc.) has become a very serious problem in recent years. There is also the problem that there is a risk of injury to the human body due to vinyl (vinyl, etc.).

Therefore, in order to prevent this polymer scale from adhering to the inner walls of the polymerization vessel, for example, polar organic compounds such as amine compounds, quinone compounds, and aldehyde compounds, dyes, and pigments are applied to the inner walls of the polymerization vessel and the stirrer. Method (Japanese Patent Publication No. 45-30343, No. 45-30835)
(see Japanese Patent Publication No. 52-2495), a method of applying a polar organic compound or dye treated with a metal salt (Japanese Patent Publication No. 52-2495
3), a method of applying a mixture of an electron-donating compound and an electron-accepting compound (see Japanese Patent Publication No. 53-28347), and the like have been proposed.

Problems to be Solved by the Invention] These scale prevention methods can achieve a remarkable scale prevention effect in suspension polymerization, but in emulsion polymerization, the scale prevention ability is extremely low or almost no effect can be obtained. There are drawbacks.

In addition, when using water-soluble vinyl monomers such as acrylic acid, methacrylic acid, and itaconic acid as monomers,
Even in the case of suspension polymerization, the scale prevention ability is very low or almost ineffective.

Therefore, the present invention provides a method for producing a vinyl polymer that can prevent polymer scale from adhering to the inner wall surface of a polymerization vessel, etc., regardless of the type of polymerization or the type of vinyl monomer. It is about providing.

[Means for solving problems]

The present invention solves the above-mentioned problems of the conventional method by adding (a) a dye selected from dyes and fluorescent brighteners to the inner wall of the polymerization vessel and other parts of the polymerization vessel that come into contact with monomers during polymerization; A vinyl polymer obtained by polymerizing a vinyl monomer in a polymerization vessel having a coating film formed by coating and drying a coating solution containing at least one type of boron compound and (b) a boron compound. The present invention provides a method for manufacturing.

The dye used as component (a) in the present invention is not particularly limited, and examples include direct dyes, acid dyes, basic dyes, mordant dyes, sulfur dyes, vat dyes, disperse dyes, oil-soluble dyes, and reactive dyes. Included. Specific examples of these are as follows.

Direct Dye C,1, Direct Yellow 26.28.39.44.
50.86.88.89.98.100, C,1, Direct Orange 39.51.107, C,1, Dai Ref Trend 79.80.81.83.84.89.2
18, C, 1, Direct Green 37.63, C,
1, Direct Violet 47.51.90.94,
C, 1, Direct Bluff 1.78.86.90.9
8.106.160.194.196.202.225
．． 226.246, C.

1. Direct Brown 1.95.106.170.1
94.211, C, 1, Direct Black 19.3
2.51.75.94.105.106.107.10
8.113.118.146 etc.

Lazy Oji 4 Makeup C, 1, Acid Yellow 7.17.23.25.40
．． 44.72.75.98.99.114.131.1
41, C, L Acid Orange 19.45.74.8
5.95, C, T, acid red 6.32.42.5
2.57.75.80.94.111.114.115
．． 118.119.130.131.133.134.
145,' 168.180.184.194.19
8.217,' 249.303, C,1, Acid Violet 34.47.48, C,1, Acid Blue 15.29.43.45.54.59.80.10
0.102.113.120.130.140.151
．． 154.184.187.229, C,1, Acid Green 7.12.16.20.44.57, C,1
, Acid Brown 39.301, C, 1, Acid Black 1.2.24.2G, 29.31.48.52
．． 63.131, 140, 155, etc.

Ship] 4 [4 Yuzu C, 1, Paysic Yellow 11.14.19.21.
28.33.34.35.36, c, r, Paysic Orange 2.14.15.21.32, C, 1, Paysic Red 13.14.18.22.23.24.29
．． 32.35.36.37.38.39.40,C,1
,Pasic Violet 7.10.15.21.25
．． 26.27, C, 1, Paysic Blue 9.24.5
4.58.60, C,1, Paysic Black 8, etc.

Mordant dye C,1, Mordant Yellow 1.23.59, C,1,
-E-Dant Orange 5, C, L Modern Trend 21
．． 26.63.89, C,1, Mordant Violet 5, C,1, Mordand Blue 1.29.47, C,1
, Mordant Gelin 11, C, 1, % - Dant Blau 7L 14.87, C0■, Mordant Blasok 1.3.
7.9.11.13.17.26.38.54.75.
84 etc.

Shodoku Toryo C,1, Sulfur Red 3.5, C,1 , Sulfur Green 2.
6.11.14, C, 1, Sulfur Brown 7.8.
C,1, Sulfur Yellow 4, C,1, Sulfur Black 1, C,1, Solbilized Sulfur Orange 3, C,I.

Solbilized Sulfur Yellow 2, C,1, Solbilized Sulfur Resod 7, C,1, Solbilized Sulfur Blue-4, C,1, Solbilized Sulfur Green 3, C,1, Solbilized Sulfur Brown 8 etc.

Vat Dye C, 1, Vat Yellow 2.4, Co 0.20.22.2
3, C, 1, Bat Orange 1.2.3.5.13, C
,1, Bunt Red 1.10.13.16.31.52
,C,1,Bat Violet 1.2.13,C,1,
Bat Blue 4.5.6, C, 1, Solbilized Bassoto Blue-6, C1 ■, Bat Blue 14.29.41.
64, C, 1, Bat Green 1, 2.3.8.9.4
3.44, C, 1, Solbilized Hasoto Green 1,
C, 1, Bat Brown 1.3.22.25.39.4
1.44.46, C, 1, Bat Black 9.14.2
5.57 etc.

, fk1Ck sleeve C,1, dispense yellow 1.3.4, C,j, dispense thread 12.80, C8■, dispense blue 27, etc.

Sakopo Toryo C, 1, Solvent Yellow 2.6.14.19.21
．． 33.61, C, 1, Solvent Orange 1.5.6
．． 14.37.44.45, C,1, Turben Trend 1.3.8.23.24.25.27.30.49.8
1.82.83.84,ioo,109.121,C
, 1, Solvent Violet 1.8.13.14.2
1.27, C, 1, Solvent Blue 2.11.12.
25.35.36.55.73, C,1, Tsuruheto Green 1.3, C,1, Solvent Brown 3.5.20
．． 37, C, 1, Solvent Black 3.5.7.22
．． 23.123 etc.

C, 1, Reactive Yellow 1.2.7.17.22
,C,1,Reactive Orange 1.5.7.14,C
,I.

Reactive Red 3.6.12, C11, Reactive Blue 2.4.5.7.15.19, C,1, Reactive Green 7, C,1, Reactive Black 1, etc.

Examples of fluorescent brighteners that can be used as component (a) in the present invention include C,1, Fluorescendo Brightening Agent 24.84.85.91.
162.163.164.167.169.172.1
74.175.176, etc.

Among the dyes and fluorescent brighteners mentioned above, particularly preferred are those used in the Examples below.

Among the dyes and fluorescent brighteners mentioned above, particularly preferred are those used in the Examples below.

The above dyes and fluorescent brighteners can be used alone or in combination of two or more.

Examples of the boron compound used as component (b) in the method of the present invention include boron oxides, various boric acids, and various boric acid salts, and specifically, the following are exemplified.

Boron suboxide, boron oxide, fluoroboric acid, oxyfluoroboric acid, dioxyfluoroboric acid, sodium fluoroborate, potassium fluoroborate, hypoboric acid, metaboric acid, boric acid, perboric acid, lithium borate, borax Boraxox), sodium metaborate, sodium pentaborate, sodium tetraborate, sodium triborate, sodium heborate, potassium metaborate, potassium pentaborate, ammonium tetraborate, rubidium tetraborate, rubidium pentaborate , cesium borate, magnesium metaborate, calcium orthoborate, strontium borate, barium borate, aluminum borate, manganese borate, iron borate, cobalt borate, nitrous borate, copper borate, zinc borate, boron acid lead, sodium perborate,
Potassium perborate, ammonium perborate, calcium perborate.

Among the above boron compounds, particularly preferred are boron oxide, boron suboxide, metaboric acid, boric acid,
Examples include lithium borate, borax, and sodium heborate.

In the coating liquid used in the present invention, (a) component and (b)
The ratio of the components is 5 to 5 parts by weight of the boron compound (B) per 100 parts by weight of the dye and/or fluorescent brightener (A).
A range of 0.00 parts by weight is preferred.

(a) The amount of the component (mouth) based on 100 parts by weight of the component is 5
This is because if the amount is less than 1 part by weight, the effect of using component (b) in combination will be difficult to manifest, and the sustainability of the scale prevention effect will be reduced. Furthermore, if the amount of component (b) exceeds 500 parts by weight,
This is because the effect of using the component (a) in combination is difficult to show, and the quality of the scale inhibitor mixed into the polymer of the product is reduced.

The coating solution is usually prepared by combining components (a) and (b) in the required proportions in a suitable solvent, preferably at a temperature of about 0.005 to 1.
A coating liquid is prepared by dissolving or dispersing it in a concentration of 0% by weight, particularly preferably 0.01 to 5% by weight, and the coating liquid is applied to the inner wall surface of the polymerization vessel and other parts that the monomer comes into contact with during polymerization, such as Apply to the stirring blades and stirring shaft, then heat to room temperature or 100℃.
It is sufficient to dry at a temperature of about °C, and if necessary, wash with water.

The solvent used for preparing the coating solution includes alcohol solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents,
Examples include halogenated hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, water, etc.
The species can be used alone or as a mixed solvent of two or more species.

In addition, the coating film formed by the method of the present invention has a solid content of 0.001 g/rd or more (solid content), particularly in the range of 0.01 to 2 g/m, on the surface where it is formed, such as the inner wall surface of the polymerization vessel. If the amount is less than 0.001 g/m, the sustainability of the scale prevention effect will decrease.

In the present invention, the coating film may be formed for each batch of polymerization, but since the coating film once formed has considerable durability and its scale prevention effect is long-lasting, it is not necessary to form the coating film for each batch. There is no need to do so. Usually, it is sufficient to form one to ten-odd hatches at a time.

Polymerization of vinyl monomers in a polymerization vessel in which a coating film has been previously formed on the inner wall surface of the polymerization vessel as described above is carried out according to a conventional method. That is, for example, water, a vinyl monomer, a polymerization initiator, and other necessary additives such as monomer dispersion aids are charged and polymerized according to a conventional method.

The method of the invention can be carried out by any type of polymerization. That is, scale adhesion can be effectively prevented in any polymerization method including suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, and gas phase polymerization.

The method of the present invention also depends on the material of the polymerization vessel, such as stainless steel or glass lined, the type of vinyl monomer used for polymerization, and the type of various additives added to the polymerization system, which will be described later. Regardless, scale adhesion can be effectively prevented.

The method of the present invention is applied to the homopolymerization or copolymerization of various vinyl monomers, and specific examples of these monomers include vinyl halides such as vinyl chloride, vinyl acetate, vinyl propionate, etc. vinyl esters; acrylic acid, methacrylic acid and their esters; maleic acid or fumaric acid and their esters or anhydrides;
Diene monomers such as butadiene, chloroprene, and isoprene; further examples include styrene, acrylonitrile, vinylidene halide, and vinyl ether.

Specific examples of water-soluble vinyl monomers used in combination with these vinyl monomers include acrylic acid, methacrylic acid, iconic acid, acrylamide, methacrylamide,
Dimethylaminoethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and acrolein.

In the method of the present invention, additives to the polymerization system include, for example, partially saponified polyvinyl alcohol, suspension side such as methyl cellulose; anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dioctyl sulfosuccinate; sorbitan; Nonionic emulsifiers such as monolaurate and polyoxyethylene alkyl ether; Fillers such as calcium carbonate and titanium oxide; Stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, and dioctyltin mercaptide; rice wax and stearin Lubricants such as acids; plasticizers such as DOP and DBP; chain transfer agents such as trichlorethylene and mercaptans; pH regulators;
Diisopropyl peroxydicarbonate, α, α′-
Examples include polymerization catalysts such as azobis-2,4-dimethylvaleronitrile, lauroyl peroxide, potassium persulfate, and cumene hydroperoxide.

[Effect]

The strong scale-preventing action obtained by the method of the present invention is due to the fact that the scale-preventing action originally possessed by the dye and fluorescent whitening agent (a) component and the boron compound (b) component are mutually exclusive by the combination of the two. This is thought to be due to excessive reinforcement.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example-1 In each experiment shown in Table 1, a dye containing a dye and a boron compound having the composition shown in the table was applied to the inner wall of a stainless steel polymerization vessel with an internal volume of 1000β and a portion of the stirrer that came into contact with the monomer. A coating solution was applied, dried at 50° C. for 15 minutes, and then washed with water.

In the polymerization vessel in which the coating film was formed, 400 kg of water,
200 kg of vinyl chloride monomer, 250 g of partially saponified polyvinyl alcohol, 25 g of hydroxypropyl methyl cellulose and 75 g of diisopropyl peroxydicarbonate were charged and polymerized at 57° C. with stirring.

After the polymerization was completed, the amount of scale deposited on the inner wall of the polymerization vessel was examined, and the results shown in Table 1 were obtained. In Experiment No. 1, no coating treatment was performed. In Table 1, the experimental results marked with * are comparative examples.

Example-2 In each experiment shown in Table 2, the internal volume was 100! Coating treatment was carried out in the same manner as in Example 1, except that a coating solution having the composition shown in Table 2 was used on the inner wall of the stainless steel polymerization vessel and the portion of the stirrer that was in contact with the monomer. In the polymerization vessel in which this coating was formed, 23 kg of styrene monomer, 7.5 kg of acrylonitrile monomer, 36 kg of water, 150 g of hydroxyapatite, 1.2 g of sodium lauryl sulfate,
150g of t-dodecyl mercaptan and 150g of lauroyl peroxide were charged, and the internal temperature was brought to 75% while stirring.
Polymerization was carried out at °C for 7 hours.

After the polymerization was completed, the amount of scale attached was examined and the results were as shown in Table 2. In Experiment No. 25, no coating film was formed at all. Experiments marked with * are comparative examples.

Example 3 In each of the experiments shown in Table 3, the coating solution with the composition shown in Table 3 was used on the inner wall of a stainless steel polymerization vessel with an internal volume of 100 mm and the part of the stirrer that came into contact with the monomer. Coating treatment was carried out in the same manner as in Example-1. 40 kg of water and 500 g of sodium oleate were placed in the polymerization vessel in which this coating was formed.
, polybutadiene latex (solid content 45%) 13kg
, styrene monomer 9kg, acrylonitrile monomer 5k
g, 40 g of t-dodecyl mercaptan, 140 g of cumene hydroperoxide were charged, and after raising the internal temperature to 65°C, 200 g of glucose, 2 g of ferrous sulfate, and 100 g of sodium pyrophosphate were charged and polymerized at 65°C for 5 hours with stirring. I did it.

After the polymerization was completed, the amount of scale attached was examined, and the results were as shown in Table 3. On experimental tooth 49, no coating film was formed at all. Experiments marked with * are comparative examples.

〔Effect of the invention〕

According to the method for producing a vinyl polymer of the present invention, scale adhesion to the inner wall surface of a polymerization vessel can be effectively prevented, and therefore a high-quality polymer product can be obtained at a high yield.

This method is effective for any type of polymerization, including suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, or gas phase polymerization, and is especially effective for emulsion polymerization, which has not been able to effectively prevent scale adhesion in the past. Even if it is adopted, it is a great advantage that scale adhesion can be effectively prevented. Furthermore, this method can prevent scale adhesion regardless of the types of vinyl monomers and additives used, and in particular, it can prevent scale adhesion using water-soluble vinyl monomers, which have conventionally been unable to prevent scale adhesion. Another great advantage is that scale adhesion can be effectively prevented even in the case of polymerization of vinyl monomers.

Furthermore, since scale adhesion is prevented regardless of the material of the polymerization vessel, for example, polymerizations that were conventionally carried out in glass-lined polymerization vessels can be carried out in stainless steel polymerization vessels according to the method of the present invention. The industrial advantages are extremely large.

Claims (1)

[Claims] 1) A coating solution containing (a) at least one selected from dyes and fluorescent brighteners and (b) a boron compound is applied to the inner wall of the polymerization vessel and other parts of the polymerization vessel that come into contact with monomers during polymerization. A method for producing a vinyl polymer, which comprises polymerizing a vinyl monomer in a polymerization vessel having a coating film formed by coating and drying the vinyl monomer.