CS195302B2 - Process for the polymerization of vinylchloride - Google Patents

Abstract

In the polymerisation of monomeric vinyl chloride, alone or mixed with one or more olefinically unsaturated, copolymerisable monomers, in the presence of a polymerisation initiator, the deposition of polymer crusts is prevented, and the quality and the productivity increased, if, before the polymerisation, the surfaces of the inside wall and other parts of the polymerisation vessel which come into contact with the monomer or the monomers are each treated with at least one compound selected from a) polar organic compounds, including polar organic dyes, and b) halides, hydroxides, oxides, and carboxylates of metals, oxygen acids of elements from the second to the sixth period of groups IIB and III to VII of the Periodic Table, and inorganic salts of these oxygen acids. The compounds a) and b) are applied separately or simultaneously, using conventional techniques.

Description

The invention relates to a process for the polymerization of vinyl chloride, alone, a monomer or a mixture thereof. %, in the presence of a polymerization initiator.

In any known types of polymerization, such as suspension polymerization, emulsion polymerization, solution polymerization, gas phase palymerization and block polymerization, deposition of polymer deposit on the inner wall of the polymerization vessel and other surfaces in contact with the monomer or monomers is a serious problem for the following reasons.

First, the deposition of the polymer deposit causes a reduction in the polymer product yield and cooling efficiency of the polymerization vessel.

Second, any deposit that falls off the surfaces is likely to be admixed to the polymerization product, resulting in a deterioration in its quality.

Third, removing deposits from surfaces requires a lot of work and time, resulting in reduced productivity.

Finally, and as a matter of considerable importance at a later time, the deposition of the deposit usually after each polymerization poses a health problem for workers due to a certain amount of unreacted monomer or monomers adsorbed onto the deposit. .

Many methods have been proposed to prevent polymer deposition on various surfaces, including coating these surfaces with polar organic compounds such as amine compounds, quinone compounds and aldehyde compounds, dyes and pigments. (See Japanese Patent Nos. 30,343/1970 and 30,385 (1970)). However, known processes are not effective in a polymerization process in which vinyl chloride is polymerized in the presence of emulsifiers or together with a comonomer or comonomers, or the polymerization mixture comprises acyl peroxides such as benzayl peroxide, lauroyl peroxide and the like or higher carboxylic acids such as lauric acid and stearic acid. or a salt thereof.

Further, by known deposition methods, this prevention can hardly be maintained by repeated polymerizations.

The main object of the present invention is to provide a process for the polymerization of a vinyl chloride or a mono-mineral blend consisting mainly of vinyl chloride, in which the deposition of polymer deposits on the inner walls of the polymerization vessel or other surfaces in contact with the monomer or monomers can be substantially prevented.

. It is a further object of the present invention to provide a process for the polymerization of vinyl chloride or a monomer mixture consisting mainly of vinyl chloride, which can greatly increase the productivity of vinyl chloride production.

Another object of the present invention is to provide a process for the polymerization of vinyl chloride or a mixture of monomers consisting mainly of vinyl chloride, by means of which high quality vinyl polymer can be easily produced.

The present invention provides a process for the polymerization of vinyl chloride, monomer alone or mixed. with a copolymerizable monomer or monomers in the presence of a polymerization initiator, characterized in that prior to polymerization, the interior wall surfaces and other parts of the polymerization reactor in contact with the monomer or monomers are subjected to treatment with at least one organic compound (a) selected. from the group consisting of nigrosine black, alcohol black, oil black, threnic gray K, aniline black, alizarin yellow, alizarin yellow R, durable light yellow G, thren golden yellow RK, pyrazoilone red, durable orange to GTR, phthalocyanine, phthalocyanine, phthalocyanine yellow S, Sudan B, nigrosine, nigrosine base, diaminonaphthalene, disodium methylenediaminotetraacetate, phytic acid, alphanaphthylamine, indulin, p-toluenesulfonic acid, oleic brown BB and daitophor AN with at least one compound. (b) selected from the group consisting of sodium silicate, potassium nitrite, boric acid, silicic acid, potassium dichromate, triphosphoric acid, polyphosphoric acid, magnesium carbonate, stannic acid, sodium molybdate, titanic acid, manganese acid, sodium borate, sodium nitrite phosphoric acid, potassium silicate, sodium borate, sodium bicarbonate, calcium tetrahydrogen diphosphate, sodium acetate, ferrous chloride, potassium sulfate and potassium aluminum sulfate, the surfaces of the "outer walls" being treated by an operation selected from the group consisting of:. covering surfaces with solution. or a dispersion of compound (a) and contacting the surfaces so coated after contact with the solution; or. dispersions of compound (b), coating of surfaces with a solution or dispersion of compounds (a) and (b), wherein the weight ratio of compounds (a) and (b) is in the range of 0.01:: 1 to 50: 1, dissolved or dispersed in a solvent and heated to a temperature ranging from 50 ° C to 50 ° C. . 100 ° C for more than 10 minutes, and covering these surfaces alternately with a solution or dispersion of compound (a) and a solution or dispersion of compound (b), wherein the weight ratio of compounds (a) and (b) ranges from 0, 1 to 50: 1 to obtain a total coating of compounds (a) and (b) of at least 0.001 g / m ² .

In describing the present invention, generally used trivial names of dyes are mentioned. The corresponding names in the Color Index are listed in Table A.

Trivial name

Table A

Corresponding name in Color Index γ methylene blue nigrosine black oil black ... <

alcohol black · brilliant Indigo B thren. red violet RH thren print black. B sulfur · blue FBB light black B Sudan B brilliant yellow G sour light yellow 2G Levafix yellow 4G

Procion. brilliant orange G. . direct durable. red GS straight claret NS brilliant red 3R acid alizarin red B straight Turkish blue GL cibacron blue 3G blankofor B.

nigrosin sirius G chrysamine G direct durable yellow GG chrome yellow G chrome yellow ME eosin G.

basic blue 9 solvent black 7 solvent black 3 solvent black 5 vat blue · 1.

vint violet 2 ..

cypress violet 13 sulfur blue 7.

sulfur black 1 solvent black · 3.

reactive yellow 14 acid yellow 17 reactive yellow 10 · reactive yellow 1.

direct red. Straight red 229 acid red 18 'stain red 9.

straight blue. 86.

Reactive Blue 2 fluorescent brightener. 121 acid black 2 direct black 74 direct yellow 24 direct yellow 26 mordant yellow 1 mordant yellow 30.

sour. červeň '....

with

19S362

Trivial name basic flavin 8G astrazone yellow 3G phodamine 6 GCP safranin T phodamine B daitophone AN auramin conc. chrysoldin ‘Bsmarck brown BG nigrosine lily black '- black oil'. Black threnal gray K anitine black alizarin yellow R durable light yellow G threnic gold RK pyrazolon red red durable orange G, TR phthalocyanine blue naphthol yellow S

The above polar organic compounds and organic dyes may be used alone or in combination.

In practicing the process of the present invention, it is preferred that compounds (a) and (b) be dissolved or dispersed separately or together in a solvent prior to use. Water, alcoholic solvents, ester solvents, ketone solvents, hydrocarbon solvents and chlorinated hydrocarbon solvents are generally used as the solvent.

The following are three preferred embodiments of the method of the present invention. ’

First, compound (a) is dissolved or dispersed in one of the above solvents and the resulting solution or dispersion is applied to the surfaces; the inner walls and other parts of the polymerization reactor coming into contact with the monomer or monomers. Then, the coated surfaces are contacted and treated with compound (b) by introducing a solution or dispersion thereof into the reactor, heating the solution or dispersion preferably at 50 to 100 degrees C for 10 minutes or more and then removing the solution or dispersion from the reactor. followed by a conventional polymerization process in the same reactor.

In this case, however, if the 'polymerization' mixture is aqueous, such as in suspension or emulsion polymerization, and if 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. .

Second, compound (a) is dissolved or dispersed in an aqueous solvent, while compound (b) is dissolved in the same or a different solvent. The solution or dispersion of compound (a) is added dropwise p ^ _t of a solution or dispersion of compound (b), followed by heating preferably at 50 to 100 ° C. The resulting mixture is applied to surfaces corresponding to the name in the Color Index basic yellow 1 basic yellow 11 basic red 1 basic red 2, basic violet 10 fluorescent brightener 122 basic yellow 2 basic orange 2. ..

alkaline brown 1 ....

solvent black 7 solvent black 5 solvent black 3 vat black 28 pigment black 1 mordant orange 1 acid yellow 11.

vat yellow 4, pigment red 38 pigment orange. 24 ..

pigment blue 15 ' acid yellow 1 '·:

The walls and other parts of the polymerization reactor in contact with the monomer or monomers.

The coated surfaces are washed with water if necessary. The polymerization is then started by a known method.

Third, separate solutions or dispersions of compounds (a) and (b) are prepared in the same or different solvents, (a) solutions or dispersions, and (b) non-dispersion solutions are alternately, one or more times, applied to surfaces in contact with monomer or monomers.

The surfaces thus coated are subjected to a heat treatment by passing hot water through the jacket or by blowing hot air into the reactor. It is preferable to apply coating solutions or dispersions while the inner wall; maintained at about 50-100 ° C by passing hot water through the jacket.

It is preferable to complete the deposition of the solutions or dispersions by passing the hot water through the jacket and at the same time blowing the hot air into the rake at each application or coating interval.

In any of the above embodiments, it is preferred that compounds (a) and (b) are contacted with each other at an elevated temperature of greater than 50 ° C. If the temperature is lower, insufficient results are obtained and more than 10 hours are required for treatment.

The ratio of compound (bJ to compound (a) used in the method of the invention may vary depending on the kind of compounds used and the type of polymerization involved. Specifically, in the above-mentioned first embodiment, wherein compound (b) has a low concentration in aqueous phase, and in a third embodiment in which compounds (aJ and (bj) do not mix well with each other, it is preferred that the weight (i.e.

19'5'302 (b) to the compound. (a) was relatively large, usually. from 0.1: 1 to 500. 1.

In a second embodiment, wherein a heated mixture of compounds (a) and (b) is used, the wt. the ratio of compound (b) to compound (a) is relatively small, e.g. from 0.01: 1 to 50: 1.

In accordance with the invention, the amount of compound (a) or (b) or mixture thereof to be used to cover the inner wall surfaces and other reactor parts may be less than or greater than the amount used when known coating materials are used. materials in accordance. with known procedures. For example, sufficient prevention of polymer deposition can be achieved with an amount of at least 0.001 g / m ² .

In conjunction with the above three embodiments, it may be added that it is optimal to use any of them not simply but in combination. For example, the surfaces are first coated with a mixed solution of compounds (a) and (b), followed by heating as in the second embodiment, and the surfaces so coated are covered with the solution of compound [a] and the solution of compound (b) in succession, followed by heating as in the third embodiment.

When two kinds of compound (a) are used together, it is possible to obtain better. results by selecting either or. two water soluble compounds and the other organic solvent soluble compounds.

It is further advantageous to add a solution or dispersion to the polymerization mixture in question in order to achieve a better inhibition of deposit formation. of compound (a) or (b) 'or mixed. and a heated solution or dispersion of compounds (a). and. In this case, the amount of such additions should be limited to. range from a few ppm to 100 ppm, based on the monomer or monomers, since excess amounts may have. adverse effects on the resulting polymer product.

In order to further increase the deposition of deposition in accordance with this. The invention proposes to add to the polymerization mixture an alkaline substance, albeit not in accordance with the definition of compound (b), such as oxides, hydroxides, carbonates, phosphates, bicarbonates, silicates and acetates of alkali metals, alkaline earth metals and ammonium. However, it is important that the alkaline substances are not added in an amount such as to cause deterioration of the resulting polymer. A suitable amount is, for example, up to 1% by weight, based on the monomer or monomer mixture.

The process of the present invention can be applied to all types of polymerization, i.e., suspension polymerization, emulsion polymerization, solution polymerization and block polymerization of vinyl chloride monomer or a mixture of monomers mainly of vinyl chloride. Further, the process of the invention does not limit the choice of various additives such as suspending agents, emulsifiers, chain transfer agents and polymerization initiators, polymerization temperatures and agitation rates.

The process of the invention can be effectively applied not only in the homopolymerization of vinyl chloride, but also in the copolymerization of vinyl chloride with a copolymerizable monomer or monomers.

Copolymerizable monomers include, for example, vinyl esters, vinyl ethers, acrylic and methacrylic acid, their esters, maleic and fumaric acids, their esters, maleic anhydride, aromatic vinyl monomers, vinyl halides other than vinyl chloride, vinylidene halides, olefins, acrylonitrile and acrylonitrile.

The invention is further illustrated by the following examples.

Example 1.

Two liter autoclaves were provided for this example. made of stainless steel, each equipped with a turbine stirrer. Inner wall surfaces of each autocave and agitator blades. were coated with a 0.1% solution in toluene, each of the various organic dyes as indicated. under the heading "Compound A" in Table I, in an amount of about 0.05 g / m 2 (as> solid) and the coated surfaces were dried at 70 ° C for 60 minutes, after which they were coated and dried for 70 minutes. a 1% aqueous solution of each of the different was applied on top. oxoacids. or a salt thereof, as ordered under the heading "Compound B" in the same table, in an amount of about 0.05 g / m ² (as a solid), followed by drying at 70 ° C for 60 minutes. 900 g of water, 0.4 g of methylcellulose and 0.8 g of polyvinyl alcohol were then impregnated into each 'coated' autoclave. Then the autoclave has been evacuated and nitrogen introduced, as was dosed 600 g of vinyl chloride monomer and 21 g of alpha-azobisvaleronitrile and the mixture was polymerized in suspension at 1000 rpm ^-1 and a temperature of 57 ° C for about 6 hours.

The polymerization runs were repeated continuously with each autoclave until the deposited deposit exceeded 1 g / m ^2, the number of these repeated polymerization runs being listed in 'Table I' under the heading. "Number of runs". The number of runs means that deposit deposition was effectively prevented during these repeated polymerization runs. Details and results are summarized in Table I.

By way of comparison, assays using compound A or B alone, not in combination, were conducted in a similar manner and under similar conditions, the results obtained being summarized in the same table.

1: 95302; 9

TABLE I

Compound A

Compound В

Merging- Merging-. Compound А а В on A on В exp. počet zk. počet zk. Run No. Run No. Run Run No

nigrosin black sodium silicate 1 18 13 12 25 2 alcohol black potassium nitrite 2 12 14 9 26 2 oil black boric acid 3 10 15 Dec 7 27 Mar: 1 thren gray К silicic acid 4 ~ 5 16 3 28 2 aniline black potassium dichromate 5 6 17 4 29 1 alizarin yellow R triphosphoric acid 6 6 18 2 30 2 durable light yellow G magnesium carbonate 7 4 19 Dec 3 31 1 thren gold yellow RK stannic acid 8 3 20 May 2 32 1 pyrazolone red sodium molybdate 9 3 21 2 33 2 Permanent orange GTR titanic acid 10 3 22nd 2 34 1 phthalocyanine blue Manganese acid 11 2 23 1 35 1 naphthol yellow sodium borate 12 3 24 2. 36 . 1

Note: Tests marked 13 to 36 are control tests.

Example 1 a d 2

Same autoclaves. as used in Example 1, were coated with compounds A and V in the combination shown in Table II and, for comparison, with Compound A or V alone as indicated in the same table, in a team, manner and under the same conditions as in Example 1. To each of the coated autoclaves. 900 g of water, 6 g of sodium lauryl sulfonate, 1 g of potassium persulfate and 600 g of vinyl chloride were metered in to perform emulsion polymerization at 48 ° C for 10 hours. Details and results of these tests are given in Table II.

TABLE II

Test no.

Compound A

Compound В

Number of runs

37 nigrosin black 38 alcohol black 39 oil black 40 nigrosin black 41 alcohol black 42 nigrosin black 43 alcohol black 44 -. 45 46 -

triphosphoric acid 5 sodium molybdate 3 sodium nitrite 2 sodium silicate .5: boric acid 3. '3 Silicate. sodium 2 1 sodium nitrite 1 phosphoric acid and-

Note: Tests 42-46 were control.

Example 3

The same autoclaves were used as in Example 1 and were coated with compounds A and V in the combination shown in Table III and for comparison with Compound A and V alone as shown in the same table, in the same manner and under the same conditions as in Example 1.

900 g of water, 0.4 g of methylcellulose, 0.8 g of polyvinyl alcohol, 600 g of vinyl chloride, 600 g of comonomer, i.e. vinyl acetate or vinylidene chloride, were metered into each of the coated autoclaves and 0.21 g of isopropyl peroxydicarbonate was dosed to perform suspension polymerization at 52 ° C for about 6 hours.

Details and results are summarized in Table III.

TABLE IÍI

Test no. Komonomer Compound A Compound В Number of runs 47 vinyl acetate nigrosin black silicic acid 8 48 vinyl acetate oil black triphosphoric acid 5 49 vinyl acetate nigrosin black potassium nitrite 7 50 vinyl acetate oil black boric acid 4 51 waveslidenchlorld nigrosin black phosphoric acid 8 52 vinylidene chloride alcohol black sodium molybdate 5 53 vinylidene chloride nigrosin black sodium silicate 8 54 vinyl acetate nigrosin black - 5 55 vinyl acetate oil black - 3 56 vinyl acetate - silicic acid 1 57 vinyl acetate - triphosphoric acid 1 58 vinylidene chloride nigrosin black - 5 59 vinylidene chloride alcohol black - 3 60 waveslidenchlorld - sodium molybdate 1

Note: Tests No. 54—60 are control tests.

Example 4

The same autoclaves as in Example 1 were coated with a 0.05% solution or dispersion of a mixture composed of compounds in the same amounts but in different combinations as shown in Table IV at 0.1 g / m ² (solids) and coated surfaces were dried at 70 ° C for 60 minutes. Slurry polymerization of vinyl chloride was then carried out in the same manner and under the same conditions as in Example 1 to test deposit deposition. Details and results are summarized in Table IV.

TABLE IV

Test no. Compound A Compound В Number of runs 61 nigrosin black sodium borate 16 62 alcohol black sodium nitrite 12 83 oil black silicic acid 11 64 thren gray К boric acid 5 65 aniline black triphosphoric acid 6 66 alizarln yellow R potassium dichromate 5 67 durable light yellow G stannic acid 3 68 thren gold yellow RK sodium silicate 3 69 pyrazolone red titanic acid 3 70 permanent orange GTR Manganese acid 2 71 phthalocyanine blue phosphoric acid 4 72 naphthol yellow S sodium molybdate 3

Example 5

The same autoclaves used in Example 1 were coated with compounds A and V in the combination shown in Table V and in the same manner and under the same conditions as in Example 4. Emulsion polymerization was performed in each covered autoclave similar to Example 2. Details and the results of these tests are given in Table V.

TABLE V

Test No. Compound A Compound В Number of runs

73 nigrosin black triphosphoric acid 4 74 alcohol black sodium molybdate 2 75 oil black sodium nitrite 2 76 nigrosin black sodium silicate 4 77 alcohol black boric acid 2

193302

Example6

The same autoclaves as in Example 1 were coated with compounds A and B in combination as shown in Table VI under the same conditions and in the same manner as in Table VI

Test No. Compound A Compound B Number of runs

78 nigrosin black silicic acid  7 79 oil black triphosphoric acid 5 80 nigrosin black potassium nitrite 7 81 oil black boric acid 4 82 nigrosin black phosphoric acid 6 83 alcohol black sodium molybdate 5 84 nigrosin black potassium silicate 6 Note: Tests no. 78-81 are from homopolymerization vinyl chloride.

Tests No. 82-84 are from the copolymerization of vinyl chloride and vinylidene chloride.

Example 7

The same autoclaves used in Example 1 were coated with a solution of nigrosine black in ethanol or toluene in various amounts as shown in Table VII, then dried at 70 ° C for 60 minutes and then. 1% solution of clade 4 silicate was applied to the coated and dried surfaces. The slurry polymerization or copolymerization was performed essentially the same as in Example 3.

Details and test results are given in Table VI.

of sodium at 0.05 g / m ² (solid) followed by drying at. at 70 ° C for 60 minutes. Then, a slurry polymerization of vinyl chloride was performed in each coated autoclave in the same manner and under the same conditions as in Example 1 to test deposit build-up.

Details and results are summarized in Table VII.

TABLE VII

Exam number

Amount of nigrosine black applied g / m ²

Number of runs

85 10 2 86 2 3 87 1 4 88 0.5 5 89 0.05 5 90 0.005 3 91 0.0005 2 92 0.5 2 93 0.5 6 94 0.01 3

Comment:

1. The nigrosine black solutions used in tests Nos. 85-91 were ethanolic, whereas the solutions used in tests Nos. 92 to 94 were in toluene.

2. In Test No. 93, the nigrosine black coating surfaces were lightly wiped with a piece of ethanol-impregnated cotton gauze after drying.

Example 8

The same coating and polymerization procedure as in Test No. 88 of Example 7 was repeated except that 5% by weight, 0.1% by weight, or 0.0001% by weight, based on wool chloride, of silicate were added. sodium to the polymerization mixture before starting the polymerization reaction. After 9, 7 and 5 polymerization runs, deposit build-up was prevented.

Example 9

The same procedure as in Test No. 61 of Example 4 was repeated except that the coated surfaces were additionally coated with nigrosine black. and sodium silicate in the same manner and under the conditions of Example 1. The number of polymerization runs in which deposition was prevented was 25.

Example 10

For this example, 100 liter stainless steel polymerization vessels were used, equipped with paddle type stirrers with blades of 600 mm diameter. · The inner wall surfaces of the vessels and the stirrer blades and the shaft were covered with a 0.5% solution of Sudan B and Nigrosin in methanol in various mixing weight ratios, as shown in Table VIII, in an amount of 0.05 g / m? (solids), with a total surface area of 4 - m ² . 500 kg of water was metered into each of the coated polymer containers to which one of the different metal salts was dispensed to dissolve, as indicated in Table VIII, followed by treatment at the temperature indicated in the table with stirring at 110 rpm ^{. 1} for 50 minutes and cooling.

Then 2.2 kg of sodium lauryl sulphate, 3 kg of cetyl alcohol, 200 g of dimethylvaleronitrile and 200 kg of vinyl chloride were added to carry out the suspension polymerization at 50 ° C for 7 hours, as in the known procedure. After completion of the reaction, the coated surfaces were washed with water and dried and then the amount of deposit deposited was determined as shown in Table VIII. '

For comparison, similar tests were performed with Sudan B or Nigrosin alone, and not in combination or without any metal salt. The results are shown in Table VIII. '

Table VIII

Exam mixing ratio tepaa metal salt amount C. Sudan B / Nigrosine Noc: 2 ° C g / m ²

95 *]. 100/0 90 sodium silicate 10 g 520 96 100710 90 sodium silicate 10 g 5 -97 100/50 . 90 sodium silicate 10 g 0 98 100/100 90 sodium silicate 10 g 0 99 100/500 90 sodium silicate 10 g 0 100 ALIGN! 100/1000 90 sodium silicate 10 g 20 May 101 *) 0/100 90 sodium silicate 10 g 780 102 100/100 70 sodium silicate 10 g 3 103 100/100 50 sodium silicate 10 g 10 104 100/100 90 sodium bicarbonate 20 g 0 105 100/100 90 primary calcium phosphate 20 g 0 106 100/100 90 sodium acetate 20 g 0 107 100/100 90 ferrous chloride-20 g 0 108 100/100 90 calcium chloride 20 g 0 109 100/100 90 potassium sulphate 20 g 0 110 100/100 90 alum 20 g. 0 111 100/100 90 sodium carbonate, 10 g 0 .112 *) 0/0 1 1 j none 1,800 113 *) 100/0 1 1 j none 960 114 *) 0/100 1 1 j none ' . 1,250

Note: *) Control, * ') No heat treatment.

Example 11

The same polymerization vessels as used in Example 10 were coated in a similar manner with a 1% solution or. a dispersion of one of the solvents listed in Table IX, a polar organic compound or an organic dye alone or in combination and a metal salt as shown in the same table that has been heated to -90 ° C for 30 minutes. Then, 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 dodecylbenzenesulfonate and 1.5 kg of cetyl alcohol were metered into each polymerization vessel, followed by emulsion polymerization at elevated temperature of 45 ° C. at 110 rpm for 8 hours. After completion of the reaction, a. the amount of deposit deposited. - The results are summarized in Table IX.

Table IX

Exam number Polar organ, compound (dye) / metal salt .mixing ratio solvent application rate g / m ² 115 *) none . - none 1,600 116 *) Sudan В - toluene 550 117 *) diaminonaftalen - methanol 630 118 *) nigrosine base - mixed **) 480 119 *) EDTA.2Na - water 1100 120 *) phytic acid .— - methanol 980 121 *) methylene blue - methanol 690 122 *) nigrosine - water 1300 123 Sudan B / Nigrosin / NazSiO 100/5/100 ethanol 23 124 Sudan B / Nigrosin / NiSiOd 100/50/100 ethanol 0 125 Sudan B / Nigrosin / NazSiOi 100/100/100 ethanol 0 126 Sudan B / Nigrosin / Na 2 SiO 4 100/1000/100 ethanol 10 127 diaminonaftalen / Nigro- sin / NaHCO 3 100/100/100 ethanol 0 128 nigrosine base / nigrosine / NaHCO 3 100/100/100 ethanol 0 129 Methylene blue / nigrosine / FeCl2 10Q / 100/100 ethanol 30 130 Sudan B / Phytic acid / / ЫаНСОз 10/10/10 ethanol 63 131 α-Naphthylamine / EDTA. . 2Na / Na2SO4 100/100/100 water 81 132 indulin / p-toluenesulfonic acid / NaCl 100/100/100 mixed ***) 53 .133 oil brown ВВ / / Daitofor AN / СаСОз 100/100/100 ‘Mixed ***) 49 134 Alcohol black / Rochelle salt / NazSiO4 100/100/100 mixed ***) 0

*Αζη .: *) Control, “) toluene and methanol,” ‘) ethanol and methylene chloride.

Example 12

The same polymerization vessels as used in Example 1 were coated in a similar manner with the same material used in Test No. 125 of Example 11 in an amount of 0.1 g / m ² (solids). 100 kg of vinyl chloride, 200 kg of water together with various initiators, suspending agents and / or other additives or comonomers as indicated in Table X were metered into each coated vessel, followed by suspension polymerization at elevated temperature, 57 ° C, with stirring at 100 rpm for hours. After completion of the reaction, the amount of deposit deposited was tested and determined. The results are summarized in Table X.

For control, similar polymerization was performed using the same additives or comonomers as above, with the polymerization vessels with one dye, nigrosine base, or not covered at all. The resulting deposit of deposition is shown in the same Table X.

In Table X, PVA is polyvinyl acetate, HMPC hydroxypropylmethylcellulose, 1PP diisopropylperoxydicarbonate, LPO lauroyl peroxide and BPO benzoyl peroxide.

Table X

Exam. Polymerization number Initiator

Suspension Agent

Aitvv / comonomer amount of deposition of this invention. control g / m ² g / m ²

135 dimethylvaler-onitrile, 0.03 kg partially saponified PVA, 0.1 kg vinyl acetate, 15 kg 0 190 136 dimethylvaleronitrile, 0.03 kg partially saponified PVA, 0.1 kg vinyl acetate, 5 kg 0 130 137 dimethylvaleronitrile, 0.03 kg HPMC, 0.1. kg Sorbltan monolaurate, 0.1 kg sodium 2-ethylhexylsulfosuccinate 0.1 kg 0 230 138 dimethylvaleronitrile, 0.03 kg HPMC, 0.1 kg 0 290 139 IPP, 0.02 kg partially saponified PVA, 0.1 kg (none) 0 210 140 LPO, 0.5 kg partially saponified PVA, 0.1 kg (none) 0 330 141 BPO, 0.7 kg partially saponified PVA, 0.1 kg . (none) 0 .310 142 *) dimethylvaleronitrile, 0.3 kg partially saponified PVA, 0.1kg (none) .. 1200

Note: *) check. No coverage.

- Example 13

The same coating materials as used in Test No. 127 of Example 11 were applied to the inner wall surfaces and other parts in the composite containers for. block polymerization, wherein the first vessel was a 2 liter vertical type stainless steel vessel and the second vessel was a horizontal type aluminum stainless steel vessel. Then all the coated surfaces were washed with water and dried. The first vessel was charged with 800 g of vinyl chloride and 0.4 g of dimethylvaleronitrile, followed by polymerization at 60 ° C, with stirring at 900 rpm for 2 hours.

The reaction mixture was transferred to a second vessel which was charged with 800 g of vinyl chloride and 0.4 g of dimethylvaleronitrile. The polymerization was carried out at 50 ° C. stirring at 100 rpm for 10 hours. After the polymerization, the deposited deposit was tested with respect to each polymerization vessel.

For comparison, similar tests were carried out without coating or with nigrosine base only.

The results of the above tests are summarized in Table XI.

Table XI

Test Coating Quantity of deposit No. 1 Container 2. Container g / m ² g / m2

143 as well as in the test C. 124 0 0 144 as well as in the test C. 127 0 0 145 as well as in the test C. 134 0 0 146 *) none 1400 2040 147 *) nigrosine base 70 180

Note: *) check.

Example 14

In the same polymerization vessel that was coated and used in Test # 125 of Example 11, suspension polymerization was carried out in the same manner and with the same additives as in Test # 135 of Example 12, for 10 hours, except that in some In the tests, the coating materials of Test No. 125 were separately added to the polymerization mixture in various amounts as shown in Table XII, and in the other tests were added alkali, sodium hydroxide, calcium hydroxide, sodium acetate as shown in Table XII. . This polymerization run was repeated to determine deposition of the deposit on the eyes or in the same manner as in Example 1. The results are shown in Table XII.

Exam number 21 added amount of cover, material (p.p.m.j 195302 Table XII alkali and added amount % 22nd time of addition number of runs 148 none none _______________ 3 149 10 none - 4 150 50 none - 6 151 100 ALIGN! none - 8 152 none NaOH 0.01 0 8 153 none NaOH 0.01 1 hour 6 154 none NaOH 0.01 2 hrs 5 155 none NaOH 0.01 3 hours 4 156 none NaOH 0.05 0 10 157 none NaOH 0.1 0 13 158 none Ca (OH) 2 0.05 1 hour 8 159 50 CH3COONa 0.1 1 hour 16 Comment: amount in ppm or % are based on weight vinyl chloride mo-

nomeru.

*) The number of hours elapsed since the start of each polymerization run.

Claims (6)

SUBJECT A process for the polymerization of vinyl chloride, alone monomer or mixed with a copolymerizable monomer or monomers in the presence of a polymerization initiator, characterized by. by undergoing treatment with at least one organic compound (a) selected from the group consisting of nigrosine black, alcohol black, oil black, threnic gray K, aniline black prior to polymerization, the internal wall surfaces and other parts of the polymerization reactor in contact with the monomer or monomers , alizarin yellow, alizarin yellow R, durable pale yellow G, thren gold RK, pyrazolone red, durable orange GtR, phthalocyanine blue, naphthol yellow S, Sudan B, nigrosine, nigrosine sodium, diaminonetraate, diaminonetraate, diaminonetraate, diaminotetinate alphanaphthylamine, indulin, p-toluenesulfonic acid, oleic BB and daitophor AN and at least one compound (b) selected from the group consisting of sodium silicate, potassium nitrite, boric acid, silicic acid, potassium dichromate, triphosphoric acid, polyphosphoric acid, magnesium carbonate, kyse tin (II) tin, sodium molybdate, titanic acid, permanganic acid, sodium borate, sodium nitrite, phosphoric acid, potassium silicate, sodium borate, sodium bicarbonate, calcium tetrahydrogen diphosphate, sodium acetate, ferric chloride, potassium sulphate and potassium aluminum sulphate, modifying the operations of the group comprising coating the surfaces with a solution or dispersion of compound (a) and contacting the surfaces so coated with a solution or dispersion of compound (bj; vynalezu. coating surfaces with a solution or dispersion of compounds (a) and (b), wherein the weight ratio of compounds (a) and (b) is in the range of 0.01: 1 to 50: 1, dissolved or dispersed in the solvent and heated to a temperature of 50 ° C to 100 ° C for more than 10 minutes; and covering said surfaces alternately with a solution or dispersion of compound (a) and a solution or dispersion of compound (b), wherein the weight ratio of compounds (a) and (b) is in the range of 0.01: 1 to 50: 1 such that. a total coating of compounds (a) and (bj) of at least 0.001 g / m ^{2 is obtained} . 2. A method according to claim 1, wherein the surfaces coated with the solution or dispersion of organic compound (a) are heated to a temperature in the range of 50 to 100 ° C for more than 10 minutes in contact with the solution or dispersion of compound (bj. 3. The process of claim 1 wherein the surfaces covered with the solution of compounds (a) and (b) are heated to a temperature of 50 ° C to 100 ° C for more than 10 minutes. 4. The method of claim 1 wherein the surfaces are treated by coating with at least two organic compounds (a), one of which is. water soluble and the other or the others are insoluble in water. 5. The process of claim 1 wherein at least one of compounds (a) and (b) is added to the polymerization mixture. 6. The process of claim 1 wherein compound (a) or (bj or a mixed and heated solution or dispersion of compounds (a) or (b) is added to the polymerization mixture in an amount of no more than 100 ppm based on the weight of the monomer or monomers.