FI58782B - FOERFARANDE FOER SUSPENSIONS- ELLER EMULSIONSPOLYMERISERING AV AV VINYLCHLORID - Google Patents

Description

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Japan-Japan (JP) 50-157 (71) Shin-Etsu Chemical Co., Ltd., 6-1 Otemachi 2-chome-Chiyoda-ku,

Tokyo, Japan-Japan (JP) (72) Shunichi Koyanagi, Niigata-ken, Hajime Kitamura, Niigata-ken,

Toshihide Shimizu, Niigata-ken, Japan-Japan (jP) (7 ^) 0y Kolster Ah (5 * 0 Method for suspension or emulsion polymerization of vinyl chloride -Förfarande för suspensions- eller emulsionspolymerisering av vinyl-chloride

In any known type of polymerization, such as suspension polymerization, emulsion polymerization, solution polymerization, gasase polymerization, and bulk polymerization, the deposition of a polymer layer on the inner wall of the polymerization vessel and other surfaces in contact with the monomer or monomers has been problematic. First, the precipitation of the polymer layer causes a decrease in the yield of the polymer product and a deterioration of the cooling of the polymerization vessel. Second, the release layer from the surfaces may mix with the polymer product, causing its quality to deteriorate. Third, removing the precipitated deposit or peeling the surfaces requires a lot of work and time and causes a decrease in productivity. Finally, a point that has become of considerable importance recently: peeling, which is usually carried out after each polymerization run, can cause health problems for workers due to the unreacted monomer or monomers that may be adsorbed on the casing.

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To prevent the deposition of polymer layers on various surfaces, some methods have been proposed in which these surfaces are coated with polar organic compounds such as amine compounds, quinone compounds and aldehyde compounds, dyes and pigments (see U.S. Patent 3,669,946 and Fi Patent No. 53,826. representative methods have not proven effective in a polymerization process in which vinyl chloride is polymerized in the presence of emulsifiers or in combination with a comonomer or comonomers, or a polymerization mixture containing acyl peroxides such as benzoyl peroxide, lauroyl peroxide and the like, or higher carboxylic acids, carboxylic acids, Also, previous methods could hardly prevent the formation of a deposit at repeated polymerization times.

It is therefore a primary object of the invention to provide a process for polymerizing vinyl chloride or a mixture containing predominantly vinyl chloride, wherein the formation of a polymer layer on the inner wall of the polymerization vessel and other surfaces in contact with the monomer or monomers can be prevented in substantially all types of polymerization.

Another object of the invention is a process for polymerizing vinyl chloride or a monomer mixture containing mainly vinyl chloride so that the productivity of the vinyl polymer can be greatly increased.

Yet another object of the invention is a process for polymerizing vinyl chloride or a monomer mixture containing mainly vinyl chloride so as to easily produce a high quality vinyl polymer.

The process of this invention for polymerizing a vinyl chloride monomer or a mixture of monomers containing predominantly vinyl chloride as a suspension or emulsion in a polymerization reactor in the presence of a polymerization initiator is characterized in that prior to polymerization nitrogen-containing organic compound, sulfur-containing organic compound 58782, oxygen-containing organic compound, phosphorus-containing organic compound, tar, pitch, resin or wax, or with an organic dye such as azo dye, anthraquinone dye, indigo dye, sulfide dye, phthalocyanine dye, diphenylmethane triphenylmethane dye, nitro dye, nitroso dye, thiazole dye, xanthene dye, acridine dye, azine dye, oxazine dye, thiazine dye, benzoquinone dye, naphthoquinone dye or cyanine dye, and (b) at least one of the following a compounds: halides, hydroxides, oxides and carboxylates of metallic elements and oxo acids of elements B, C, N, Al, Si, P, S, Ti, Cr, Mn, Mo and Sn and inorganic salts of these oxo acids.

Examples of the polar organic compounds referred to in (a) above include (1) nitrogen-containing organic compounds monoamino-mononitroazo, EDTA, N-naphthylamine, (2) sulfur-containing organic compounds p-toluenesulfonic acid, (3) oxygen-containing organic compounds R -salt (Na, K-tartrate), (4) phosphoric acid from phosphorus-containing organic compounds, and (5) tars, resins, resins and waxes with a difficult-to-determine chemical structure.

Further examples of organic dyes used as compounds in (a) (Color Index name in parentheses) are the following:

Azo dyes such as monoazo dyes, polyazo dyes, metallic azo dyes, naphthol dyes (azo dyes and inactive dyes) and dispersed azo dyes; anthraquinone dyes such as anthraquinonic acid dyes, anthraquinone dyes, anthrone dyes, alizarine dyes and dispersed anthraquinone dyes; indigo colors such as Brilliant Indigo B (Vat Blue UI), Threne Red Violet RH (Vat Violet 2) and Threne Printing Black B (Vat Black 2); sulphide dyes such as Sulfur Blue FBB (Sulfur Blue 7) and Sulfur Black B (Sulfur Black 1) and Sudan B (Solvent Black 3); xanthene dyes, acridine dyes, azine dyes, oxazine dyes, thiazine dyes, benzoquinone and naphthoquinone dyes and cyanine dyes, water-soluble organic dyes such as Direct Brilliant Yellow G (Direct Yellow 14) * 58782 (direct dye), Acid Light Yellow 2G (Acid Yellow Yellow) ), Levafix Yellow 4G (Reactive Yellow 10) (reaction color), Procion Brilliant Orange G (Reactive Yellow 1) (reaction color), Direct Fast Scarlet GS (Direct Red 4) (direct color), Direct Bordeaux NS (Direct Red 229) (direct color) ), Brilliant Scarlet 3R (Acid Red 18) (acid color), Acid Alizarine Red B (Mordant Red 9) (acid stain / commercial), Direct Turkish Blue GL (Direct Blue 86) (direct color) CibacronBlue 3G (reactive Blue 2) ( color reaction) Blankophor B (Fluorescent Brightening Agent 121) (acid color), Nigrosine (Solvent Black 7) (acid color), Sirius G (Direct Black 74) (direct color), Chrysamine G (Direct Yellow 24) (direct color), Direct Fast Yellow GG (direct color) Yellow 26) (direct color), Chrome Yellow G (Mordant Yellow 1) (acid coating color), Chrome Yellow ME (Mordant Yellow 30) (acid coating color), Eosine G (Acid Red 37) (acid color), Basic Flavin 8G (Basic Yellow 1) (basic color), Astr-azcn Yellow 3G (Basic Yellow 11) (basic color), Rhodamien 6GCP (Basic Red 1) (basic color), Safranine T (Basic Red 2) (basic color), Rhodamine B ( Basic Volet 10) (alkaline color), Daitophor AN (Fluorescent Brightening Agent 172) (alkaline color), Auramine Cone (Basic Yellow 2) (alkaline color), Chrysoidine (Basic Orange 2) (alkaline color) and Bismarck Brown BG (Basic color) Brown 1) (alkaline color).

The above-mentioned polar organic compounds and organic dyes can be used alone or in combination.

Suitable compounds (b) for use in the process of the present invention are, on the other hand, halides, hydroxides and lower carboxylates of metal elements, examples of which include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, aluminum, titanium, tin, iron, chromium molybdenum. , and manganese. Examples of these compounds are sodium acetate. ferric chloride, calcium chloride, sodium tartrate and sodium chloride.

On the other hand, the compounds (b) are oxo acids and / or inorganic salts of the elements B, C, N, Al, Si, P, S, Ti, Cr, Mn, Mo and Sn.

The following are examples of their oxo acids and salts: boric acid, aluminum acid, carbonic acid, silicic acid, tin acid, titanium acid, phosphoric acids (including condensed phosphoric acids such as tripolyphosphoric acid and malic acid), sulfuric acid, chromic acid, moleic acid, molybdic acid, molybdic acid ammonium, alkali metal and alkaline earth metal salts.

In carrying out the process of the present invention, it is preferable to dissolve or disperse the compounds (a) and (b) separately or together in a solvent before use. As the solvent, water, alcohol solvents, ester solvents, ketone solvents, hydrocarbon solvents and chlorinated hydrocarbon solvents are generally used.

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The following is a preferred embodiment of the method 3 according to the invention.

In the first embodiment, compound (a) is dissolved or dispersed in one of the above solvents, and the resulting solution or dispersion is applied to the inner wall surfaces of the polymerization reactor and other parts which come into contact with the monomer or monomers. The coated surfaces are then contacted with compound (b) by placing its solution or dispersion in a reactor and heating the solution or dispersion, preferably at 50-100 ° C for 10 minutes or longer, after which the solution or dispersion is removed from the reactor and the reactor is subjected to conventional polymerization. rointiprosessi. However, when the mixture to be polymerized is aqueous, such as in suspension and emulsion polymerization, and the solvent used to form the solution or dispersion of compound (b) is water, it is not always necessary to remove the heated aqueous solution or dispersion.

Another possibility is that compound (a) is dissolved or dispersed in a suitable solvent, and compound (b) is dissolved or dispersed in the same or different solvent. The solution or dispersion of compound (a) is added dropwise to the solution or dispersion of compound (b), then heated, preferably at 50-100 ° C. The resulting mixture is applied to the surfaces of the inner wall of the polymerization reactor and to other parts of the reactor that come into contact with the monomer or monomers. The surfaces thus coated are washed with water as required. The polymerization is then started by the usual method.

A third way is to prepare separate solutions or dispersions of compounds (a) and (b) in the same or different solvents. The solution or dispersion (a) and the solution or dispersion (b) are applied alternately once or several times to surfaces which come into contact with the monomer or monomers. The surfaces thus coated are heated by passing hot water through the jacket or by blowing hot air into the reactor. It is most preferred to apply the coating solutions or dispersions at an inner wall temperature of about 50-100 ° C by passing hot water through the jacket. It is even more advantageous to carry out the application of the solutions or dispersions by passing hot water through the jacket and at the same time blowing hot air into the reactor every coating after application.

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In all the process embodiments described above, it is preferable to contact the compounds (a) and (b) with each other at an elevated temperature above 50 ° C. At lower temperatures, satisfactory results are not obtained and more than 10 hours of treatment are required.

The ratio of compound (b) to compound (a) used in the process of the present invention may vary depending on the nature of the compounds used and the type of polymerization. In particular, in the first process described above, in which the concentration of compound (b) in the aqueous phase is low, and in the third process, in which compounds (a) and (b) do not mix well with each other, the ratio of compound (b) to compound (a) is preferably relatively high, generally 0.1: 1 to 500: 1 by weight. In another process in which a heated mixture of compound (a) and (b) is applied, the ratio of compound (b) to compound (a) may be relatively small, e.g. 0.01: 1 to 50: 1 by weight.

The amount of the compound (a) and (b) used according to the present invention or the mixture thereof used to coat the surfaces or other parts of the inner wall of the reactor may be approximately the same as the amount of the coating agent used in the conventional prior art method. Adequate prevention of precipitation of the polymer layer can be obtained, for example, in an amount of at least 0.001 g / m 2.

With respect to the three methods described above, it may be added that, of course, any of them may be used not only alone but also in combination. For example, surfaces may be first coated with a solvent mixture of compounds (a) and (b), then heated as in the second method, after which the surfaces so coated are sequentially coated with a solution of compound (a) and a solution of compound (b) and heated as in the third method.

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In addition, two different compounds (a) can be used together, in which case in some cases it is possible to obtain better results by selecting one of the compounds from water-soluble compounds and the other from those soluble in organic solvents.

It is further suitable to add a solution or dispersion of the compound (a) or (b) or a heated solution or dispersion mixture thereof to the polymerizable polymerization mixture in order to obtain better anti-deposition results. In this case, the amount of such addition should be limited to a range of some ppm to 100 ppm with respect to the monomer or monomers, as excessive amounts may potentially adversely affect the resulting polymer product.

In order to further enhance the deposition prevention according to the present invention, it has been proposed to add an alkaline substance to the polymerization mixture which does not meet the definition of compound (b), such as alkali metal, alkaline earth metal and ammonium oxides, hydroxides, carbonates, phosphates, bicarbonates, silicates and acetates. . However, it is important that the amount of alkaline added is such that it does not cause spoilage of the polymer produced. A suitable amount is, for example, up to 1% by weight of the weight of the monomer or monomer mixture.

The process of the present invention can be used for all types of polymerization, i. for suspension polymerization, emulsion polymerization, solution polymerization and bulk polymerization, which are used for vinyl chloride monomers or monomer mixtures containing mainly vinyl chloride. The process also does not place any restrictions on the addition of various additives such as suspending agents, emulsifiers and chain transfer agents, polymerization initiators, nor on the polymerization temperature or mixing rate.

In addition to the homopolymerization of vinyl chloride, the process according to the invention can also be used effectively for the copolymerization of vinyl chloride with a copolymerizable monomer or monomers. Examples of copolymerizable monomers which may be mentioned are vinyl esters, vinyl ethers, acrylic and methacrylic acids and their esters, maleic and fumaric acids and their esters, aromatic vinyl monomers, vinyl halides and vinyl halides, vinyl chloride, methyl aldehydes,

58782

The invention is further illustrated by the following examples:

Example 1 In this example, 2-liter stainless steel autoclaves were used, each equipped with a turbine stirrer. The inner wall surface of each autoclave and the agitator blades were each coated with a 0.1% toluene solution of a different organic dye, as shown in column "Compound A" of Table I, at a rate of about 0.05 g / m 2 (solid), and the coated surfaces were dried at 70 ° C: 60 minutes, after which a 1% aqueous solution of various oxo acids or their salts, as shown in column 2 "Compound B" in the same table, was applied to the coated and dried surfaces in amounts of about 0.05 g / m (solid), and then dried. At 70 ° C for 60 minutes. 900 g of water, 0.4 g of methylcellulose and 0.8 g of polyvinyl alcohol were then placed in each autoclave thus coated. The autoclave was deaerated and refilled with nitrogen, then charged with 600 g of vinyl chloride monomer and 0.21 g of N-azobisdimethylvaleronitrile, and the mixture was subjected to suspension polymerization at a stirring speed of 1,000 rpm. at 57 ° C for 6 hours. The polymerization runs were repeated continuously in each autoclave until the deposition precipitate was more than 1 g / m 2; the number of these repeated polymerization runs is mentioned in Table I in the column "Number of runs". In other words, the number of runs means that the precipitation of the deposit was effectively prevented during these repeated polymerization times. Details and results are shown in Table I.

For comparison purposes, experiments were performed using Compound A or B alone, not together, in the same manner and under the same conditions to give the results shown in the same table.

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Table I

Compound Compound Compound A and B A 3

Compound Compound Test Run Test Run Test Run A B No. Chapter No. Chapter No. No. Chapter

Nigrosine Sodiumr

Black silicate 1 18 13 12 25 2

Spirit Potassium

Black nitrite 212 14 9 262

Oil Boric acid 3 10 15 7 27 1

Black

Threne

Gray K Silicic acid 4 5 16 3 28 2

Aniline Potassium

Black chromate 5 6 17 4 29 1

Alizarine Tripolyfos-

Yellow R formic acid 66 18 2 30 2

Fast Magnesium

Light carbonate 7 4 19 3 31 1

Yellow G

Threne

Golden Tin Acid 8 3 20 2 32 1

Yellow RK

Pyrzolone Sodium

Red molybdate 9 3 21 2 332

Permanent

Orange Titanium Acid 1Q 3 22 2 34 1

GTR

Phthalocy- Permanganic aniline acid 11 2 23 1 35 1

Blue

Naphthol Sodium

Yellow S borate 12 3 24 2 36 1

Huan: Experiments Nos. 13-36 are comparative experiments 10,58782

Example 2

The same autoclaves as in Example 1 were coated with Compounds A and B together as shown in Table II, and for comparison purposes with Compound A or B alone, as seen in the same table, in the same manner and under the same conditions as in Example 1. Each autoclave was charged with 900 g of water. g of sodium lauryl sulfate, 1 g of potassium persulfate and 600 g of vinyl chloride, and emulsion polymerization was performed at 48 ° C for 10 hours. The details and results of these experiments are summarized in the following table.

Table II

The runs

Experiment No. Compound A Compound B Chapter 37 Nigrosine Black Tripolyphosphoric Acid 5

38 Spirit Black Sodium Molybdate 3 I

39 Oil Black Sodium Nitrite 2 40 Nigrosine Black Sodium Silicate 5 41 Spirit Black Boric Acid 3 42 Nigrosine Black - 3 43 Spirit Black - 2 .. Sodium Silicate 44 - 1 45 Sodium Nitrite] 48 Phosphoric Acid 1

Note: Experiments Nos. 42-46 are comparative experiments.

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Example 3

The same autoclaves as in Example 1 were coated with Compounds A and B together as shown in Table III, and in the comparative experiments with Compound A or B alone, as seen in the same table, in the same manner and under the same conditions as in Example I. Each coated autoclave was charged with 900 g of water. 4 g of methylcellulose, 0.8 g of polyvinyl alcohol, 600 g of vinyl chloride, 60 g of comonomer, i.e. vinyl acetate or vinylidene chloride, and 0.21 g of isopropyl peroxydicarbonate, and the suspension polymerization was carried out at 52 ° C for about 6 hours. Details and results of the experiments are shown in Table III.

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Table III

.,. The runs

Test Comonomer Compound A Compound B Chapter ------- * --------- 47 Vinyl Weapon- Nigrosine Black Silicic Acid 8 Taate 48 Oil Black Tripolyphosphoric- 5 Acid 49 «Nigrosine Black Potassium Nitrite 7 50 ** Oil Black Boric acid 4 51 Vinylidene- NigTOSine Black Phosphoric acid 8 chloride 52 Spirit Black Sodium molybdate 5 * * Nigrosine Black Potassium silicate g 54 Vinyl weapon Nigrosine Black - 5 taat 55 Oil Black - '3 56 - Silicic acid 1 5 * 7 “Tripolyphosphoric acid ^ acid 58 'Vinylidee- Nigrosine Black - 5 nichloride 59 "Spirit Black - 3 ♦ 80" —— Sodium molybdate ^ mM — m — mmmwmmmmmmwmmmmmm «Jmmm · w

Note: Experiments No. 5 * 4-60 are comparative experiments 13,58782

Example M ·

The same autoclaves as in Example 1 were coated with a 0.05% solution or dispersion of equal amounts of Compound A and Compound B, but in different combinations, as seen in Table 2; the amount of coating was 0.1 g / m (solid), and the coated surfaces were dried at 70 ° C for 60 minutes. Then, to test the formation of a deposit, the suspension polymerization of vinyl chloride was carried out in the same manner and under the same conditions as in Example 1. Details and results are shown in Table IV.

Table IV

Experiment Run No. Compound A Compound B Chapter 61 Nigrosine Black Sodium Borate 16 62 Spirit Black Potassium Nitrite 12 63 Oil Black Silicic Acid ^ 64 Threne Gray K Boric Acid 5 65 Aniline Black Tripolyphosphoric Acid 6 66 Alizarine Potassium Dichromate 5

Yellow R

67 Yeflow ^ f ^ * Tin acid 3 68 Threne Golden Sodium silicate. 3

Yellow RK

69 Pyrazolone Red Titanium Acid 3 ^ OrSg ^ GTR Permanganic Acid 2 71 Phthalocyanine Phosphoric Acid 4

Blue 72 Naphthol Sodium molybdate 3

Yellow S

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Example 5

The same autoclaves as in Example 1 were coated with a combination of compounds A and B as shown in Table V and under the conditions of Example 4. Each of the coated autoclaves was subjected to a similar emulsion polymerization as in Example 2. The details and results of these experiments are shown in Table V.

Table V

Experiment Run No. Compound A Compound B .. _ Chapter 73 Nigrosine Black Tripolyphosphoric Acid 4 74 Spirit Black I Sodium Mololyte j j> 75 Oil Black Sodium Nitrate 2 76 Nigrosine Black Sodium Silicate 4 77 Spirit Black I Boric Acid I 2 of 58782

Example 6_

The same autoclaves as in Example 1 were coated with a combination of compounds A and B as shown in Table VI and under the conditions of Example 4. Substantially similar suspension polymerization or copolymerization as in Example 3 was performed on each of the coated autoclaves. Details and results of the experiments are shown in Table VI.

Table VI

Koe. 'Run n.Q Compound A Compound B Chapter 78 Nigrosine Black Silicic Acid 7 79 Oil Black Tripolyphosphoric Acid 5 80 Nigrosine Black Potassium Nitrite 7, 81 Oil Black Boric Acid ^ 82 Nigrosine Black Phosphoric Acid ^ 83 Spirit Black Sodium Molybdate 5 84 Nigrosine Black Potassium Silicate ^

Note: Experiments Nos. 78 to 81 concern the homopolymerization of vinyl chloride

Experiments No. 82-84 concern the copolymerization of vinyl chloride and vinylidene chloride.

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Example 7

The same autoclaves as in Example 1 were coated with a solution of Nigrosine Black dye in ethanol or toluene using different amounts as shown in Table VII, the coating was dried at 70 ° C for 60 minutes and then a 1% sodium silicate solution in water was applied to the coated and dried surface in 0.05 g / m 2 (solid), then dried at 70 ° C for 60 minutes. Each coated autoclave was then subjected to suspension polymerization of vinyl chloride to test the formation of a deposit in the same manner and under the same conditions as in Example 1. Details and results are shown in Table VII.

Table VII

-. «Used Nigrosine Experience Black Number of runs?: °. _ K / m2 ___ figure - 85 10 2 86 2 '· 3 87 1 4 88 0,5 5 89 0,05 5 90 0,005 3 91 0, o 005 2 92 0,5 2 93 0,5 6 94 0,01 3

Huorn: 1) The Nigrosine Black solutions used in Experiments No. 85-91 were in ethanol, while those used in Experiments No. 92-94 were in toluene.

2) In Experiment No. 93, the surfaces of Nigrosine Black coatings were lightly wiped after drying with a cotton gauze cloth dipped in ethanol.

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Example 8

The same coating and polymerization procedure as in Experiment No. 88 in Example 7 was repeated except that 5% by weight, 0.1% by weight or 0.0001% by weight of sodium silicate, based on the weight of vinyl chloride, was added to the polymerization mixture before starting the polymerization. The number of polymerization runs during which deposition was prevented was 9, 7 and 5, respectively.

Example 9

The same procedure as in Experiment No. 61 in Example 4 was repeated except that the coated surfaces were further coated with Nigrosine Black dye and sodium silicate in the same manner and under the same conditions as in Experiment 1 of Example 1. The number of runs in which deposition was prevented was 25.

Example 10 In this example, stainless steel polymerization vessels of 1000 lirta were used, each equipped with a melatype mixer with blade diameters of 600 mm. The surfaces of the inner walls of the vessels and the blades and stems of the stirrer were coated with a 0.5% methanol solution containing

Sudan B and Nigrosine dyes in different mixing ratios, as shown in Table 2 2, with coating rates of 0.05 g / m (solid) and a total surface area of 4 m. Each polymerization vessel thus coated was charged with 500 kg of water in which each of the various metal salts indicated in Table VIII was dissolved, followed by the heat treatment shown in the same table with stirring at 110 rpm. For 30 minutes, and cooled. The vessels were then charged with 2.2 kg of sodium lauryl sulfate, 3 kg of cetyl alcohol, 200 g of dimethylvaleronitrile and 200 kg of vinyl chloride, and the suspension polymerization was carried out in a complete manner at 50 ° C for 7 hours. Upon completion of the reaction, the coated surfaces were washed with water and dried, and then the amounts of deposition precipitates shown in Table VIII were determined.

For comparison purposes, similar experiments were performed with Sudanese B and Nigrosine dyes alone, rather than together, and without metal salt. The results are similar in Table VIII.

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Table VIII

Experience Mixing Ratio Temperature Metal Salt Deposition

Sudan B / quantity

Nigrosine (g / m2) 95 * 100/0 90 ° C Sodium silicate 10 g 520 96 100/10 "" 5 97 100/50 "" 0 98 100/100 "" 0 99 100/500 "" 0 100 100/1000 "" 20 101 * 0/100 "" 780 102 100/100 70 ° C "3 103 100/100 50 ° C" 10 104 "" Sodium bicarbonate, 20 g 0 105 "" Primary calcium phosphate, 20 g 0 106 "" Sodium acetate, 20 g 0 107 M "Ferrochloride, 20 g 0 108" "Calcium chloride, 20 g 0 109" "Calcium sulphate 20 g 0 110 M" Alum, 20 g 0 111 "" Sodium carbonate, j 10 g 0 112 * Q / Q xx (no increase) 1800 113 * 100/0 xx (no increase) 960 114 * 0/100 xx (no increase) 1250 i__

Note: x Comparison xx No heat treatment 19 58782

Example 11 The same polymerization vessels were used as in Example 10 and were coated in the same manner with a 1% solution or dispersion of the polar organic compound or organic dye shown in Table IX alone or in combination with a metal salt in a solvent or suspension in the same table. At 90 ° C it was 30 minutes. The coated surfaces were washed with water, 100 kg of vinyl chloride, 200 kg of water, 0.05 kg of diisopropyl peroxydicarbonate, 1 kg of sodium dodecylbenzenesulfonate and 1.5 kg of cetyl alcohol were charged to the vessel, then emulsion polymerization was performed at elevated temperature, such as at 45 ° C. ./min for 8 hours. Upon completion of the reaction, the precipitation of the deposits was examined and determined. The results are shown in Table IX.

20 5 8 7 8 2

Table IX

Experience Polar Organic compound / dye / layered metal salt Mixing ratio Amount of solvent i (g / m2) jll5 * (no addition) (no addition) 1 600 | lggx Sudan B --- Toluene 550 117 * Diaminonaphthalene --- Methanol 630 118 * Nigrosine Base --- Mixed * * 480 119 * EDTA.2Na Water 1 100 120 * Phytic Acid --- Methanol 980 121 * Methylene Blue --- "690 122 * Nigrosine Water 1 300 123 Sudan B / Nigrosine / 100/5 / 100 Ethanol 23

Na 2 SiO 4, 124 "100 / 50/100" 0 125: "100 / 100/100" o 126 "100/1000/100" 10 j127 Diaminonaphthalene / 100 / 100/100 "0

Nigrosine / NaHCOg j128 Nigrosine Base / j Nigrosine / NaHCOg "" 0 il29 Methylene Blue /

Nigrosine / FeCl2 "" 30 130 Sudan B / phytic acid / "" 63

NaHCO 3 131 N-naphthylamine / Water 81

EDTA.2Na / Na 2 SO

| 132 Indoline / p-toluene- "Mixture 53 with sulfonic acid / NaCl • 133 Oil Brown BB /" "49 I Daitophor AN / CaCO ^ 134 Spirit Black / i KNa-tartrate / Na 2 SiO 4" "0

Note ·: x Comparison

Jtx Toluene and methanol xxx Ethanol and methylene chloride 21 58782

Example 12

The same polymerization vessels as in Example 10 were coated in the same manner with the same material as in Example 11 in Experiment No. 125 at a rate of 0.1 g / m 2 (solid). Each coated vessel was charged with 100 kg of vinyl chloride, 200 kg of water, and various initiators, suspending agents, and / or other additives or comonomers, as shown in Table X. The suspension was then polymerized at an elevated temperature, such as 57 ° C, at a stirring speed of 100 rpm. 10 hours. Upon completion of the reaction, the precipitation of the deposits was examined and determined. The results are shown in Table X.

As control experiments, similar polymerization was performed using the same additives or copolymers in polymerization vessels coated with a single dye, such as Nigrosine Base dye, or not coated at all. The resulting sedimentation is shown in the same Table X.

In Table X, PVA = polyvinyl acetate, HPMC = hydroxypropyl methylcellulose, IPP = diisopropyl peroxydicarbonate, LPO = lauroyl peroxide, and ΒΡ0 = benzoyl peroxide.

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Table X

Number of deposits

Additive / -

Experiment Polymerization- Suspension- Comono- This No. Initiator Substance Mere Invention Control (g / m ^) (g / m ^) 140 Dimethyl- Partially Vinyl- Valeronium-Saponated Acetate 0 190 Ril PVA, 15 kg 0.03 kg 0 .1 kg 135 "" Vinyl 0 130 acetate, 5 kg 136 "HPMC, Sorbitan 0 230 0.1 kg monolaurate 0.1 kg 137" "Sodium 2- 0 290 ethylhexyl sulfosuccinate 0.1 kg 138 IPP, Partially (no increase) 0 210 0.02 kg saponified PVA, 0.1 kg 139 LPO "(no increase) 0 330 0.5 kg 140 BPO" (no increase) 0 310 0.7 kg 141 Dimethyl- " (no addition) --- 1,200 valeronitrile 0.3 kg

Note: x Check. No coating 23 58782

Example 13

The same coatings as in Experiment No. 127 in Example 11 were used to coat the surfaces of the inner walls and other parts of the composite vessel for bulk polymerization, with the first portion being a 2 liter stainless vertical vessel and the second portion being a 4 liter stainless horizontal vessel. All coated surfaces were then washed with water and dried. The first vessel was charged with 800 g of vinyl chloride and 0.4 g of dimethylvaleronitrile, then pulp polymerized at 60 ° C at 900 rpm for 2 hours. The reaction mixture was transferred to another vessel charged with 800 g of vinyl chloride and 0.4 g of dimethylvaleronitrile, and the polymerization was carried out at 57 ° C with stirring at 100 rpm. For 10 hours. Upon completion of the polymerization, the precipitation of the polymer layer was examined at both polymerization stages.

As a control, a similar experiment was performed without coating treatment or by coating only with Nigrosine Base dye.

The results of the above experiments are shown in Table XI.

Table XI

_Amount of deposition

Experiment No.__Coating Agent_1. container 2nd container (β / m 2) (g / m2)

1 ^ 2 Same as in Experiment No. 125 0 O

1 ^ 3 Same as in test n 129 o 0

1 ^ Same as in Experiment No. 136 0 O

1 ^ 5 * (no coating) 1,400 2,040 1 ^ 6 * Nigrosine Base 70 i8o

Note: * Check 2 “5 8782

Example 14

At the same polymerization stage and coated as in Example 11, Experiment No. 125, suspension polymerization was carried out for 12-10 hours in the same manner and using 0.03 kg of dimethylvaleronitrile as initiator, 0.1 kg of partially saponified PVA as suspending agent and 0.1 kg of stearic acid as additive, that in some experiments the coating agent of Experiment No. 125 was added separately to the polymerization mixture in various amounts shown in Table XII, and in other experiments an alkaline agent such as sodium hydroxide, calcium hydroxide or sodium acetate was added as shown in the table. This polymerization was repeated, and the deposition was examined visually or in the same manner as in Example 1. The results are shown in Table XII.

Table XII

Coating- Alkaline. . .., ...

Test substance additive And Addition ^ Number of runs n * o__Addition__Addition a ^ is ° a__u u_ (pprn) (%) 1 ^ 7 (no increase) (no increase) ---- 3 1 ^ * 8 10 (no increase) k 1 ^ 9 50 (no increase) 6,150,100 (no increase) 8,151 (no increase) NaOH 0.01 0 8,152 (no increase) NaOH 0.01 1 h 6,153 (no increase) NaOH 0.01 2 h 5 15 ^ (no increase) NaOH 0.01 3 hk 155 (no increase) NaOH 0.05 0 10 156 (no increase) NaOH 0.1 0 13 157 (no increase) Ca (0H) 20.05 05 h 8 158 50 CH 2 COONa, 0 1 1 h 16

Note: Amounts in ppm or% are based on the weight of the vinyl chloride monomer.

Number of hours from the beginning of each polymerization run.

Claims (15)

A process for suspending or emulsifying polymerization of a vinyl chloride monomer alone or in admixture with a copolymerizable monomer or monomers in the presence of a polymerization initiator, characterized in that the internal walls of the polymerization reactor and others contact the surfaces of the polymer with the monomer or monomers. is treated with (a) at least one organic polar compound which is a nitrogen containing organic compound, a sulfur containing organic compound, an oxygen containing organic compound, a phosphorus containing organic compound, tar, pitch, resin or wax, or with an organic dye , which is an azo dye, an anthraquinone dye, an indigo dye, a sulphide dye, a phthalocyanine dye, a diphenylmethane dye, entriphenyl methane dye, a nitro dye, a nitro dye a thiazo dye, a xanthene dye, an acrid dye, an acrid dye, an acrid dye a benzoquinone color, a naphthoquinone color or a cyanine color, and (b) at least one of the following compounds: halides, hydroxides, oxides and carboxylates of metal elements and oxo acids of elements B, C, N, AI, Si, P, S, Ti, Cr, Mn, Ho and Sn and the inorganic salts of these oxo acids. Process according to claim 1, characterized in that said surfaces are coated with a solution or dispersion of the compound (a) and the thus coated surfaces are brought into contact with a solution or dispersion of the compound (b). Process according to claim 1, characterized in that said surfaces are coated with a solution or dispersion of compounds (a) and (b) formed in a solvent and having a weight ratio of 1: 0.01 - 1: 50 between ( a) and (b), after which a heating treatment is carried out at a temperature of 50-100 ° C for more than 10 minutes. Method according to claim 1, characterized in that said surfaces are alternatively coated with a solution or dispersion of the compound (a) and a solution or dispersion of the compound (b) in the treatment. 5. A method according to claim 2, characterized in that the surfaces coated with a solution or dispersion of the compound (a) are subjected to a heating treatment at a temperature of 50-100 ° C for more than 10 minutes, in contact with a solution or dispersion of the compound. compound (b). 29 5 8 7 8 2 Method according to claim 4, characterized in that the surfaces coated with the solution of compounds (a) and (b) are subjected to a heating treatment at a temperature of 50-100 ° C for more than 10 minutes. Process according to claim 1, characterized in that in the treatment, at least two of the steps are carried out: i) said surfaces are coated with a solution or dispersion of said compound (a) and the thus coated surfaces are contacted with a solution or dispersion of the compound. (b); ii) said surfaces are coated with a solvent or dispersion solution of compounds (a) and (b), after which a heating treatment is carried out at a temperature of 50-100 ° C for more than 10 minutes, and iii) said surfaces are alternately coated with a solution or dispersion of compound (a) and with a solution or dispersion of compound (b). Process according to claim 1, characterized in that said surfaces are coated with at least two compounds (a) in the treatment, one of which is water-soluble and the other or insoluble in water. Process according to claim 1, characterized in that at least one of the compounds (a) and (b) is added to the polymerization mixture. Process according to Claim 1, characterized in that as organic dye, at least one of the following is used: Direct Brilliant Yellow G (CI Direct Yellow 14), Acid Light Yellow 2G (CI Acid Yellow 17), Levafix Yellow 4G (CI Reactive Yellow 10) ), Procion Brilliant Orange G (CI Reactive Yellow 1), Direct Fast Scarlet GS (CI Direct Red 4), Direct Bordeaux NS (CI Direct Red 229), Brilliant Scarlet 3R (CI Acid Red 18), Acid Alizarine Red B (CI Mordant Red 9), Direct Turkish Blue GL (CI Direct Blue 86), Cibacron Blue 3G (CI Reactive Blue 2), Blankophor B (CI Fluorescent Brightening Agent 121), Nigrosine (CI Solvent Black 7), Sirius G (CI Direct Black) 74), Chrysamine G (CI Direct Yellow 24), Direct Fast Yellow GG (CI Direct Yellow 26), Chrome Yellow G (CI Mordant Yellow 1), Chrome Yellow ME (CI Mordant Yellow 30), Eosine G (CI Acid Red 37) ), Basic Flavin 8G (CI Basic Yellow 1), Astrazon Yellow 3G (CI Basic Yellow 11), Rhodamine 6GCP (C. I. Basic Red 1), Safranine T (C. I. Basic Red 2), Rhodamine B 1 ·. · (