Process for production of vinyl polymer

This invention relates to a process for producing a vinyl polymer, particularly to improvement of scaling prevention on the inner wall surfaces of a polymerizer, etc. in the course of polymerization of vinyl chloride, etc.
In processes for suspension polymerization or emulsion polymerization of vinyl monomer such as vinyl chloride monomer in the presence of a polymerization catalyst, there is involved the problem that polymer scales stick to the inner wall surface of the polymerizer or the portions of the auxiliary equipment of the polymerizer which may come into contact with the monomer, such as stirrer, during polymerization. Scales sticking to the inner wall of the polymerizer, etc. will result in a lower polymer yield and cooling capacity of the polymerizer, and may also cause so-called fish eyes formed by the adhering scales peeling off the inner wall of the polymerizer and mixing in with the product, thereby lowering the quality of the product. Further, the removal of the adhering scales requires enormous an amount of labor and time; in addition, unreacted monomers (vinyl chloride, etc.) are absorbed into the scales which may involve disadvantageously the danger of bringing about hazards to the human body.
As the method for preventing scaling of polymer, it is known in the art to apply a coating of a chemical reagent (hereinafter referred to as "scaling preventive") on the inner wall surface of the polymerizer; various such scale preventives have been proposed. Among the various known methods, there is known a particularly good method in which a dye and/or a pigment is used as the scaling preventive (Japanese Patent Publication No. 30835/1970). However, this method is not always effective and sure in preventing scaling, and thus is not always satisfactory.
Accordingly, an object of the present invention is to provide a process for production of a vinyl polymer which can surely prevent scaling in the course of polymerization of one or more kinds of vinyl monomers.
The present inventors in attempting to improve on the method disclosed in Japanese Patent Publication No. 30835/1970 have consequently found that scaling can be prevented effectively and surely by use of a dye, a pigment or a specific compound having at least 5 conjugated .pi. bonds as a scaling preventive, and also by controlling the surface roughness of the inner wall surfaces of the polymerizer, etc. to be coated with the scaling preventive to a predetermined value or below.
According to the present invention, there is provided a process for production of a vinyl polymer by suspension polymerization or emulsion polymerization of at least one kind of vinyl monomer in an aqueous medium, characterized in that the polymerization is carried out in a polymerizer, the inner wall surface and portions of the auxiliary equipment thereof which may come into contact with the monomer during polymerization having a surface roughness of not greater than 5 .mu.m and being previously coated with a scaling preventive comprising at least one selected from dyes, pigments and aromatic or heterocyclic compounds having at least 5 conjugated .pi. bonds.
According to the process of the present invention, the scaling preventive action possessed by the above scaling preventive can be induced surely and potently, whereby scaling can effectively be prevented. Accordingly, no labor or time is required for scale removal, enabling continuous use of the polymerizer and improved running efficiency. Also, the cooling capacity of the polymerizer can be maintained constantly, without any fear of entrainment of scales into the product, thereby improving the quality of the product polymer.
The term "surface roughness" used herein means the Rmax (maximum height) as defined in Japanese Industrial Standard (JIS) B 0601. The surface roughness Rmax can be measured by a probe method (JIS B 0651) or an optical method (JIS B 9652), or the like.
It is difficult to elucidate the reason why scaling can be prevented effectively when the surface roughness of the surface to be coated with the scaling preventive is previously controlled to 5 .mu.m or below, preferably 3 .mu.m or below, in accordance with the present invention. However, where the surface roughness is in excess of 5 .mu.m, the effect of the abovementioned scaling preventive is not fully displayed; namely, the scaling cannot be prevented effectively, even if the scaling preventive is applied to the inner wall surfaces of the polymerizer, etc.
The process of the present invention can be applied irrespective of the materials constituting the inner wall surface of the polymerizer and the portions of the auxiliary equipment thereof which may come into contact with the monomer. The polymerizer and its auxiliary equipment are generally formed of such materials as stainless steel, carbon steel, Monel metal, titanium, etc., and in some cases the inner wall surface of the polymerizer is lined with glass. In the case of any such materials, scaling can be prevented effectively by controlling the surface roughness to 5 .mu.m or below prior to coating the surface with the scaling preventive.
Where the original surface roughness of the inner wall surfaces of the polymerizer, etc. is in excess of 5 .mu.m, the surface roughness should be controlled to 5 .mu.m or below by an appropriate polishing method, prior to coating the surface with the scaling preventive. The polishing methods which can be employed are not particularly limited; examples of such methods include buffing, electrolytic polishing, and polishing with emery paper.
According to the present invention, one or more compounds selected from dyes, pigments and aromatic or heterocyclic compounds having at least 5 conjugated .pi. bonds (hereinafter referred to simply as "conjugated .pi. bond compounds") may be used singly or in combination. However, it is preferable to use a dye or pigment, and more preferably an azine dye.
The dyes and pigments which can be used as the scaling preventive in the process of the present invention may be exemplified by:
azo dyes such as monoazo and polyazo dyes and pigments, metal complex azo dyes and pigments, stilbene azo pigments, thiazole azo dyes and the like;
anthraquinone dyes and pigments such as anthraquinone derivatives, anthrone derivatives and the like;
indigoid dyes and pigments such as indigo derivatives, thioindigo derivatives and the like;
phthalocyanine dyes and pigments;
carbonium dyes and pigments such as diphenylmethane dyes, triphenylmethane dyes and pigments, xanthene dyes, macridine dyes and the like;
quinoneimine dyes such as azine dyes, oxazine dyes, thiazine dyes and the like;
methine dyes such as polymethine or cyanine dyes and the like;
quinoline dyes;
nitro dyes;
benzoquinone and naphthoquinone dyes;
naphthalimide dyes and pigments;
perinone dyes;
sulfide dyes;
fluorescent dyes;
azoic dyes; and
reactive dyes.
These can be used either singly or in any desired combination of two or more compounds. Of these dyes and pigments as exemplified above, particularly preferred are azine dyes, as mentioned above. More specifically, typical examples of these dyes and pigments are enumerated below.
Azo dyes and pigments include the following compounds. Exemplary monoazo and polyazo dyes are Basic Yellow 32, 34 and 36; Basic Orange 2, 32, 33 and 34; Basic Red 17, 18, 22, 23, 24, 32, 34, 38, 39 and 40; Basic Violet 26 and 28; Basic Blue 58, 59, 64, 65, 66, 67 and 68; Basic Brown 1, 4, 11 and 12; Basic Black 8; Azoic Diazo Component 4, 21, 27 and 38; Disperse Yellow 3, 4, 5, 7, 8, 23, 50, 60, 64, 66, 71, 72, 76, 78 and 79; Disperse Orange 1, 3, 5, 13, 20, 21, 30, 32, 41, 43, 45, 46, 49, 50 and 51; Disperse Red 1, 5, 7, 12, 13, 17, 43, 52, 54, 56, 58, 60, 72, 73, 74, 75, 76, 80, 82, 84, 88, 90, 97, 99, 101, 103, 113, 117, 122, 125, 126, 128 and 129; Disperse Violet 10, 24, 33, 38, 41, 43 and 96; Disperse Blue 85, 92, 94 and 106; Disperse Brown 3 and 5; Disperse Black 1, 2, 10, 26, 27, 28, 29, 30 and 31; Solvent Yellow 2, 6, 14, 15, 16, 19, 21 and 56; Solvent Orange 1, 2, 5, 6, 14 and 45; Solvent Red 1, 3, 23, 24, 25, 27 and 30; Solvent Brown 3, 5 and 20; Solvent Black 3; Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73 and 83; Pigment Orange 1, 2, 5, 13, 14, 15, 16, 17, 24 and 31; Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 112, 114 and 163; Pigment Blue 25; Pigment Green 10; Pigment Brown 1 and 2; Pigment Black 1; Direct Yellow 1, 8, 11, 12, 24, 26, 27, 28, 33, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100 and 110; Direct Orange 1, 6, 8, 10, 26, 29, 39, 41, 49, 51, 57, 102 and 107; Direct Red 1, 2, 4, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230 and 231; Direct Violet 1, 7, 9, 12, 22, 35, 51, 63, 90, 94 and 98; Direct Blue 1, 2, 6, 8, 15, 22, 25, 71, 76, 77, 78, 80, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 203, 207, 225, 236, 237, 246, 248 and 249; Direct Green 1, 6, 8, 28, 30, 31, 33, 37, 59, 63, 64 and 74; Direct Brown 1A, 2, 6, 25, 27, 44, 58, 59, 101, 106, 173, 194, 195, 209, 210 and 211; Direct Black 17, 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 94, 105, 106, 107, 108, 112, 113, 117, 118, 132, 133 and 146; Acid Yellow 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 61, 70, 72, 75, 76, 78, 79, 110, 127, 131, 135, 141, 142, 164 and 165; Acid Orange 1, 7, 8, 10, 19, 20, 24, 28, 33, 41, 43, 45, 51, 56, 63, 64, 65, 67 and 95; Acid Red 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 57, 75, 77, 85, 88, 89, 97, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 249, 252, 254, 257, 262, 265, 266, 274, 276, 282, 283 and 303; Acid Violet 7, 11, 97 and 106; Acid Blue 29, 60, 92, 113, 117 and 120; Acid Green 19, 20 and 48; Acid Brown 2, 4, 13, 14, 20, 53, 92, 100, 101, 236, 247, 266, 268, 276, 277, 282, 289, 301 and 302; Acid Black 1, 7, 24, 26, 29, 31, 44, 76, 77, 94, 109 and 110; Mordant Yellow 1, 3, 5, 23, 26, 30, 38 and 59; Mordant Orange 1, 4, 5, 6, 8, 29 and 37; Mordant Red 7, 9, 17, 19, 21, 26, 30, 63 and 89; Mordant Violet 5 and 44; Mordant Blue 7, 13, 44, 75 and 76; Mordant Green 11, 15, 17 and 47; Mordant Brown 1, 14, 15, 19, 21, 33, 38, 40, 52 and 87; Mordant Black 1, 3, 7, 9, 11, 17, 26, 32, 38, 43, 44, 51, 54, 65, 75, 77, 84, 85, 86 and 87; Food Yellow 3 and 4; Food Red 7 and 9;
exemplary metal complex azo dyes are Solvent Yellow 61 and 80; Solvent Orange 37, 40 and 44; Solvent Red 8, 21, 83, 84, 100, 109 and 121; Solvent Brown 37; Solvent Black 23; Acid Black 51, 52, 58, 60, 62, 63, 64, 67, 72, 107, 108, 112, 115, 118, 119, 121, 122, 123, 131, 132, 139, 140, 155, 156, 157, 158, 159 and 191; Acid Yellow 59, 98, 99, 111, 112, 114, 116, 118, 119, 128, 161, 162 and 163; Acid Orange 74, 80, 82, 85, 86, 87, 88, 122, 123 and 124; Acid Red 180, 183, 184, 186, 194, 198, 199, 209, 211, 215, 216, 217, 219, 256, 317, 318, 320, 321 and 322; Acid Violet 75 and 78; Acid Blue 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 184, 187, 192, 199, 229, 234 and 236; Acid Green 7, 12, 35, 43, 56, 57, 60, 61, 65, 73, 75, 76, 78 and 79; Acid Brown 19, 28, 30, 31, 39, 44, 45, 46, 48, 224, 225, 226, 231, 256, 257, 294, 295, 296, 297, 299 and 300; Direct Yellow 39; Direct Violet 47 and 48; Direct Blue 90, 98, 200, 201, 202 and 226; Direct Brown 95, 100, 112 and 170;
an exemplary stilbene azo dye is Direct Black 62, and
exemplary thiazole azo dyes are Direct Red 9 and 11.
Anthraquinone dyes and pigments include the following compounds.
Exemplary anthraquinone derivatives are Basic Violet 25; Basic Blue 21, 22, 44, 45, 47, 54 and 60; Azoic Diazo Component 36; Vat Yellow 2, 3, 10, 20, 22 and 33; Vat Orange 13 and 15; Vat Red 10, 13, 16, 31, 35 and 52; Vat Violet 13 and 21; Vat Blue 4, 6, 8, 12, 14, 64, 66, 67 and 72; Vat Green 8, 13, 43, 44 and 45; Vat Brown 1, 3, 22, 25, 39, 41, 44, 46, 57, 68, 72 and 73; Vat Black 8, 14, 20, 25, 27, 36, 56, 59 and 60; Disperse Orange 11; Disperse Red 4, 9, 11, 15, 53, 55, 65, 91, 92, 100, 104, 116 and 127; Disperse Violet 1, 4, 8, 23, 26, 28, 30 and 37; Disperse Blue 1, 3, 5, 6, 7, 20, 26, 27, 54, 55, 56, 60, 61, 62, 64, 72, 73, 75, 79, 81, 87, 90, 91, 97, 98, 99, 103, 104 and 105; Disperse Yellow 51; Solvent Violet 13 and 14; Solvent Blue 11, 12, 35 and 36; Solvent Green 3; Pigment Red 83 and 89; Pigment Blue 22; Acid Violet 31, 34, 35, 41, 43, 47, 48, 51, 54, 66 and 68; Acid Blue 23, 25, 27, 40, 41, 43, 45, 54, 62, 72, 78, 80, 82, 112, 126, 127, 129, 130, 131, 138, 140, 142, 143, 182, 183, 203, 204 and 205; Acid Green 25, 27, 28, 36, 40, 41 and 44; Acid Brown 27; Acid Black 48 and 50; Mordant Red 3 and 11; Mordant Blue 8 and 48; Mordant Black 13; Pigment Violet 5;
exemplary anthrone derivatives are Vat Yellow 1 and 4; Vat Orange 1, 2, 3, 4 and 9; Vat Violet 1, 9 and 10; Vat Blue 18, 19 and 20; Vat Green 1, 2, 3 and 9; Vat Black 9, 13, 29 and 57; Vat Red 13; Acid Red 80, 82 and 83.
Indigoid dyes and pigments include the following compounds.
Exemplary indigo derivatives are Vat Blue 1, 3, 5, 35 and 41; Reduced Vat Blue 1; Pigment Violet 19 and 122; Acid Blue 74 and 102; Solubilized Vat Blue 5 and 41; Solubilized Vat Black 1; Food Blue 1;
exemplary thioindigo derivatives are Vat Orange 5; Vat Red 1, 2 and 61; Vat Violet 2 and 3; Pigment Red 87 and 88; Vat Brown 3.
Phthalocyanine dyes and pigments may include, for example, Solvent Blue 55; Pigment Blue 15, 16 and 17; Pigment Green 36, 37 and 38; Direct Blue 86 and 199; Mordant Blue 58.
Carbonium dyes and pigments include the following compounds.
An exemplary diphenylmethane dye is Basic Yellow 2;
exemplary triphenylmethane dyes are Basic Red 9; Basic Violet 1, 3 and 14; Basic Blue 1, 5, 7, 19, 26, 28, 29, 40 and 41; Basic Green 1 and 4; Solvent Violet 8; Solvent Blue 2 and 73; Pigment Violet 3; Pigment Blue 1, 2 and 3; Pigment Green 1, 2 and 7; Direct Blue 41; Acid Violet 15 and 49; Acid Blue 1, 7, 9, 15, 22, 83, 90, 93, 100, 103 and 104; Acid Green 3, 9 and 16; Mordant Violet 1; Mordant Blue 1, 29 and 47; Food Violet 2; Food Blue 2; Food Green 2;
exemplary xanthene dyes are Basic Red 1; Solvent Red 49; Pigment Red 81 and 90; Pigment Violet 1, 2 and 23; Acid Red 51, 52, 87, 92 and 94; Mordant Red 15 and 27; Food Red 14;
exemplary acridine dyes are Basic Orange 14 and 15.
Quinoimine dyes include the following compounds.
Exemplary azine dyes are Basic Red 2; Basic Black 2; Solvent Black 5 and 7; Acid Blue 59; Acid Black 2;
exemplary oxiazine dyes are Basic Blue 3; Direct Blue 106 and 108;
exemplary thiazine dyes are Basic Yellow 1; Basic Blue 9, 24 and 25.
Methine dyes include the following compounds.
Exemplary polymethine (or cyanine) dyes are Basic Yellow 11, 13, 14, 19, 21, 25, 28, 33 and 35; Basic Orange 21 and 22; Basic Red 12, 13, 14, 15, 27, 29, 35, 36 and 37; Basic Violet 7, 15, 21 and 27.
Quinoline dyes may be exemplified by Basic Green 6; Disperse Yellow 54 and 56; Solvent Yellow 33; Acid Yellow 3.
Nitro dyes may be exemplified by Disperse Yellow 1, 33, 39, 42, 49 and 54; Acid Yellow 1.
Benzoquinone and naphthoquinone dyes may be exemplified by Disperse Blue 58 and 108; Acid Brown 103, 104, 106, 160, 161, 165 and 188.
Naphthalimide dyes and pigments may be exemplified by Pigment Red 123; Vat Violet 23 and 39; Acid Yellow 7.
Perinone dyes may be exemplified by Vat Orange 7 and 15.
Sulfide dyes may include, for example, Solubilized Sulfur Yellow 2; Sulfur Yellow 4; Sulfur Orange 3, Sulfur Red 2, 3, 5 and 7; Solubilized Sulfur Blue 15; Sulfur Blue 2, 3, 4, 6, 7, 9 and 13; Sulfur Green 2, 3, 6, 14 and 27; Solubilized Sulfur Brown 1 and 51; Sulfur Brown 7, 12, 15 and 31; Sulfur Black 1, 2, 5, 6, 10, 11 and 15; Vat Yellow 35, 42 and 43; Vat Blue 43 and 56.
Fluorescent dyes may include, for example, fluorescent brightening agents 14, 22, 24, 30, 32, 37, 45, 52, 54, 55, 56, 84, 85, 86, 87, 90, 91, 104, 112, 121, 134, 135, 153, 162, 163, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 and 177.
Azoic dyes may include, for example, Azoic Diazo Component 17, 20, 22, 24, 26, 31, 35, 41, 47, 48, 109 and 121; Azoic Coupling Component 2, 3, 4, 5, 7, 8, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20, 23, 26, 28, 29, 35, 36, 37, 41 and 108; Azoic Brown 2, 7, 11 and 15; Azoic Black 1 and 5; Azoic Yellow 1 and 2; Azoic Orange 2, 3 and 7; Azoic Red 1, 2, 6, 9, 16 and 24; Azoic Violet 1, 2, 6, 7, 9 and 10; Azoic Green 1.
Reactive dyes may include, for example Reactive Yellow 1, 2, 3, 4, 6, 7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37 and 42; Reactive Orange 1, 2, 4, 5, 7, 13, 14, 15, 16, 18, 20, 23 and 24; Reactive Red 1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 49, 50, 58, 59, 63 and 64; Reactive Violet 1, 2, 4, 5, 8, 9 and 10; Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21, 25, 26, 27, 28, 29, 31, 32, 33, 34, 37, 38, 39, 40, 41, 43, 44 and 46; Reactive Green 5, 6, 7 and 8; Reactive Brown 1, 2, 5, 7, 8, 9, 10, 11, 14 and 16; Reactive Black 1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14 and 18.
Further, pigments may be exemplified by inorganic pigments such as Chrome Yellow, Zinc Yellow, ZTO type zinc chromate, red lead, iron oxide powder, zinc white, aluminum powder and zinc powder.
The "conjugated .pi. bond" possessed by the conjugated .pi. bond compound which may be used as the scaling preventive in the process of the present invention herein means two or more double bonds and/or triple bonds in conjugated relationship. And, the aromatic compounds having at least 5 conjugated .pi. bonds which may be used in the present invention may include benzene derivatives, naphthalene derivatives, polynuclear aromatic compounds, quinones, non-benzene type aromatic compounds, etc., having at least five conjugated .pi. bonds. On the other hand, the heterocyclic compounds having at least 5 .pi. bonds may include, for example, oxygen-containing heterocyclic compounds, nitrogen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds, bicyclic compounds having a nitrogen atom in common, alkaroids, etc., having at least 5 conjugated .pi. bonds. Specific examples of these compounds are enumerated below.
The aromatic compounds having at least 5 bonds include the following compounds.
First, as benzene derivatives, there may be included:
phenols and derivatives thereof, such as 2,6-ditert-butylphenylphenol, catecholphthalein, 2,2-diphenylolpropane, 3,7-dioxy-10-methylxanthene, phenolphthalein, 7-oxy-2,4-dimethylbenzopyrooxonium chloride, oxyanthraquinone, purpurogallin, Gallein, diphenylether, .alpha.-methoxyphenazine, chloroglucide, 2,3-dioxyanthraquinone, 5,7-dioxy-4-methylcoumarine, dioxyacridone, salicylic acid, .alpha.-hydrindone, .beta.-phenylbutyrophenyl, N-2,4-dinitrophenyl-N-phenylhydroxylamine, 1-(4-nitrophenyl)-3,5-dimethylpyrazole, 9,10-diphenylphenanthrene, acetophenone;
aromatic amines and derivatives thereof, such as N-phenyl-p-benzoquinonediamine, quinoline, Safranine B, Rosaniline, Indiurine Spirit Soluble, Aniline Black, Para-Rosaniline, Methyl Violet, Methyl Orange, Methyl Red, Indigo, carbazole, Methylene Blue, o-phenanthroline, p-phenanthroline, 3,6-diaminoacridine, Indanthrene Scarlet 2G, 4-aminodiphenylamine, Acridine Yellow, 3-aminophenothiazine, N'-diphenyl-p-phenylenediamine, Rhodamine, 7-amino-4-methylcoumarine, 2-aminophenazine, phenothiazine, diphenylamine, N-methylphenylamine, N-phenyltolylamine, ditolylamine, 2-oxy-4-methylquinoline, Hansa Yellow G, N,N'-diphenylformamidine, phenanthrophenazine, Bismarck Brown G, 2,3-diaminophenazine, 2-aminodiphenylamine, Chrysodine R, 2,3,7,8-tetraaminophenazine, aminophenoxazone, oxyphenoxazone, Triphenylenedioxazine, 2,4-dinitrophenoxazine, 2',4'-dinitro-4-oxy-3-aminophenylamine;
nitro and nitroso derivatives, such as p-nitrosodiphenylhydroxylamine, phenazine, phenazine oxide, 1-phenylazo-2-naphthol, 4-nitroxanthone, 4'-nitroso-2-nitrodiphenylamine;
phenylhydroxylamine derivatives, such as 4,4'-dinitrodiphenylamine, oxalic acid bis(.beta.-phenylhydrazine), malonic acid bis(.beta.-phenylhydrazine), succinic acid bis(.beta.-phenylhydrazine), phthalic acid bis(.beta.-phenylhydrazine);
aromatic halides, such as biphenyl chloride;
aromatic aldehydes, such as 2-phenyl-1-benzyl-benzimidazole, Leucomalachite Green, Malachite Green, tetrachlorohydroquinone monobenzoate, benzoflavin, 2-phenylbenzthiazole, 4-benzhydrylbenzaldehyde, bisphenylhydrazone, bis(4-nitrophenylhydrazone);
aromatic ketones such as triphenylisooxazole, benzophenone potassium, 4-methylbenzophenone, p-toluyl acid anilide, benzoic acid toluidide, duryl phenyl ketone, 2,4,2',4'-tetramethylbenzophenone, calchonphenylhydrazone, 1,3,5-triphenylpyrazoline, dinitrobenzyl;
benzoic acids, phthalic acids and derivatives thereof, such as quinizaline, nitrodiphenylether;
benzene derivatives having further one substituent other than aldehyde group, such as disalicylaldehyde, coumarine, 2-benzoylcoumarone, 1-oxy-2,4-dimethylfluorone, 3-phenylcoumarone, ethyl coumarine-3-carboxylate, 3-acetylcoumarine, hydrovaniloin, 4-oxy-3-methoxy-.omega.-nitrostyrene, .alpha.-(nitrophenyl)-.beta.-benzoylethyleneoxide, dinitrophenylindazole, 5-chloro-3-(4-oxyphenyl)anthranil, 3-nitroacridone, 6-nitro-3-phenylanthranil, 2,8-dimethyl-1,9-anthrazoline, carbostyril, 1,3-dioxyacridine, oxyquinacdine, Phlorchinyl, 2-methylquinazoline, 3-acetyl-2-methylquinoline, 2-oxy-3-phenylquinoline, 3-nitroquinoline, quinoline-2,3-dicarboxylic acid ester;
benzene derivatives having further one substituent other than acyl group, such as 7-oxyflavanone, 7-oxyflavone, 7,8-dioxyflavone, 7-acetoxy-4-methyl-3-phenylcoumarine, 7,8-diacetoxy-4-methyl-3-phenylcoumarine, o-oxybenzophenone, xanthone, 2-phenylbenzooxazole, m-oxybenzophenone, p-oxybenzophenone, 2-benzoylxanthone, 2,4-dioxybenzophenone, 2,5-dioxybenzophenone, 2,2'-dioxybenzophenone, xanthene, aurin, trioxybenzophenone, 6,7-dimethoxy-3-phenylcoumarone, o-nitrobenzophenone, m-nitrobenzophenone, 4,4'-dibenzoylazoxybenzene, 2-(2-aminophenyl)-4-methylquinone, 2-oxy-4-methylquinone, acridone, 2,4-dimethylquinazoline, 3-cyan-2-oxy-4-methylquinoline, fluorene, anhydro(2-aminobenzophenone) dimer, 2-oxy-3-phenylindazole, 3-phenylindazole, 2-phenylbenzimidazole, 2-methyl-8-benzoylquinoline, 2-methyl-4-phenylquinoline, 4-phenyl-2-quinazolone, aminobenzophenone, chlorobenzophenone, 4-phenylbenzo-1,2,3-triazine-3-oxide, diaminobenzophenone, 7-methyl-3-phenyl-4,5-benzo-1,2,6-oxydiazine, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenoneimide, 2,4-dinitro-9-phenylacridine, 4,4'-dibenzoyldiphenyl;
benzene, toluene derivatives having three or more different substituents, such as tetramethoxyindigo, 5,6,5',6'-bismethylenedioxyindigo, 7-acetoxy-8-methoxy-3-(2-nitrophenyl)carbostyril, 2,2'-dinitrodiphenyldisulfide-4,4'-dialdehyde, 6-chloro-3-benzoylflavone, 1,3,8-trinitrophenoxazine;
aralkyl compounds, such as 9-benzylacridine;
diazo compounds and azo compounds, such as azobenzene, azotoluene, 2,2-dimethoxyazobenzene, 4,4'-dichloroazobenzene, 1,1'-azonaphthalene, 2,2'-dioxyazobenzene, 2,2'-dioxy-5,5'-dimethylazobenzene, p-bromoazobenzene, p-nitroazobenzene, phenoazoxide;
aromatic unsaturated compounds, such as 2,3,4,5-tetraphenylcyclopentane-2-ene-1-one, 1,2,3-triphenyleneazulene, 2,2'-dimethyldiphenylacetylene, 4,4'-diethyldiphenylacetylene, 3,4,3',4'-tetramethyldiphenylacetylene, 2,2'-dichlorodiphenylacetylene, 2,2'-dibromodiphenylacetylene, 2-nitrodiphenylacetylene, 2,2'-dinitrodiphenylacetylene, 2,2'-diaminodiphenylacetylene, 2,2'-dimethoxydiphenylacetylene, stilbene, .alpha.-methylstilbene, .alpha.-ethylstilbene, .alpha.,.beta.-dimethylstilbene, .alpha.,.beta.-diethylstilbene, .alpha.,.beta.-dichlorostilbene, .alpha.,.beta.-debromostilbene, 2-chlorostilbene, 4,4'-diiodostilbene, .alpha.-nitrostilbene, .alpha.,.beta.-dinitrostilbene, 2,4,6-trinitrostilbene, 2-aminostilbene, 2,2'-diaminostilbene, 4,4'-di(dimethylamino)stilbene, 2,2'-dicyanstilbene, 2-oxystilbene, 2-methoxystilbene, 2,2'-dioxystilbene, 2,2'-dimethoxystilbene, 4,4'-dialkoxystilbene, 3,5,2',4'-tetraoxystilbene; and
polyphenyls and derivatives thereof, such as biphenyl, terphenyl, quaterphenyl, quinophenyl, sexiphenyl, septiphenyl, octiphenyl, noviphenyl, deciphenyl, etc.
Next, as naphthalene derivatives, there may be included:
alkyl, alkenyl and phenylnaphthalenes, such as 1-methylnaphthalene, 2-methylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 1,2-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 1,7-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, 2,7-dimethylnaphthalene, 1-propylnaphthalene, 1-isopropylnaphthalene, 2-isopropylnaphthalene, trimethylnaphthalene, diisopropylnaphthalene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-propenylnaphthalene, 1-allylnaphthalene, 1-isopropenylnaphthalene, 2-isopropenylnaphthalene, 1-phenylnaphthalene, 2-phenylnaphthalene, 1,4-diphenylnaphthalene, 1,2,4-triphenylnaphthalene;
dinaphthyls, such as 1,1'-dinaphthyl, 1,2'-dinaphthyl, 2,2'-dinaphthyl;
naphthylarylmethanes, such as 1-benzylnaphthalene, 2-benzylnaphthalene, 1-(.alpha.-chlorobenzyl)naphthalene, 1-(.alpha.,.alpha.-dichlorobenzyl)naphthalene, diphenyl-.alpha.-naphthylmethane, diphenyl-.beta.-naphthylmethane, 1,8-dibenzylnaphthalene, di-.alpha.-naphthylmethane, .alpha.-naphthyl-.beta.-naphthylmethane, di-.beta.-naphthylmethane;
naphthylarylethanes, such as 1-phenethylnaphthalene, 1,2-di-.alpha.-naphthylethane, 1,2-di-.beta.-naphthylethane, 1,1-.alpha.-dinaphthylethane;
hydronaphthalenes such as 1,2-dihydronaphthalenes, 1,4-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalene;
nitronaphthalenes and derivatives thereof, such as dinaphthylpyridazine, 7,8-benzoquinone, 5,6-benzoquinone, naphthazarine, diperimidine, nitromethylnaphthalene, nitromethylnaphthalene, nitrophenylnaphthalene, halo-nitronaphthalene, halo-dinitronaphthalene, nitrosonaphthalene, dinitrotetraline, dibenzophenazine, methylbenzoindole, 9-chloro-1azaanthracene, quinolinoquinoline, 1,2,3-triazaphenarene, perimidone, perimidine, dibenzoacridine, benzophenazine-12-oxide, diaminonaphthalene, triaminonaphthalene, tetraaminonaphthalene, N-ethyl-.alpha.-naphthylamine, N-methylnaphthylamine, N,N-dimethylnaphthylamine, N-methyl-N-ethylnaphthylamine, N-methyl-N-ethylnaphthylamine, trimethylnaphthyl ammonium salt, N-phenylnaphthylamine, N-benzylnaphthylamine, N-naphthylethylenediamine, N-naphthylglycine, N-.beta.-cyanomethylnaphthylamine, N-acetylnaphthylamine, N-formylnaphthylamine, N-benzoylnaphthylamine, N-phthaloylnaphthylamine, aminomethylnaphthalene, nitronaphthylamine, dinitronaphthylamine, halo-nitronaphthylamine, aminotetraline, diaminotetraline;
halogenated naphthalenes, such as 1-fluoronaphthalene, 1-chloronaphthalene, 1-chloro-3,4-dihydronaphthalene, 1-iodonaphthalene, 1-bromonaphthalene, 1-chloro-4-chloromethylnaphthalene, 1-bromo-2-(bromometh)naphthalene, 1,4-difluoronaphthalene, 1,2-dichloronaphthalene, 1,6-dichloronaphthalene, 1,7-dichloronaphthalene, 1,5-dichloronaphthalene, 1,8-dichloronaphthalene, 2,3-dichloronaphthalene, 1,4-dibromonaphthalene, 1,4-diiodonaphthalene, perylene, 1,2,3-trichloronaphthalene, 1,2,4-tribromonaphthalene, 1,2,3,4-tetrachloronaphthalene, 1,4,5-tribromo-3,8-dimethylnaphthalene, 1,3,6,7-tetrachloronaphthalene, 1,3,5,8-tetrabromonaphthalene, 1,2,3,4,5-pentachloronaphthalene;
naphthylhydroxylamines, naphthylpyrazines and naphthylureas, such as .alpha.-naphthylhydroxylamine, N'-phenyl-N-.alpha.-naphthyl-N-oxyurea, .beta.-naphthylthiohydroxylamine, N-nitroso-.alpha.-naphthylhydroxylamine, Neocupferron, 2-oxy-1,1'-azonaphthalene, .alpha.-naphthylhydrazine, 1,2-dibenzocarbazole, 4,4-diamino-1,1'-binaphthyl, 3,4-benzcarbazole, 2,2'-diamino-1,1'-binaphthyl, N'-acetyl-N-.beta.-naphthylhydrazine, N'-lauroyl-N-.beta.-naphthylhydrazine, N'-phenyl-N-.beta.-naphthylhydrazine, N'-(2,4-dinitrophenyl)-N-.alpha.-naphthylhydrazine, 2-.alpha.-naphthyl-5-nitrobenztriazole, N,N'-di-.alpha.-naphthylhydrazine, 1,1'-diamino-2,2'-binaphthyl, N,N'-di-5-tetralylhydrazine, N'-(2,4-dinitrophenyl)-N-.beta.-naphthylhydrazine, 2-.beta.-naphthyl-5-nitrobenztriazole, N'-triphenylmethyl-N-.beta.-naphthylhydrazine, N,N'-di-.beta.-naphthylhydrazine, N-methyl-N-(2,4-dinitro-1-naphthyl)hydrazine, 2-amino(naphtho-1',2'-:4,5-thiazole), 1,2:5,6-dibenzophenazine, 2-amino-(naphtho-2',1':4,5-thiazole), 2,3-dihydrazinonaphthalene, 2-phenyl-1,3-bisbenzylideneamino(naphtho-2',3':4,5-imidazoline), N-acetyl-.alpha.-naphthylnitrosoamine, N-ethyl-.alpha.-naphthylnitrosoamine, N-phenyl-.alpha.-naphthylnitrosoamine, .alpha.,.alpha.'-dinaphthylnitrosoamine, succinic acid bis(.beta.-naphthylnitrosoamide), N-ethyl-.beta.-naphthylnitrosoamine, N-phenyl-.beta.-naphthylnitrosoamine, N-acetyl-2-methyl-1-naphthylnitrosoamine, 4,5-benzindazole, naphthylnitrosoamine, 1-nitro-2-naphthylamine, .alpha.-naphthylurea, N,N'-di-.alpha.-naphthylurea, 4-chloro-1-naphthylcarbamoylchloride, 2,4'-dichloro[naphtho-1',2':4,5-thiazole], 2-mercapto[naphtho-1',2'-:4,5-thiazole], 2-chloro[naphtho-1',2':4,5-thiazole], 2-mercapto[naphtho-2',1':4,5-thiazole], 2-chloro[naphtho-2',1':4,5-thiazole];
naphthalene type aralkyl compounds, such as dibenzoanthracene, acenaphthene, .alpha.-chloroethylnaphthalene, phenylnaphthylchloromethane, diphenylnaphthylchloromethane, nitromethylnaphthalene, aminomethylnaphthalene, (naphthylmethyl)amine, .alpha.-phenyl(naphthylmethyl)amine, N-benzyl(naphthylmethyl)amine, trimethyl(naphthylmethyl)ammonium salt, tri(naphthylmethyl)amine, di(naphthylmethyl)amine, (.beta.-naphthylethyl)alcohol, dimethylnaphthylcarbinol, phenylnaphthylcarbinol, diphenylnaphthylcarbinol, 9-phenylbenzofluorene, naphthylpropyleneoxide, ethyl(naphthylmethyl)ether, phenyl(naphthylmethyl)ether, naphthylacetaldehyde, naphthylacetone, .omega.-naphthylacetophenone, acenaphthenone, dihydrophenarone, phenarone, benzoindanone, naphthylacetonitrile, 9,9'-dichlorodibenzofluorene, .alpha.-nitro-.beta.-naphthylethylene, .gamma.-naphthylallyl alcohol, .beta.-naphthylacrolein, methyl(.beta.-naphthylvinyl)ketone, naphthylphenanthrene dicarboxylic acid anhydride;
naphthol, naphthalenesulfonic acids, such as 9-oxynaphthacenequinone, 2'-naphthalene-2-indoleindigo, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-phenoxynaphthalene, .alpha.-naphtholsalicylic acid ester, .beta.-naphthol, .alpha.-naphthol, .alpha.-naphtholbenzoic acid ester, .alpha.-naphtholacetic acid ester, phenyl-.beta.-oxynaphthylbenzaliminomethane, .beta.-naphtholphenylmethylamine, methylene-di-.beta.-naphthol, dinaphthopyrane, 1'-naphthol-2-indoleindigo, 2-methoxynaphthalene, 2-ethoxynaphthalene, N-p-oxyphenyl-2-naphthylamine base, .beta.-naphtholsalicylic acid ester, 2-methyl-1-naphthol, 1,2-naphthamethylenequinone, 1,2-dioxynaphthalene, naphthaleneindoleindigo, .alpha.,.beta.-naphthophenoxazine, .beta.,.gamma.-naphthophenoxazine, 4-oxy-10-methyl-1',2'-benzocarbazole, dioxynaphthfluorane, dinaphthoquinone, 2,6-naphthoquinone, oxybenzoacridine, 9-oxy-3-dimethylaminonaphthophenoxazine, 1,2,4-trioxynaphthalene, 1,4,5,6-tetraoxynaphthalene, thio-.alpha.-naphthol, 4-mercapto-1-naphthol, 1,5-naphthalenedithiol, methyl-.alpha.-naphthyl sulfide, 1,1'-naphthyl sulfide, 1,1'-thiodi-2-naphthol, 1,1'-naphthyl disulfide, 1,1'-thiodi-1-naphthol, thio-.beta.-naphthol, naphthothioindigo, 1-amino-2-naphthalenethiol, naphthothianthrene, 2-mercapto-1,2-naphthothiazole;
naphthoaldehydes and derivatives thereof, such as .alpha.-naphthoaldehyde, 2-(2,4-dinitrophenyl)-1-(.alpha.-naphthyl)ethylene, 2-methyl-1-naphthoaldehyde, 2,3-dimethyl-1-naphthoaldehyde, 4-bromo-1-naphthoaldehyde, 4-nitro-1-naphthoaldehyde, 2,4-dinitro-1-naphthoaldehyde, 4-amino-1-naphthoaldehyde, 2-oxy-1-naphthoaldehyde, 1-naphthalene-2'-indoleindigo, 1,2-bis(2-oxy-1-naphthyl)ethylene, 1,2:7,8-dibenzoxanthilium chloride, 2-oxy-1-naphthylethenyl pyrylium salt, 5,6-benzocoumarin, bis(2-methyl-3-indolyl)(2-oxy-1-naphthyl)methane, 4,5-benzindoxazene, 2-acetoxy-1-naphthonitrile, 4-methoxy-1-naphthoaldehyde, 1,4-bis(4-methoxy-1-naphthyl)-1,3-butadiene, 2-naphthalene-2'-indoleindigo, 3-acetyl-6,7-benzocoumarin, 4-chloro-1-oxy-2-naphthoaldehyde, naphthalenedialdehyde, 5-oxy-2-naphthaleneindoleindigo, 5,6,7,8-tetrahydro-2-naphthoaldehyde, imide chloride, naphthoamide, naphthoanilide, naphthonitrile, ethyl .beta.-naphthoimidate, .beta.-naphthamidine, .alpha.-naphthoamidoxime, .alpha.-naphthohydrazide, naphthostyryl, oxynaphthonitrile, 1,2:7,8-dibenzoxanthone, 1,2-benzoxanthone, 1,1'-binaphthylene-2,8';8,2'-dioxide, 2,3;6,7-dibenxozanthone, 3-oxy-2-naphthoanilide, 1,3-bis(3-oxy-2-naphthoyloxy)benzene, 2,4-dioxyphenyl-3-oxy-2-naphthyl ketone, 4-arylazo-3-oxy-2-naphthoanilide, 3,4-dihydronaphthalene-1,2-dicarboxylic acid anhydride, 2-aminonaphthalimide, naphthalohydrazide, .alpha.-pyridonaphthalone, N-methylnaphthalimide; and
acetonaphthenes, benzoylnaphthenes, such as 1,2:5,6-dibenzanthracene, 2'-methyl-2,1'-dinaphthyl ketone, 2-methyl-1,1'-dinaphthyl ketone, styryl-2-naphthyl ketone, .beta.-naphthoyl acetone, .beta.-naphthoylacetophenone, 1-(.beta.-naphthyl)-1-chloroethylene, 2-[tris(.beta.-cyanoethyl)acetyl]naphthalene, 1,3,5-tris(.beta.-naphthyl)benzene, dimethyl-2-naphthylcarbinol, 4,5:4',5'-dibenzothioindigo, styryl-1-naphthyl ketone, .beta.-acetonaphthone, 1-propionylnaphthalene, 1-butylnaphthalene, 1-isobutylnaphthalene, 1-stearoylnaphthalene, 1-benzoylnaphthalene, 1-o-toluylnaphthalene, p-biphenyl-1-naphthyl ketone, 1,2,5,6-dibenzanthracene, 1-acetyl-3,4-dihydronaphthalene, 1-acetyl-7-bromonaphthalene, 1-aminoacetylnaphthalene, 2-aminobenzoylnaphthalene, 1-acetyl-2-oxynaphthalene, 1-acetyl-2-methoxynaphthalene, 1-acetyl-4-ethoxynaphthalene, 2-cinnamoyl-1-naphthol, 7,8-benzochromone, 3-acetyl-2-methyl-7,8-benzochromone, 3,4-dimethyl-7,8-benzocoumarin, 4-methyl-3-phenyl-7,8-benzocoumarin, 1-benzoyl-2-oxynaphthalene, 4-oxybenzanthrone, 4-benzoyl-1-naphthol, 3-oxy-1,2-benzofluorenone, 2-acetyl-4-chloro-1-oxynaphthalene, .alpha.-naphthylglyoxal, .beta.-naphthylglyoxal, 1,4-dibenzoylnaphthalene, phenyl-4-methyl-1-naphthyldiketone, and the like.
Also, as the polynuclear aromatic compounds, there may be included:
anthracenes and derivatives thereof, such as anthracene, 1,2-dihydroanthracene, 1-chloroanthracene, 1,4-dichloroanthracene, 1,2,7-trichloroanthracene, 1,2,3,4-tetrachloroanthracene, 1-nitroanthracene, 9,10-dinitroanthracene, 1-aminoanthracene, 2-dimethylaminoanthracene, 2-anilinoanthracene, 9-methylaminoanthracene, 1,4-diaminoanthracene, 1-oxyanthracene, 9,10-dihydroanthrol, 10-methylanthranol, 10-phenylanthranol, 10-nitroanthranol, 2-amino-1-anthranol, 1,2-dioxyanthracene, 9,10-dioxyanthracene diacetate, 1-methylanthracene, 4-chloro-1-methylanthracene, 1,5-dichloro-2-methylanthracene, 9-ethylanthracene, 9-vinylanthracene, 9-propylanthracene, 9-isopropylanthracene, 9-butylanthracene, 9-isobutylanthracene, 9-isoamylanthracene, 1,3-dimethylanthracene, 9,10-diethylanthracene, 1-phenylanthracene, 9-phenylanthracene, 1,5-dichloro-9-phenylanthracene, 10-nitro-9-phenylanthracene, 9-benzylanthracene, 1-benzhydrylanthracene, 9,10-diphenylanthracene, 9,10-dibenzylanthracene, 9,10-diphenyl-9,10-dihydroanthracene, 1-(.beta.-naphthyl)anthracene, 9-(.alpha.-naphthyl)-10-phenylanthracene, 9,10-di(.alpha.-naphthyl)anthracene, 1,1'-bianthryl, 2,2'-bianthryl, 9,9'-bianthryl, anthracene-9-aldehyde, 1-acetylanthracene, 9-benzoylanthracene, 10-nitroanthraphenone, 9,10-dibenzoylanthracene, anthrone, 9-mercaptoanthracene, 9,10-disodium-9,10-dihydroanthracene, 10-bromo-9-anthrylmagnesium bromide, Anthryl-mercury chloride;
phenanthrenes and derivatives thereof, such as phenanthrene, 9,10-dihydrophenanthrene, 1,2,3,4-tetrahydrophenanthrene, 1-chlorophenanthrene, phenanthrene-9,10-dichloride, 1-bromophenanthrene, 1-iodophenanthrene, 9-(chloromethyl)phenanthrene, 1-(bromomethyl)phenanthrene, 4,5-bis(bromomethyl)phenanthrene, 1-nitrophenanthrene, 10-bromo-9-nitrophenanthrene, 1-aminophenanthrene, 9,10-diaminophenanthrene, 9,9'-azoxyphenanthrene, 9,9'-azophenanthrene, 1-oxyphenanthrene, cholesterol, estrone, androsterone, 10-bromo-9-phenanthrol, 9-nitro-3-phenanthrol, 4-amino-1-phenanthrol, 10-benzoazo-9-phenanthrol, 1,2-dioxyphenanthrene, retene-3,8-diol, 2,3,5,6-tetraoxyphenanthrene, 1-methylphenanthrene, 1-ethylphenanthrene, 1-vinylphenanthrene, 1,2-dimethylphenanthrene, 9,10-diethylphenanthrene, 9,10-dipropylphenanthrene, 2-ethyl-1-methylphenanthrene, 7-isopropyl-1-methylphenanthrene, 9,10-dihydroretene, aminoretene, 3-acetoaminoretene, 6-acylaminoretene, 9-phenylphenanthrene, 9-benzylphenanthrene, 1-(.alpha.-naphthyl)phenanthrene, 1,1'-biphenanthryl, 9,9'-biphenanthryl, 1-phenanthraldehyde, 2-phenanthraldehyde, 9-phenanthraldehyde, 1-acetylphenanthrene, 2-propionylphenanthrene, 3-acetylretene, 1-benzoylphenanthrene;
phenanthrenequinones, such as phenanthrene-1,2-quinone, phenanthrene-1,4-quinone, phenanthrene-3,4-quinone, phenanthrene-9,10-quinone, 2-phenyl-3-acetoxy-4,5-biphenylfuran, 7-isopropyl-1-methylphenanthrenequinone, 1-chlorophenanthrenequinone, 2-bromophenanthrenequinone, 2-iodophenanthrenequinone, 2,7-dibromophenanthrenequinone, 2-nitrophenanthrenequinone, 2,5-dinitrophenanthrenequinone, 2-aminophenanthrenequinone, 2,7-diaminophenanthrenequinone, 3,6-diaminophenanthrenequinone, 2,5-diaminophenanthrenequinone, 2-oxyphenanthrene-1,4-quinone, 3-oxyphenanthrenequinone, 2-oxyretenequinone, 3-oxyretenequinone, 6-oxyretenequinone, 2-oxy-3,4-dinitrophenanthrenequinone, 2-amino-3-oxyphenanthrenequinone; and
polynuclear aromatic compounds and derivatives thereof, such as pentacene, hexacene, benzophenanthrene, benzo[a]anthracene, naptho[2,1,a]pyrene, dibenzo[a,j]anthracene, pyrene, coronene, 1,12-benzopyrene, ovalene, dibenzoanthracene, naphthacene, Terramycin, Aureomycin, rubrene, o-toluoyl-1-naphthalene, benzoanthraquinone, 5,6-dioxy-5,6-dihydrobenzoanthracene, chrysene, triphenylene, dibenzonaphthacene, hexahydropyrene, perylene, 3,9-dichloroperylene, tetrachloroperylene, 3,9-dibromoperylene, 3,10-dinitroperylene, 4,6-dibenzoyl-1,3-dimethylbenzene, 6,13-dihydropentacene, naphtho[2,3-a]anthracene, dispirane, dibenzo[a,h]anthracene, picene, picyleneketone, picene-5,6-quinone, dibenzo[c,g]phenanthrene, benzo[a]pyrene, benzo[a]pyrene-1,6-quinone, mesobenzoanthrone pericarboxylic acid anhydride, anthraceno[2,1-a]anthracene, dibenzo[a,1]naphthacene, phenanthrene[2,3-a]anthracene, naphtho[2,3-a]pyrene, dibenzo[a,h]pyrene, dibenzo[a,1]pyrene, zethrene, anthanthrene, benzo[1,12]perylene, heptacene, tetrabenzo[a,c,h,j]anthracene, tribenzo[a,i,1]pyrene, tetrahydrodimethyldinaphthyl, mesonaphthodianthrene, mesoanthrodianthrene, 2,3;8,9-dibenzocoronene, pyranthrene, and the like.
As quinones and derivatives thereof, there may be included:
benzoquinones and derivatives thereof, such as dibenzoquinoyl disulfide, 2,5-bis(phenylthio)-p-benzoquinone, bibenzoquinone, bitoluquinone, phoenicin, Oosporein, indophenol, indoaniline, Hydron Blue, indamine, Meldola's Blue, Wurster's Blue, Wurster's Red, 4,4'-diphenoquinone, 4,4'-stilbenequinone, 3,5,3',5'-tetramethyl-4,4'-diphenoquinone, 3,5,3',5'-tetra-tert-butyl-4,4'-diphenoquinone, 3,5,3',5'-tetramethyl-4,4'-stilbenequinone, 3,5,3',5'-tetra-tert-butyl-4,4'-stilbenequinone;
naphthoquinones and derivatives thereof, such as 1,2-naphthoquinone, 3-oxy-2,2'-binaphthyl-1,4;3',4'-diquinone, 5,6-benzoquinoxaline, 1,2-benzophenazine, 2-benzoazo-1-naphthol, 4-(2,4-dioxyphenyl)-1,2-dioxynaphthalene, 4-(3,4,5-trioxyphenyl)-1,2-dioxynaphthalene, 1,2-naphthoquinone-1-phenylimide, 1,2-benzophenoxazine, 1,2-naphthoquinone-2-chloroimide, 1,2-naphthoquinone-bis-chloroimide, 2-anilino-1,4-naphthoquinone-4-anil, 2-oxy-1,4-naphthoquinone-4-anil, 1,2-naphthoquinone-1-oxime benzoate, 1,2-naphthoquinone-1-oxime methyl ether, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, naphtho[1',2':3,4]furazane, 1,2-naphthoquinone-2-oxime benzoate, 1,2-naphthoquinone-2-oxime methyl ether, 3-anilino-1,2;8,9-dibenzophenazine, Naphthyl Blue, Naphthyl Violet, 1,2;5,6-dibenzophenazine, naphtho[1',2':3,4]furazane-2-oxide, triphthaloylbenzene, hexaoxynaphthalene anhydride, 2,2'-binaphthyl-1,4;1',4'-diquinone, 1',4'-dioxynaphtho(2',3':3,4)pyrazole, 4,7-dioxy-3,3-diphenyl-5,6-benzindiazene, 2-diphenylmethyl-1,4-naphthoquinone, methylnaphtho[2',3':4,5]triazole-1',4'-quinone, 1,2,4-triacetoxynaphthalene, 1,4-naphthoquinonephenylimide, 1,4-naphthoquinone-mono(p-dimethylaminoanil), 1,4-naphthoquinonealkylimide, 4-nitroso-1-naphthol, phenylcarbamate, 4-nitroso-1-naphthylamine, 4-benzhydryl-1,2-naphthoquinone, 2-benzhydryl-1,4-naphthoquinone, 3-benzhydryl-2-methyl-1,4-naphthoquinone, 3-geranyl-2-methyl-1,4-naphthoquinone, 3-farnesyl-2-methyl-1,4-naphthoquinone, 2-methyl-3-phytyl-1,4-naphthoquinone, Vitamin K1, Vitamin K2, 3-allyl-2,6-dimethyl-1,4-naphthoquinone, 2,6-dimethyl-3-phytyl-1,4-naphthoquinone, 2,3-diallyl-6,7-dimethyl-1,4-naphthoquinone, 2-phenyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2,6-dimethyl-3-phenyl-1,4-naphthoquinone, 3-benzyl-2-methyl-1,4-naphthoquinone, 2-methyl-3-(.beta.-phenylethyl)-1,4-naphthoquinone, 3-cinnamyl-2-methyl-1,4-naphthoquinone, 2-benzhydryl-1,4-naphthoquinone, 4,7-diketo-8-diphenylmethyl-4,7,8,9-tetrahydro-5,6-benzindiazene, 2-methyl-3-diphenylmethyl-1,4-naphthoquinone, 2,3-diphenyl-1-naphthol, naphtho[2',3':3,4]-pyrazole-1',4'-quinone, 3,4-dichloro-1,2-benzophenazine, 2-iodo-1,4-naphthoquinone, 1,4,5,8-tetraoxy-2,3;6,7-dibenzothianthrene, 5,8-dioxy-2,3;6,7-dibenzothianthrene-1,4-quione, 2,3-diphenoxy-1,4-naphthoquinone, dinaphtho[2',3':2,3][1"2":5,4]furan-1',4'-quinone, 2,3,5,8-tetrachloro-1,4-naphthoquinone, N,N'-bis-(1,4-naphthoquinone-2-yl)-benzidine, 2-anilino-1,4-naphthoquinone-4-anil, 4-anilino-1,2-naphthoquinone-2-anil, phenylrosindarine, 2-anilino-1,4-naphthoquinone-4-(p-dimethylaminoanil), 2-anilino-1,4-naphthoquinonedianil, 2-anilino-3-phenyl-1,4-naphthoquinone, 2-anilino-3-bromo-1,4-naphthoquinone, 2-anilino-4-chloro-1,4-naphthoquinone, 2,3-dianilino-1,4-naphthoquinone, 2,3-dianilino-1,4-naphthoquinonedianil, nitrosoaminonaphthoquinone, 3-chloro-2-phenylnitrosoamino-1,4-naphthoquinone, phenyl-bis-(3-anilino-1,4-naphthoquinone-2-yl)amine, 3-chloro-2-(p-tolylnitrosoamino)-1,4-naphthoquinone, 2,7-dioxy-1-nitrosonaphthalene, 4-benzeneazo-1,3-dioxynaphthalene, di-(3-oxy-1,4-naphthoquinonyl-2-yl)-methane, anhydroalkannin, diquinoxalino[2',3':1,2:2",3":3,4]-naphthalene, 3,4-phthaloylfurazene; and
anthraquinones and derivatives thereof, such as 1,2-anthraquinone, 2,3-anthraquinone, 1,4-anthraquinone, 9,10-anthraquinone, 1,5-anthraquinone, 2,6-anthraquinone, 1,10-anthraquinone, 9,9-bis(p-oxyphenyl)anthrone, anthraquinone bisdiphenylmethide, bisphenylhydrazone, benzanthrone, anthrahydroquinone, .beta.-ethylanthraquinone, 1,3,5,7-tetramethylanthraquinone, 2,2'-dianthraquinonylethane, 2,2'-dianthraquinonylethylene, 1,2,3-trioxyanthraquinone, anthrachrysone, erythrooxyanthraquinone, alizarin, quinizarin, anthrarufin, chrysazin, hystazarin, anthraflavin, isoanthraflavin, anthragallol, purpin, oxyanthrarufin, anthrapurprin, oxychrysazin, oxyflavopurpurin, Rufiopin, quinazarin, alizarinpentacyanine, rufigallol, Anthracene Blue WR, alizarinhexacyanine, 2-chloroquinizarin, 1-nitroanthraquinone, 2,4,6,8-tetrabromoanthrachrysone, 3-aminoanthrapurpurin, 1,8-dinitroanthraquinone, .alpha.-aminoanthraquinone, 1,1'-dianthraquinonyl, dianthraquinoneimide, 1,4-dimethylaminoanthraquinone, 5-amino-1-nitro-6,8-dibromoanthraquinone, 1,5-tetramethyldiamino-4,8-dinitroanthraquinone, anthraquinoneacridone, bis-N-(2-oxyanthraquinolyl)p-phenylenediamine, leucoquinazarin, Quinazarin Green, 1-amino-2,4-dibromoanthraquinone, 1,4-diacylaminoanthraquinone, anthraquinone-.beta.-aldehyde, o-diazine, 6,7-phthaloyl-1,9-benzanthrone, oxynitrosoanthraquinone, 1,1'-dianthraquinolyl, azoxyanthraquinone, 8-chloropyrazoleanthrone, 2,6-dihydrazinoanthraquinone, anthraquinone diazonium salt, .beta.-anthraquinonehydrazine, azoxyanthraquinone, pyrazoleanthrone, 1-(anthraquin-2-yl)-3-methylpyrazolone, 1-hydroxylaminoanthraquinone, 1,5-dihydroxylaminoanthraquinone, 1-nitrosoanthraquinone, 1-hydrazinoanthraquinone, 1,5-dihydrazinoanthraquinone, 1-azidoanthraquinone, 2-azidoanthraquinone, anthraquinonemethylsulfoxide, 1,4-dirhodaneanthraquinone, .beta.,.beta.'-dianthraquinolyl sulfide, anthraquinonesulphenyl chloride, 2,2'-dianthraquinonyl, 1,1'-dianthraquinonyl, helianthrone, mesobenzodianthrone, 2,2'-diamino-1,1'-dianthraquinolyl, flavanthrone, 2,2'-dianthryl, mesonaphthodianthrone, 1,1'-dianthraquinolylamine, quinizarinquinone, hystazarinquinone, alizarinquinone, 6-oxyquinizarinquinone, and the like.
Further, as the non-benzene type aromatic compounds, there may be included, for example, azulene, cyclodecapentane, cyclotetradecaheptane, cyclooctadecanonaene, cyclotetracosadodecaene, heptalene, fulvalene, sesqui-fluvalene, heptafluvalene, perinaphthene, indeno[2,1-a]perinaphthene, dibenzo[bf]oxepine, dibenzo[bf]thiepine, indolizine, cyclo[3,2,2]azine, 4,5-benzotropolone, 3,4-benzotropolone, 5H-benzocycloheptane, 7H-benzocycloheptane, colchicine, colchiceine, colchinol methyl ether, ditropyl ether, ditropyl sulfide, cyclopentadienyltropylidene, benzoazulene, carbinol, 4,5-benzotropone, 2-phenyltropone, naphthocycloheptadienone, naphtotropone, tribenzotropone, 1-amino-1,3-dicyanoazulene, benzoylhydrazone, 3-phenyl-1-oxaazuranone-2,2-benzyltropone, 3-methyl-2-phenyltropone, 2,7-diphenyltropone, 2-(.alpha.-naphthyl)tropone, 2,7-tetramethylene-4,5-benzotropone, 2,7-diphenyl-4,5-benzotropone, naphtho[2',3'-4,5]tropone, naphtho[2',1'-2,3]tropone, dibenzosuberane, naphtho[1',2'-2,3]tropone, dibenzosuberol, 4-oxy-2-phenyltropone, 4,5,7-tribromo-2-phenyltropone, 3,5'-ditropolone, 3-(p-methoxyphenyl)tropolone, 4-oxy-2-phenyltropone, 3-(.alpha.-naphthyl)tropolone, 3,4-diphenyltroporon, 3,7-dibenzyltroplone, 4-(65 -phenylpropyl)tropolone, 3,5'-bitropolonyl, 4-(p-nitrostyryl)tropolone methyl ether, 2-amino-1,3-dicyanoazurene, benzo[b]tropothiazine, 5-bromo-2-phenyltropone, 4-bromo- 2,7-diphenyltropone, diphenylbiphenylcarbinol, thiazinotropone, and the like.
Next, typical examples of the heterocyclic compounds having 5 or more conjugated .pi. bonds include the following compounds.
First, as the oxygen-containing heterocyclic compounds, there may be included:
furan and derivatives thereof, such as 2,5-diphenylfuran, 2-phenylfuran, 3-methyl-diphenylfuran, lepidene, pyridoxine, 2,4-diphenylfuran;
benzofuran, isobenzofuran, dibenzofuran and derivatives thereof, such as dibenzofuran, furano[2',3'-7,8]flavone, egonol, Euparin, 1,3-diphenylisobenzofuran, tetraphenyl glycol, tetraphenylphthalan, 9-phenylanthracene, o-oxymethyltriphenylcarbinol, 3,3'-diphenylphthalide, 1-phenylphthalan, 1,1-phenylphthalan, 3,3-diphenylphthalide, rubrene, .alpha.-sorinine, dibenzofuran, 2,2'-dioxybiphenyl, 2,2'-diaminobiphenyl, phenazone, dibenzoquinone, 2-hydroxybenzofuran, 2-methylbenzofuran, benzo[a]benzofuran, benzo[b]benzofuran, dibenzo[a,f]dibenzofuran, dibenzo[c,d]dibenzofuran, dibenzo[c,e]dibenzofuran, bis(2-dibenzofuryl), bis(3-dibenzofuryl);
pyran and pyrone derivatives, such as 2-p-oxyphenyl-4,6-diphenylpyrylium ferrichloride, anhydrobase, benzopyran, 4-p-oxyphenyl-2,6-diphenylpyrylium ferrichloride, 6-phenylcoumarin;
chromenol and chromene derivatives, such as 6-methyl-2,3-diphenylchromone, 6-methyl-2,3-diphenyl-4-(p-tolyl)-1,4-benzopyran-4-ol, chromanol, .gamma.-chromene, oxychmarone, chromene, cyanizine chloride, fisetin, 6-oxy-3-methoxy-5,7-dimethylflavirium chloride, 4,4'-diflavilene-3,3'-oxide, chrysinidine, apigenidin, rotoflavinidine, lutosonidine, galanginidine, fisenidine, molinidine, flavoneimine, peralgonidin, cyanidin, delphinidin, petunidin, syringidin, hirsutidin, apigeninidin, carajurin, dracorhodin, dracorubin;
flavone, flavonol and isoflavon derivatives, such as flavonol, flavone, fukugetin;
coumarin and isocoumarin derivatives, such as 7-oxy-3,4-benzocoumarin, dicoumarol, angelicin, psoralen, bergapten, bergaptol, xanthotoxin, xanthotoxal, isopimpinellin, pimpinellin, oroselol, oroselone, peucedanin, oxypeucedanin, ostruthol, medakenine, nodakenetin, seselin, xanthyletin, xanthoxyletin; and
xanthone and related compounds; such as dixanthylene, 9-phenylxanthene, isoxanthone, 1,2,7,8-dibenzoxanthene, 3,9-diphenylxanthene, 9,9-diphenylxanthene, and the like.
Next, the nitrogen-containing heterocyclic compounds may include:
pyrroles, such as 1-phenylpyrrole, 5-phenylpyrrole-2-aldehyde, phenyl-2-pyrrylketoneoxime, 2-phenylpyrrole, 2-methyl-1-phenylpyrrole, 2-methyl-4-phenylpyrrole, 2-methyl-5-phenylpyrrole, 3-methyl-5-phenylpyrrole, 2,4-diphenylpyrrole, 2,5-diphenylpyrrole, 2,3-diphenylpyrrole, 2,3,5-triphenylpyrrole, 1,2,3,5-tetraphenylpyrrole, 2,3,4,5-tetraphenylpyrrole, diphenyl-2-pyrrolylcarbinol, pyrrolecyclotrimethylene dye, pyrrolepolymethylene dye, biliverdin, bilirubin, prodigiosin, stercobilin;
indoles, such as 5,7-dichloro-2-phenylindole, 7-chloro-2-phenylindole, 5,7-dibromo-2-phenylindole, 7-bromo-5-chloro-2-phenylindole, 2-(3'-indolyl)-3-isonitroindolenine, Roseindole, Triptophan Blue, Indolo[3,2-c]quinoline, indolo[1,2-c]quinazoline, 2-phenylindole, 3-nitro-2-phenylindole, 3-phenylindole, N-methyl-3-phenylindole, 3-(o-nitrophenyl)indole, 2,3-diphenylindole, 3-triphenylmethylindole, 2-methyl-3-triphenylmethylindole, 2-phenyl-3-triphenylmethylindole, 2-(1-naphthyl)-3-triphenylmethylindole, 2-(2-naphthyl)-3-triphenylmethylindole, 3,3'-diindolyl, 3,2'-diindolyl, 3,3'-dehydrodiindole, Roseindole, 3-nitroso-2-phenylindole, 3-nitro-2-phenylindole, 2-methyl-3-phenylazoindole, 2-phenyl-3-phenylazoindole, 6-oxy-3-phenylindole, triptophan, 4,5-benzotriptophan, 6,7-benzotriptophan, violasein;
oxoderivatives of indole, such as 3-(4-ethoxy-1-naphthyl)oxyindole, indophenine, indigoazine, indigoyellow 3G;
isoindoles, such as 1-chloro-4-methylphthalazine, 1-benzilidenephthalimidine, 2-methyl-3-phenylphthalimidine, 2-methyl-1,3-diphenylisoindole, 2,5-diphenylisoindole, .beta.-isoindigo, dimethylimino-.beta.-isoindigo;
carbazoles, such as 1-phenyl-1,2,3-benzotriazole, 2,2'-diaminodiphenyl, 1,1'-dicarbazole;
porphyrins, such as porphyrazine, magnesium octamethyltetraazaporphyrin, azadipyromethine, phthalocyanine, diazacoproporphyrin, porphine, mesotetraphenylporphyrin, chlorophyll-b, chlorophyll-a;
oxazoles, such as 2-phenyloxazole, 4-phenyloxazole, 5-phenyloxazole, 2-methyl-4-phenyloxazole, 2-methyl-5-phenyloxazole, 4-methyl-2-phenyloxazole, 5-methyl-2-phenyloxazole, 4,5-dimethyl-2-phenyloxazole, 2,4-diphenyloxazole, 2,5-diphenyloxazole, 4,5-diphenyloxazole, 2-methyl-4,5-diphenyloxazole, 2,4,5-triphenyloxazole, 2-(o-nitrophenyl)oxazole, 2-(p-nitrophenyl)oxazole, 2-amino-5-phenyloxazole, 2-(p-aminophenyl)oxazole, 2-(o-aminophenyl)oxazole, 4,5-dimethyl-2-phenyloxidooxazole, 4-methyl-2,5-diphenyloxidooxazole, 2,4,5-triphenyloxidooxazole, 4-(o-methoxycarbonylbenzal)-2-phenyl-5-oxazolone, oxacarbocyanine dye, phenanthrooxazole;
isooxazoles, such as 4-nitro-3-phenylisooxazole, 5-amino-3-methyl-4-phenylisooxazole, 5-benzoyl-3,4-diphenylisooxazole;
thiazoles, such as 4-phenylthiazole, 5-phenylthiazole, 5-(p-fluorophenyl)thiazole, 2-methyl-4-phenylthiazole, 4-methyl-5-phenylthiazole, 5-methyl-4-phenylthiazole, 4,5-diphenylthiazole, 2-methyl-4,5-diphenylthiazole, 1,4-bis(4-methyl-2-thiazolyl)benzene, p,p'-bis(4-methyl-2-thiazolyl)biphenyl, 2-amino-4-phenylthiazole, 2-amino-5-phenylthiazole, 2-amino-4,5-diphenylthiazole, 2-phenylazothiazole, 2-amino-4-methyl-5-phenylazothiazole, 4-methyl-2-phenylazothiazole, .alpha.-naphthothiazole, .beta.-naphthothiazole, naphtho[2,3]thiazole, naphtho[1,2]thiazole, 2-methyl[1,2]thiazole, 2-phenylnaphtho[1,2]thiazole, 2-methylnaphtho[2,1]thiazole, 4-bromo-2-phenylnaphtho[2,3]thiazole, 2-oxynaphtho[2,1]thiazole, 2-aminonaphtho[1,2]thiazole, 2-aminonaphtho[2,1]thiazole, 2-mercaptonaphtho[1,2]thiazole, 2-mercaptonaphtho[2,1]thiazole;
imidazoles, such as 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2-phenylimidazole, 2,4-diphenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-bromo-4-phenylimidazole, 5-chloro-1-ethyl-2-phenylimidazole, 5-chloro-1,2-diphenylimidazole, 2-phenylazoimidazole, 2-methyl-4-phenylazoimidazole, 2-(o-aminophenyl)benzoimidazole;
pyrazoles, such as 3-phenylpyrazole, 5-phenylpyrazole, 4-phenylpyrazole, 1-methyl-3-phenylpyrazole, 1-methyl-5-phenylpyrazole, 3-methyl-5-phenylpyrazole, 1,3-diphenylpyrazole, 1,5-diphenylpyrazole, 1,3,4-triphenylpyrazole, 1,3,5-triphenylpyrazole, 1,4,5-triphenylpyrazole, 5-amino-3-phenylpyrazole, 3-amino-5-phenylpyrazole, 5-methyl-1,3-diphenylpyrazole-4-aldehyde, 3,5-diacetyl-4-phenylpyrazole, 4-benzoyl-1,5-diphenylpyrazole;
oxadiazoles, such as 3-phenylfurazane, 3,4-diphenylfurazane, naphtho[1,2]furazane, phenylfuroxane, 3-methyl-5-phenyl-1,2,4-oxadiazole, 2,5'-diphenyl-1,3,4-oxadiazole;
thiadiazoles, such as 5-phenyl-1,2,3-thiadiazole, 2-phenyl-1,3,4-thiadiazole, 5,5'-diphenyl-2,2'-bis(1,3,4-thiadiazole), 2-oxy-5-phenyl-1,3,4-thiadiazole, 2-methylsulfonyl-5-phenyl-1,3,4-thiadiazole;
triazoles, such as 2-phenyl-1,2,3-triazole, 5-(p-aminophenyl)-3-mercapto-1,2,4-triazole;
tetrazoles, such as 5-phenyltetrazole, 1,5-diphenyltetrazole, 1-oxy-5-phenyltetrazole, 1-amino-5-phenyltetrazole;
pyridine related compounds, such as 2-phenylpyridine, 2,2'-dipyridyl, 2-chloro-6-phenylpyridine, 2,6-dichloro-3-phenylpyridine, 2,2'-azopyridine, 3,3'-azopyridine, benzene-4-azopyridine, 5-chloro-2,2'-azopyridine, 5,5'-dichloro-2,2'-azopyridine, 4-pyridylazoresorcin, 4-pyridyl-m-phenylenediamine, 3-pyridyl-m-phenylenediamine;
quinoline and related compounds, such as quinoline, quinaldine, quinaldine-N-oxide, ethylquinoline, 2-phenylquinoline, 3-methylquinoline, 3-phenylquinoline, 4-methylquinoline, 4-phenylquinoline, 6-methylquinoline, 6-ethylquinoline, 6-phenylquinoline, 2,4-dimethylquinoline, 2,4-diphenylquinoline, quinoline-4-methanol, quinoline[6,5-f]quinoline, quinophthalone, flavaaniline, Quinoline Blue, Ethyl Red, pinacyanol, naphthocyanol, cryptocyanine, xenocyanine, azacyanine, 6,6'-octahydroquinone, Besthorn's red, 2,3'-biquinoline, 2,5'-biquinoline, 2,6'-biquinoline, 2,7'-biquinoline, 3,3'-biquinoline, 4,5'-biquinoline, 4,6'-biquinoline, 5,5'-biquinoline, 6,6'-biquinoline, 6,7'-biquinoline, 6,8'-biquinoline, 7,7'-biquinoline, 8,8'-biquinoline, 2-fluoroquinoline, 3-fluoroquinoline, 4-fluoroquinoline, 5-fluoroquinoline, 6-fluoroquinoline, 7-fluoroquinoline, 8-fluoroquinoline, 3-bromoquinoline, 4-chloroquinoline, 2,4-dichloroquinoline, 3-nitroquinoline, 4-nitroquinoline, 2,3-quinolinediol, quinoline-2-thiol, 2-oxyquinoline-3-thiol, 2-aminoquinoline, 8-aminoquinoline, 2-hydraziquinoline, pyroloquinoline, thiazoloquinoline, pyrimido[4,5-b]quinoline, benzo[f]quinoline;
isoquinoline and related compounds, such as 1-methylisoquinoline, 3-bromomethylisoquinoline, 1-phenylisoquinoline, 4-phenylisoquinoline, 1,1'-biisoquinoline, 5,5'-biisoquinoline, 1-chloroisoquinoline, 5-iodoisoquinoline, 5-bromoisoquinoline, 5-nitroisoquinoline, isoquinoline-1,3-diol, 6,7-methylenedioxyisoquinoline, 1-aminoisoquinoline, 1-cyanoisoquinoline, 1-phenylbenzo[g]3,4-dihydroisoquinoline, 3-(p-aminophenyl)-5,6-dihydro-8,9-dimethoxyimidazo[5,1-a]isoquinoline;
acridine and related compounds, such as acridine, 1-methylacridine, 9-phenylacridine, 9-(3-pyridinyl)acridine, 2-chloroacridine, 2-bromoacridine, 2-acridinol, acridine-3,6-diol, 4-methoxyacridine, 9-phenoxyacridine, 1-nitroacridine, 4-aminoacridine, 1-aminoacridine, 9-phenylaminoacridine, 9-oxyacridine, chrysaniline, acriflavine, 3,6-diamino-4,5-dimethylacridine, acrynol;
phenanthridines, such as 3,4-benzoquinoline, 6-methylphenanthridine, 6-aminomethylphenanthridine, 6-phenylphenanthridine, 6-chlorophenanthridine, 6-bromophenanthridine, 6-nitrophenanthridine, 1-aminophenanthridine, 3-oxyphenanthridinone;
anthrazolines, such as pyrido[2,3-g]quinoline, 2,7-diphenyl[2,3-g]quinoline, 2,8-diphenylpyrido[3,2-g]quinoline;
phenanthroline and related compounds, such as 1,7-phenanthroline, 1,10-phenanthroline, 4,7-phenanthroline, 8-methyl-1,7-phenanthroline, 4,10-dioxy-1,7-phenanthroline, 3,5-dichloro-1,10-phenanthroline, 2-amino-1,10-phenanthroline, 5-oxy-4,7-phenanthroline, 5-amino-4,7-phenanthroline;
pyridoindoles, such as 1,9-pyridoindole, 2,9-pyridoindole, 4,9-pyridoindole;
naphthyridine and related compounds, such as 1,5-naphthyridine, 1,7-naphthyridine, 1,8-naphthyridine, 1,6-naphthyridine, 2,6-naphthyridine, 2,7-naphthyridine, 1,5-naphthyridine-4-ol, 3-amino-1,5-naphthyridine, 2-amino-1,5-naphthyridine, 2-oxy-1.7-naphthyridine;
oxazine and related compounds such as phenoxazinone, resazurin, carocyanin, Nile Blue A, Meldora's Blue, Brilliant Cresyl Blue;
thiazine and related compounds, such as o-benzaminophenyl-.beta.-phenoxycarbonylethyl sulfide, phenothiazine, nitrophenothiazine, 3-chloro-10-ethylphenothiazine, 4-amino-4'-anilinodiphenyl disulfide, 2-chloro-10-(3-dimethylaminopropyl)phenothiazine, chloropromazine, 10-(2-dimethylamino-1-propyl)phenothiazine hydrochloride, 10-[2-(1-pyrrolidyl)ethyl]phenothiazine hydrochloride, 10-[1-methyl-3-piperidylmethyl]phenothiazine, 2-acetyl-10-(3-dimethylaminopropyl)phenothiazine, Methylene Blue;
pyridazine and related compounds, such as cinnoline, 3-methylcinnoline, 4-chlorocinnoline, 3-bromocinnoline, 4-cinnolinol, 4-aminocinnoline, phthalazine, 4-ethyl-2-phenylphthalazinone, phthalazine thiol, 1(2H)-phthalazinone, 3-phenylpseudophthalazine, 4-methyl-3-phenylpseudophthalazine, 2,3-dihydro-1,4-phthalazinedione;
pyrimidine and related compounds, such as 2-cinnamethylpyrimidine, 4,6-dimethyl-2-phenylpyrimidine, 2,4,6-triphenylpyrimidine, alloxantin, 2,6-dioxy-4-phenylpyrimidine, 4,6-dioxy-2-phenylpyrimidine, 5-chloro-4,6-dioxy-2-phenylpyrimidine, sulfadiazine, sulfisomidine, thonzylamine hydrochloride, Vitamin B1, thiochrome, co-carboxylase, allomycin, 6-(2-furfuryl)aminopurine, pteridine, 2,4-pterine diol, 2-amino-6-methyl-4-pteridinol, xanthopterine, leucopterine, isoxanthopterine, quinazoline, 4-chloroquinazoline, 2,4-dichloroquinazoline, 4-quinazoline, 2,3-diphenyl-4-quinazoline;
pyrazine related compounds, such as 3,4-diphenylpyrazinol, quinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline, 2-chloroquinoxaline, 2,3-dichloroquinoxaline, 2-(o-aminoaniline)quinoxaline, N,N'-diphenyl-2,3-piperazione, 2-quinoxalinol, 2,3-quinoxaline diol, 2-aminoquinoxaline, 2,3-diaminoquinoxaline, methylquinoxaline-2-carboxylic acid ester, 2-(d-arabotetraoxybutyl)quinoxaline, flavazole, glucazidone, phenazine, phenazine-5-oxide, phenazine-5,10-dioxide, 5-methylphenazinium-methylsulfate, 10-methyl-5,10-dihydro-2-phenazinecarbonitrile, 2-phenazinecarbonitrile, 1-phenazinol, 1-methoxyphenazine, 2-phenazinol, 1,6-dioxyphenazine-5,10-dioxide, 1-aminophenazine, 2-aminophenazine, 2,3-diaminophenazine, Neutral Red, 5,10-dihydrophenazine, 5-methyl-5,10-dihydrophenazine, 1,2,3,4-tetrahydrophenazine;
tri- and tetra-hetero six-membered cyclic compounds, such as 2,4,6-triphenyl-s-triazine, 2,4-dichloro-6-o-chloroaniline-s-triazine, 5,6-diphenyl-as-triazine, 2,6-diphenyl-2,3,4,5-tetrahydro-as-triazine, 5,6-diphenyl-as-triazine-3-ol, 1,2,4-benzotriazine, 1,2,4-benzotriazine-3-ol, 3-phenyl-1,2,3-benzotriazine-4-(3H)-one, 1,2,3-benzotriazine-4-ol, 1,2,3-benzotriazine-4-thiol, 3-amino-1,2,3-benzotriazine, 2,3-diphenylosotetrazine, 5,6-dimethyl-2,3-diphenylosotetrazine, 5-cyano-2,3-diphenylosotetrazine, 5,6-dibenzoyl-2,3-diphenylosotetrazine, 2,3-dibenzoyl-5-methylosotetrazine, 2,3-dibenzoyl-5,6-dimethylosotetrazine, 2,3-dibenzoyl-5,6-diphenylosotetrazine, 2,3-bis(2,4-dichlorophenyl)-5,6-diphenyl-1,2,3,4-tetrahydro-.nu.-tetrazine, 1,2,3,4-tetraethoxycarbonyl-5,5-diphenyl-1,2,3,4,5,6-hexahydro-.nu.-tetrazine, 7-methyl-2-(4-methylphenyl)-1,2-dihydrobenzotetrazine, 3,6-diphenyl-1,2-dihydro-s-tetrazine, 1,3-diphenyl-1,4,5,6-tetrahydro-s-tetrazine, 3,3,6,6-tetraphenyl-1,2,3,6-tetrahydro-s-tetrazine, and the like.
Further, the sulfur-containing heterocyclic compounds may include:
sulfur-containing heterocyclic compounds, such as 2-phenylthiophene, 2,4-diphenylthiophene, 2,3,4,5-tetraphenylthiophene, metaphenylene hydrochloride, metapyrylene hydrochloride, chloroethene citrate, thenyldiamine hydrochloride, .alpha.-quinquithienyl, .alpha.-sexithienyl;
fused thiophene type compounds, such as 3,3'-diiminothioindigo, indigoron, dihydronaphtho[2,1-b]thianaphthene, 1,3-diphenylisothianaphthene, dibenzothiophene, 2-nitrodibenzothiophene, aminodibenzothiophene, 2,8-diaminodibenzothiophene, dibenzothiophene-5-dioxide, 4-oxydibenzothiophene, 2,8-dioxydibenzothiophene, 2-chlorodibenzothiophene, 1-bromodibenzothiophene, 2,8-dibromodibenzothiophene, 2-iodo-dibenzothiophene, 2-acetyldibenzothiophene, 2,8-diacetyldibenzothiophene, naphthothiophene, 3-oxythiophanthrene, 2,3-thiophanthrene, naphtho[2,3-c]thiophene, naphtho[1,2-b]thiophene, naphtho[2,1-b]thiophene, naphtho[1,2-c]thiophene, 1,2-naphtho[2,1-b]thiophenequinone, 1-oxy-2-naphtho[2,1-b]thiophenealdehyde, naphtho[1,2-c]thiophene, 2H-naphtho[1,8]thiophene, benzo[b]thiophanthrene, 6,11-benzo[b]thiophanthraquinone, benzo[g]thiophanthrene, 4,5-benzothiophanthrene, 8,9-benzothiophanthrene;
five-membered monocyclic compounds containing 2 hetero atoms, such as 5-phenyl-1,2-dithiol-3-thione, 3,4-dihydronaphtho-2,1-trithione, thiaflavone, thiacoumarin, thiaxanthene, thiaxanthohydrol, thiaxanthone, Milacil D, bisthiaxanthylene;
six-membered cyclic compound having two or more hetero atoms, such as 2,5-diphenyl-1,4-dithiadiene, thiophenealdehyde, thianthrene, 2,7-dimethylthianthrene, 1-thianthrenyl lithium, 1-chlorothianthrene, phenoxthine, 2-vinylphenoxthine, 2-aminophenoxthine, 2-nitrophenoxthine, 3,7-dinitrophenoxthine, 10,10-diphenylphenoxthine, 2,5-diphenylthiophene, and the like.
Further, other useful compounds may include:
dicyclic compounds having commonly a nitrogen atom, such as cinchonine, 2-phenylpyrrocoline, 3-ethyl-2-phenylpyrrocoline, 3-benzyl-2-phenylpyrrocoline, 3-nitroso-2-phenylpyrrocoline, 2:3-benzopyrrocoline, 1,5,8-trimethyl-2:3-benzopyrrocoline, 1-ethyl-5,8-dimethyl-2:3-benzopyrrocoline, 1,8-dimethyl-2:3-benzopyrrocoline, 3-phenyl-7:8-benzopyrrocoline, cyclo[3.3.3]azine, cyclo[3.2.2]azine, 2-phenylcyclo[3.2.2]azine, 2,3-diphenylcyclo[3.2.2]azine, tricycladine, 7-methylbenzo[a]quinolinium bromide, 7-phenylbenzo[a]quinolidinium bromide, benzo[b]quinolidinium salt, tetrahydro-.PSI.-berberine, tetrahydroberberine, laudanosoline, tetrahydro-2,3,9,10-tetraoxy-7-methyldibenzopyrrocolium chloride, homolaudanosoline, octadehydromatrine, canadinemethoiodide, tetrahydropalmatinemethoiodide;
alkaloids, such as nicotyrine, 3',2-dipyridyl, cusparine, galipoline, 1-methyl-2-quinolone, casimiroin, 2-pentylquinoline, 4-oxy-2-pentylquinoline, 4-methoxy-2-pentylquinoline, 1-methyl-2-pentyl-4-quinoline, 4-methoxy-2-phenylquinoline, 7-methoxy-1-methyl-2-phenyl-4-quinoline, cuspareine, dictamnine, skimmianine, evolitrine, maclurin, kokusagine, kokusaginine, maculosidine, flindersiamine, evoxoidine, evoxine, evolatine, acronycidine, medicosmine, acronidine, .gamma.-fagarine, cinchonin, quininone, quinotoxin, N-bromoquinotoxin, dihydrocinchonicine, heteroquinine, evoxantidine, xanthoquinoline, 1,3-dimethoxy-10-methylacridone, evoxanthine, xanthevodine, melicopine, melicopidine, melicopicine, acronycine, flindersine, papaverin, papaveraldine, laudanosine, laudanine, codamine, protopapaverine, almepavine, 4,4,5'-trimethoxy-2-vinylstilbene, coclaurine, d-isococlaurine, neprotin, corpaverine, phellodendrine, magnocurarine, coclanoline, narcotin, narcotoline, aponarceine, cinchonin, cinchotoxine, dihydrohydrastine, bicuculline, adlumidine, corlumidine, cordrastine, magnolamine, berbamine, o-methylberbamine, etc.
Among the conjugated .pi. bond compounds described above, preferred are the ones having at least one amino group. Particularly preferred such compounds include, for example, aminonaphthalenes such as diaminonaphthalenes, triaminonaphthalenes and tetraaminonaphthalenes, 1,4-diaminoanthracens, 9,10-diaminophenanthrene, 2,2'-diaminodiphenyl, 1,1'-diamino-2,2'-dinaphthyl, 2-amino-5-phenyl oxazole, 1-aminophenanthridine, 2-amino-4-phenylthiazole, 2-amino-5-phenylthiazole, 3-amino-1,5-naphtyridine, 1-aminophenanthridine, aminoacridines such as 4-aminoacridine, 2-aminoacridine, 1-aminoacridine and 3,6-diaminoacridine, and aminophenazines such as 1-aminophenazine, 2-aminophenazine and 2,3-diaminophenazine.
In a preferred embodiment of the present invention, the scaling preventive to be used in the present invention further contains, in addition to at least one of dyes, pigments and conjugated .pi. bond compounds, at least one inorganic compounds. Although an inorganic compound alone has no scaling preventive action, the scaling preventive action possessed by dyes, pigments or conjugated .pi. bond compounds has unexpectedly been found to be further enhanced when combined with the inorganic compound. It has also been found that this effect can further be exhibited, if the surface roughness of the surfaces to be coated with the scaling preventive is controlled by 5 .mu.m or below. With a surface roughness in excess of 5 .mu.m, the scaling preventive effect is not enough to prevent effectively scaling.
When a mixture of a dye, a pigment or a conjugated .pi. bond compound with an inorganic compound is to be applied by coating on the inner wall surface of a polymerizer, etc., the proportion of the both components may preferably be 0.1 to 2000 parts by weight of the inorganic compound, more preferably 1 to 1000 parts by weight, per 100 parts by weight of the dye, pigment or conjugated .pi. bond compound.
Such inorganic compounds may include silicic acids or silicates, such as orthosilicic acid, metasilicic acid, mesodisilicic acid, mesotrisilicic acid, mesotetrasilicic acid, sodium metasilicate, sodium orthosilicate, sodium disilicate, sodium tetrasilicate, potassium metasilicate, potassium hydrogen disilicate, lithium orthosilicate, hexalithium orthodisilicate, water glass, 12-silicotungstic acid, iso-12-silicotungstic acid, 10-silicotungstic acid, potassium 12-silicotungstate, potassium iso-12-silicotungstate, potassium 10-silicotungstate, sodium 12-silicotungstate, sodium iso-12-silicotungstate, silicomolybdic acid, potassium silicomolybdate, sodium silicomolybdate, and the like;
metal salts such as oxyacid salts, acetates, nitrates, hydroxides or halides of metals selected from alkaline earth metals such as magnesium, calcium, barium, etc., aluminum family metals such as aluminum, etc., tin family metals such as titanium, tin, etc., iron family metals such as iron, nickel, etc., chromium family metals such as chromium, molybdenum, etc., manganese family metals such as manganese, etc., copper family metals such as copper, silver, etc., platinum family metals such as platinum, etc.;
inorganic colloids prepared by mechanical crushing, irradiation of ultrasonic wave, electrical dispersion or chemical methods, such as gold colloid, silver colloid, sulfur colloid, colloid of ferric hydroxide, colloid of stannic acid, colloid of silicic acid, colloid of manganese dioxide, colloid of molybdenum oxide, colloid of barium sulfate, colloid of vanadium pentoxide, colloid of aluminum hydroxide, colloid of lithium silicate and so on.
Among the above inorganic compounds, silicates, silicic acid colloid and ferric hydroxide colloid are particularly preferred.
For coating of the scaling preventive on the inner wall of a polymerizer, etc., it can be applied as such or as a coating solution prepared by dissolving or dispersing in an appropriate solvent. The concentration of the scaling preventive in the coating solution is generally preferred to be 0.01% by weight or higher.
The solvent which may be used in preparation of the coating solution may be water or various organic solvents, including, for example:
aliphatic hydrocarbons such as gasoline, petroleum, benzine, mineral spirit, petroleum naphtha, V.M. & P. naphtha, decalin, tetralin, p-cymene, and the like;
aromatic hydrocarbons such as benzene, toluene, xylene, and the like;
halogenated hydrocarbons such as trichloroethylene, perchloroethylene, chloroform, carbon tetrachloride, ethylene trichloride, benzene monobromide, benzene monochloride, benzene dichloride and the like;
alcohols such as amyl alcohol, ethyl alcohol, isopropyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methyl alcohol, methylamyl alcohol, benzyl alcohol, butyl alcohol and the like;
ketones such as acetone, acetonylacetone, diisobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, methyl butyl ketone, methylcyclohexanone, methyldipropyl ketone, methyl ethyl ketone, methyl n-hexyl ketone, methyl isobutyl ketone, methyl propyl ketone, mesityl oxide, and the like;
esters such as acetates, butyrates, propionates, formates and the like;
alcohol esters such as butyl lactate, isopropyl lactate, ethyl lactate, ethyl oxypropionate, diethyl maleate and the like;
ketone esters such as ethyl acetoacetate, ethyl pyruvate and the like;
ethers such as isopropyl ether, ethyl ether, diethyl carbitol, diethyl cellosolve, butyl ether, and the like;
ketone alcohols such as acetonylmethanol, diacetone alcohol, dihydroxyl acetone, pyruvyl alcohol and the like;
ether alcohols such as isopropyl cellosolve, carbitol, glycidol, cellosolve, glycol ether, benzyl cellosolve, butyl carbitol, butyl cellosolve, methyl carbitol, methyl cellosolve, triethyleneglycol monoethyl ether and the like;
ketone ethers such as acetal ethyl ether, acetonylmethanol ethyl ether, methyl ethoxyethyl ether, and the like;
ester ethers such as butylcarbitol acetate, butyl cellosolve acetate, carbitol acetate, cellosolve acetate, 3-methoxybutyl acetate, methylcarbitol acetate, methyl cellosolve acetate, and the like.
When organic solvents highly compatible with water are employed, water may be added to the coating solution in an amount within the range which does not impair solubility or dispersibility of the scaling preventive, whereby the coating solution can be improved in economy and safety during transportation and storage. Such solvents includes:
alcohols such as methyl alcohol, ethyl alcohol, allyl alcohol, n-propyl alcohol, isopropyl alcohol, and the like;
ketones such as acetone, acetonylacetone, diacetone alcohol and the like;
esters such as ethyleneglycol monomethyl ether acetate, diethyleneglycol methyl ether acetate, monoethyl ether acetate and the like;
ethers such as dioxane, ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether and the like;
furans such as tetrahydrofuran, furfuryl alcohol and the like;
aprotic solvents such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide and the like.
When the scaling preventive to be used is a water-soluble sulfonic acid type or carboxylic acid type dye having sulfonic acid groups or carboxylic acid groups in the form of an alkali metal salt or ammonium salt, water can be used as the solvent in which the preventive is to be dissolved, as disclosed in Japanese Patent Publication No. 5442/1981, whereby there is the advantage in safety and hygiene that the solvent is non-toxic and harmless. If water is used as the solvent as described above, wettability of the coating solution for the inner wall of a polymerizer, etc. can be enhanced by addition of alcohols, preferably C.sub.3 -C.sub.6 monohydric alcohols, such as n-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, iso-amyl alcohol, sec-amyl alcohol, sec-hexyl alcohol, etc., as disclosed in Japanese Patent Publication No. 5444/1981. Also, as disclosed in Japanese Patent Publication No. 5442/1981, for the purpose of making drying of the coating solution after coating easier, an organic solvent compatible with water such as alcoholic solvents, ester solvents, ketone solvents, may be added to the coating solution. In carrying out coating of the coating solution containing the scaling preventive on the inner wall of a polymerizer, etc. according to the process of the present invention, various fixing agents can be used for enhancement of the fixing characteristic, if desired. The fixing agent may be used according to various methods, for example, the method in which it is incorporated in the coating solution containing the scaling preventive, the method in which the fixing agent or a solution thereof is previously applied on the wall surface prior to coating of the scaling preventive, followed by overlaying of the scaling preventive thereon, and the suitable method may be selected depending on the kind of the scaling preventive and the kind of the fixing agent.
Such fixing agents may include the polymeric compounds as shown below:
olefin polymers, such as polyethylene, polyethylene sulfonic acid, polypropylene, poly(1-butene), polyisobutene, polycyclopentene, polycyclopentylethylene, polycyclohexylethylene, poly(3-cyclohexyl-1-propene), poly(4-cyclohexyl-1-butene), poly(5-cyclohexyl-1-pentene), poly(cyclotrifluoroethylene), poly(tetrafluoroethylene);
diene polymers, such as polyallene, polybutadiene, polyisoprene, polychloroprene, poly(1-methoxybutadiene), poly(2-tert-butyl-1,3-butadiene), poly(cyclopentadiene), poly(1,3-cyclohexadiene), poly(dimethylfulvene), poly(4-vinyl-1-cyclohexane), poly(1,5-hexadiene), poly(1,5-cyclooctadiene), poly(bicyclo-[2,2,1]-hepta-2,5-diene), poly(5,7-dimethyl-1,6-octadiene), poly(diallylphthalate), poly(diallylmethylsilane), poly(diallylphenylphosphineoxide);
acetylene polymers, such as polyacetylene, poly(cyanoacetylene), poly(hydroxymethyl)acetylene), poly(butoxyacetylene), poly(phenylacetylene), poly(diphenyldiacetylene), poly(pyridylacetylene);
aliphatic vinyl polymers and vinylidene polymers, such as polyvinyl alcohol, polyallyl alcohol, poly(vinylformal), poly(vinylacetal), poly(vinylbutyral), poly(vinylisobutyral), poly(vinylcyclohexanoneketal), poly(vinyl acetate), poly(vinylchloroacetate), poly(vinyl isobutyrate), poly(vinyl pivalate), poly(vinyl n-caproate), poly(vinyl caprylate), poly(vinyl laurate), poly(vinyl palmitate), poly(vinyl benzoate), poly(vinyl sulfate), poly(vinyl chloride), poly(vinylidene chloride), poly(vinyl bromide), poly(vinyl methyl ether), poly(vinyl ethyl ether), poly(vinyl n-propyl ether), poly(vinyl isopropyl ether), poly(vinyl n-butyl ether), poly(vinyl isobutyl ether), poly(vinyl tert-butyl ether), poly(vinyl neopentyl ether), poly(vinyl carbomethoxymethyl ether), poly(vinyl-2-methoxyethyl ether), poly(vinyl-2-chloroethyl ether), poly(vinyl 2,2,2-trifluoroethyl ether), poly(vinyl benzyl ether), poly(vinyl methyl ketone), poly(methyl isopropenyl ketone), poly(1-nitropropylene), poly(vinylsulfofluoride), poly(vinylsulfonic acid), poly(vinyl diphenylphosphineoxide), poly(vinyl diphenylphosphinesulfide), poly(dimethyl-2-cyano-2-propene-1-phosphonate), poly(diethyl-2-cyano-2-propene-1-phosphonate), poly(maleic anhydride);
aromatic vinyl polymers, such as polystyrene, poly(.alpha.-methylstyrene), poly(4-chlorostyrene), poly(4-bromostyrene), poly(dichlorostyrene), poly(4-methoxystyrene), poly(2,5-dimethoxystyrene), poly(vinyl-bis(1-ethoxyethyl)hydroquinone), poly(4-vinyl-phthalic acid), poly(4-vinylphenylboric acid), poly(diphenyl-4-styrylphosphine oxide), poly(diphenyl-4-styrylphosphine sulfide), poly(9-vinylanthracene), poly(4-vinylbiphenyl), poly(acenaphthylene), polyindene;
heterocyclic vinyl polymers, such as poly(N-vinylcarbazole), poly(9-.DELTA..sup.5 -pentenylcarbazole), poly(9-.DELTA..sup.5 -hexenylcarbazole), poly(N-vinylpyrrolidone), poly(2-vinylpyridine), poly(4-vinylpyridine), poly(2-methyl-2-vinylpyridine), poly(2,4-dimethyl-6-vinyl-S-triazine), poly(N-vinyl-1,2,4-triazine), poly(N-vinylbenztriazole), poly(N-morpholinone-(3)), polycoumarone;
acrylic and methacrylic polymers, such as polyacrylic acid, polymethacrylic acid, poly(methyl acrylate), poly(ethyl acrylate), poly(butyl acrylate), poly(5-cyano-3-thia-phenylacrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-propyl methacrylate), poly(n-butyl methacrylate), poly(isobutylmethacrylate), poly(n-hexyl methacrylate), poly(2-ethylbutyl methacrylate), poly(n-octyl methacrylate), poly(n-lauryl methacrylate), poly(4-(tert-butyl)phenyl methacrylate), poly(bornyl methacrylate), poly(.beta.-(N-carbazyl)ethyl methacrylate), poly(tert-butyl crontonate), polyacrylonitrile, polymethacrylonitrile, polyacrylamide, poly(N,N-dimethylacrylamide), poly(N-(1,1-dimethyl-3-oxobutyl)acrylamide, poly(acrylopiperidine), poly(acrylomorpholide), poly(9-acryloylcarbazole), polymethacrylamide, polyacrolein, poly(.alpha.-methylacrolein), poly(diacryloylmethane), poly(acrylic anhydride), poly(methacrylic anhydride);
polyethers, such as polyformaldehyde, polyacetaldehyde, poly(mono-chloroacetaldehyde), polychloral, polypropionaldehyde, polyacrolein, poly(2-formyl-.DELTA..sup.5 -dihydropyrane), poly(trans-1,2-cyclohexanedicarboxyaldehyde), poly(glutardialdehyde), poly(.beta.-methylglutardialdehyde), poly(.beta.-phenylglutardialdehyde), poly(dimethylketene), polyacetone, poly(monobromoacetone), poly(7-oxa-bicyclo[2,2,1]heptane), poly(3-phenoxylene), poly(2,6-xylenol), poly(ethylene oxide), poly(propylene oxide), poly(cyclopentene oxide), poly(cyclohexene oxide), poly(phenylglycidyl ether), poly(1,2-di(epoxyethyl)benzene), poly(3,3-bis(chloromethyl)oxetane), poly(tetrahydrofuran);
polysulfides, polysulfones, such as poly(thiocarboxylfluoride), poly(ethylenedichloride-sodium tetrasulfide), poly(dichlorodiethyl ether-sodium disulfide), poly(dichlorodiethyl ether-sodium tetrasulfide), poly(phenylenesulfide), poly(ethylenesulfone), poly(propylenesulfone), poly(1-butenesulfone), poly(5-norbornenesulfone), poly(styrenesulfone), poly(1-pentylsulfone), poly(1-hexylsulfone), poly(1-heptylsulfone), poly(butadienesulfone), poly(isoprenesulfone), poly(dimethylbutadienesulfone), poly(1,5-hexadienesulfone), poly(cis,cis-cyclooctadienesulfone), poly(norbornadienesulfone);
various addition polymers, such as poly(methylene diisocyanate), poly(ethylene diisocyanate), poly(trimethylene diisocyanate), poly(tetramethylene diisocyanate), poly(5-iminohydantoin, poly(perfluoroglutarodinitrile), poly(1-(perfluorobutyryl)aziridine);
formaldehyde resins, such as phenol-formaldehyde resin, melamine-formaldehyde resin, urea-formaldehyde resin, aniline-formaldehyde resin, p-toluenesulfonamide-formaldehyde resin;
polyesters, such as poly(11-oxyundecanoate), poly(hexamethylene succinate), poly(hexamethylene sebacate), poly(hexadecamethylene sebacate), poly(hexamethylene-.alpha.,.alpha.'-dibutylsebacate), poly(octamethylene cis-hexahydroterephthalate), poly(octamethylene transhexahydroterephthalate), poly(hexamethylene maleate), poly(hexamethylene fumarate), poly(hexamethylene acetylenedicarboxylate), poly(ethylene terephthalate), poly(p-phenylene isophthalate), poly(4,4'-biphenylene isophthalate), poly(hexamethylene carbonate), poly(p-phenylene carbonate), poly(m-phenylene carbonate), poly(4,4'-isopropylidenediphenylene carbonate), poly(4,4'-(2-pentylene)diphenylene carbonate), poly(1,2-bis(hydroxymethyl)carborane-adipic acid), poly(allylsulfonate), poly(hydroquinone-aryloxyphosphoryl dichloride), poly(hydroquinone-(chloromethyl)phosphoryl dichloride), poly(hydroquinone-(N-dimethyl)phosphoramidic acid)dichloride;
polyamides, such as poly(isocyanate), poly(vinylisocyanate), poly(butylisocyanate), poly(3-aminopropionic acid), poly(6-aminopropionic acid), poly(11-aminoundecanoic acid), poly(hexamethylene adipamide), poly(decamethylene adipamide), poly(3,3'-(methylimino)bistrimethylene adipamide), poly(benzidine-isophthalic acid), poly(pyrromelliticdianhydride-aromatic diamine), poly(1,6-hexamethylene-bis(carboxyethyl)sulfide), poly(1,6-hexamethylenediamine-benzene-1,3-bis-sulfonic acid chloride), poly(trans-2,5-dimethyl-piperazine-4,4'-sulfonyl-dibenzoyl chloride), poly(bis(3-aminopropyl)phenylphosphine-adipic acid), poly(bis(3-aminopropyl)phenylphosphine-terephthalic acid), poly(bis(3-aminopropyl)methylphosphine oxide-adipic acid), poly(bis(3-aminopropyl)n-octylphosphine-adipic acid), poly(bis(3-aminopropyl)phenylphosphine oxide-adipic acid), poly(hexamethylenediamine-bis(2-carboxyethylene)phenylphosphine oxide), poly(hexamethylenediamine-bis(p-carboxyphenyl)phenylphosphine oxide), poly(piperazine-bis(2-carboxyethyl)phenylphosphine oxide);
polyureas, polyurethanes, such as polyureas, poly(1,10-decamethylenediamine-1,6-hexamethylene-bis-ethylurethane), poly(diphenylmethane-4,4'-diisocyanate-4,4'-diphenylmethane), poly(toluene-2,4-diisocyanate-N,N'-bis(trimethysilyl)-p,p'-diaminodiphenyl ether, polyurethane, polyurethane poly(propyleneoxide) basis;
various linear condensed polymers, such as poly(diethylcarbodiimide), poly(diallylcarbodiimide), poly(di-n-butylcarbodiimide), poly(methylisopropylcarbodiimide), poly(di-n-hexylcarbodiimide), poly(diphenylcarbodiimide), poly(4,4'-diphenylenemethanecarbodiimide), poly(hexamethylenecarbodiimide), poly(1,3-xylylenecarbodiimide), poly(3-methyl-1,4-phenylenecarbodiimide), poly(2,2'-dimethyl-biphenylenecarbodiimide), poly(2,2'-dimethoxy-biphenylenecarbodiimide), poly(1,5-naphthylenecarbodiimide), poly(adipyldihydrazide-succinoyl chloride), poly(adipyldihydrazide-isophthaloyl chloride), poly(isophthalicdihydrazide-terephthaloyl chloride), poly(2,5-dimethylbenzylene), poly(-xylylene), poly(2,5-dimethylxylylene), poly(2,5-dimethoxy-p-xylylene), poly(p-xylylidene), poly(.alpha.-cyano-m-xylylidine), poly(.alpha.-cyano-p-xylylidine), poly(nitrophenylene), poly(tetramethyl-p-phenylenedimethylene), poly(2,5-dihydrdoxy-p-phenylenedimethylene), poly(4,4'-oxydiphenylenedimethylene), poly(2,5-dimethoxy-p-phenylenedimethylene);
heterocyclic condensed polymers, such as poly(benzoimidazole), poly(alkylene-5,5'-dibenzoimidazole), poly(allylene-5,5'-dibenzoimidazole), poly(pyromellitimide), poly(benzooxazole), poly(oxadiazole), poly(oxadiazolidine), poly(dithiazole), poly(benzothiazole), poly(1,4-xylenyl)-2-methylpiperazine), poly(quinoxaline), poly(S-triazinyleneimide);
natural polymers, modified natural polymers, such as natural rubber, cyclized rubber, hydrochloric acid rubber, chlorinated rubber, guttapercha, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, benzyl cellulose, hydroxyethyl cellulose, carboxylmethyl cellulose, cyanoethyl cellulose, cellulose triformate, cellulose acetate, cellulose triacetate, cellulose tripropionate, cellulose tributyrate, cellulose tricaproate, cellulose tricarbanilate, cellulose nitrate, cellulose trinitrate, starch, amylose, amylose acetate, amylose carbanilate, amylopectin, alginic acid, chitin, glycogen, gum arabic, gum tragacanth, heparine, pectin, rosin, kopal, shellac, casein, collagen(calf-skin), collagen(ichthyocol), gelatin, peanut-protein, soybean-protein, nucleic protein (calf thymus), nucleic protein (sperm of sea urchin), poly(sarcosine), sericin, silk, wool, zein, polyadenylic acid, deoxyribonucleic acid, ribonucleic acid;
polysiloxanes, such as polysiloxane, polydimethylsiloxane;
organic metal polymers, such as poly(bis(imidazolate)-metal(II)), poly(aluminumtriisopropylateethylenediamine); and
inorganic polymers such as polymetaphosphate, and so on.
In the process of the present invention, the above-mentioned scaling preventive is applied on the inner wall surface of a polymerizer and the portions of the auxiliary polymerizer equipment where scales may be sticked, namely the portions which monomers may come into contact with during polymerization (including portions which monomers can possibly contact), for example, stirring blades, stirring shaft, condenser, header, baffles, search coil, bolts, nuts, etc. Preferably, the scaling preventive is further applied on the portions of recovery system of unreacted monomers where scales may be sticked, for example, the inner surfaces of monomer distillation columns, condensers, monomer storage tanks, valves, etc.
The method for applying the scaling preventive on the inner surface of a polymerizer, etc. as mentioned above is not particularly limited, and may be inclusive typically of the brush coating, spray coating, the method of filling the polymerizer with a coating solution followed by withdrawal thereof, and otherwise the automatic coating methods as disclosed in Japanese Laid-open Patent Publication (Kokai) Nos. 61001/1982, 36288/1980, Japanese Laid-open Patent Publication (Kohyo) Nos. 501116/1981, 501117/1981 and Japanese Laid-open Patent Publication (Kokai) No. 11303/1984.
The process of the present invention can be applied to various polymerizations of vinyl monomers in aqueous media. Typical examples of such polymerizations include the production of polymers by suspension polymerization or emulsion polymerization of a vinyl halide such as vinyl chloride or a monomeric mixture containing the vinyl halide as a main constituent, such as a mixture of vinyl chloride and vinyl acetate; the production of beads or latex of polymers such as polystyrene, polymethacrylate, polyacrylonitrile and the like; the production of synthetic rubbers such as SBR, NBR, CR, IR, IIR and the like (such synthetic rubbers are generally produced by emulsion polymerization); the production of ABS resins, etc. The system of polymerization may be either suspension polymerization or emulsion polymerization. Vinyl monomers which can be provided for polymerization may be exemplified by vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate, vinyl propionate, acrylic acid, methacrylic acid or their esters or salts, maleic acid or fumaric acid, and their esters or anhydrides, diene monomers such as butadiene, chloroprene or isoprene, further styrene, acrylonitrile, vinylidene halide, vinyl ether, etc. In carrying out the polymerization of one or more of such monomers, the object of scaling prevention can be effectively attained irrespective of the system or formulation for the polymerization.
In the suspension or emulsion polymerizations, the polymerization catalysts generally employed are, for example, organic peroxides such as t-butylperoxyneodecanate, di-2-ethylhexylperoxydicarbonate, 3,5,5-trimethylhexanoylperoxide, .alpha.-cumylperoxyneodecanoate, cumene hydroperoxide, cyclohexanoneperoxide, t-butylperoxypivalate, di-2-ethoxyethylperoxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropylperoxydicarbonate and acetylcyclohexylperoxide, etc., azo catalysts such as .alpha.,.alpha.'-azobisisobutyronitrile, .alpha.,.alpha.'-azobis-2,4-dimethylvaleronitrile, water soluble persulfates such as potassium persulfate, ammonium persulfate, etc. Also, as a dispersant, there may be employed, for example, suspending agents such as natural or synethtic polymeric compounds, e.g., partially saponified product of polyvinyl acetate, polyacrylic acid, copolymer of vinyl acetate and maleic anhydride, cellulose derivative such as hydroxypropylmethyl cellulose and gelatin; emulsifiers as exemplified by nonionic emulsifiers such as sorbitane monolaurate, sorbitane trioleate, anionic emulsifiers such as sodium laurylsulfonate, sodium alkylbenzenesulfonate. As other additives, fillers such as calcium carbonate, titanium oxide, etc., stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin laurate, dioctyltin mercaptide, etc., lubricants such as lice wax, stearic acid, cetyl alcohol, etc., plasticizers such as DOP, DBP, etc., chain transfer agents such as trichloroethylene, mercaptans, etc. and pH controllers may be added into the polymerization system. According to the process of the present invention, irrespectively of which catalysts, dispersants or additives may be employed, scaling can effectively be prevented in any polymerization system.

The present invention is described in more detail below with reference to the following Examples, by which the scope of the present invention is not limited. In the following, all parts are by weight unless otherwise noted.
(Note: In the following Examples, Experiment Nos. 277 to 300 are skipped.)
EXAMPLE 1
As shown in Table 1, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 1, a dye or a pigment was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound or the polymeric compound and the concentration of the dye or pigment in the coating solution are also shown in Table 1. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 parts of vinyl chloride monomer, 200 parts of deionized water, 0.022 part of partially saponified polyvinyl alcohol, 0.028 part of hydroxymethyl cellulose and 0.03 part of t-butyl peroxyneodecanate, and polymerization was carried out at 52.degree. C. for 7 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 1. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
Also, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually according to the standards shown below, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 1.
A: no sticking of scale
B: several percent sticking of sandy scales
C: scales sticking thinly over part of the surface (about 10% of surface)
D: scales sticking thickly over part of the surface (about 10% of surface)
E: scales sticking thinly over part of the surface (about 50% of surface)
F: scales sticking thickly over part of the surface (about 50% of surface)
G: scales sticking thinly over the entire surface
H: scales sticking thickly over the entire surface
In Table 1, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 1 to 6 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound. Also, the coating solution employed in Experiment Nos. 23 and 57 was prepared by dissolving one part of sodium sulfide in 100 parts of water and adding 0.5 part of a dye to the resultant solution, followed by heating at 80.degree. C. for 30 minutes.
TABLE 1__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Dye or pigment (a) compound weight compound weight conc. SolventNo. (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 1* -- -- -- -- 2* -- -- -- -- 3* -- -- -- -- 4* -- -- -- -- 5* -- -- -- -- 6* -- -- -- -- 7* Solvent Black 5 -- -- 0.5 Methanol 8* " Colloidal silica 100/100 -- 0.5 " 9* -- " 0/100 -- 0.4 " 10* Solvent Black 5 -- Atactic polypropylene 100/70 0.7 Acetone 11* -- -- " 0/100 0.5 "12 Solvent Black 5 -- -- 0.5 Methanol13 Solvent Black 5 Colloidal silica 100/100 -- 0.6 "14 " Fe(OH).sub.3 sol 100/5 -- 0.6 "15 Acid Blue 82 -- -- 0.5 Water/Methanol (90/10)16 " Water glass 100/100 -- 0.7 Water/Methanol (90/10)17 " Colloid of sulfur 100/5 -- 0.6 Water/Methanol (90/10)18 " CuCl.sub.2 100/2 -- 0.5 Water/Methanol (90/10)19 Acid Violet 47 -- -- 0.8 Water20 Acid Red 83 -- -- 0.5 "21 Acid Blue 102 -- -- 0.7 "22 Direct Blue 199 -- -- 0.7 "23 Food Blue 2 -- -- 2.0 "24 Food Green 2/Acid Red 52 Colloidal silica 100/50 -- 0.8 Water/Isobutyl (90/10) alcohol (90/10)25 Direct Blue 108 -- -- 0.9 Water26 Acid Brown 165 -- -- 1.0 "27 Acid Yellow 7 Zn(CH.sub.3 COO).sub.2 100/5 -- 0.5 "28 Sulfur Blue 2 -- -- 0.9 "29 Fluorescent Brightening -- -- 0.8 " Agent 5630 Reactive Yellow 2 -- -- 0.9 "31 Reactive Green 7 -- -- 0.7 "32 Basic Red 2 Metasilicic acid -- 0.8 " (100/80)33 Reactive Blue 7 -- -- 0.5 "34 Reactive Black 8 -- -- 0.8 "35 Azoic Brown 2 -- Polystyrene 100/30 0.7 Toluene36 Azoic Orange 7 -- -- 0.9 Water37 Basic Yellow 34 -- -- 0.5 "38 Basic Orange 2 -- -- 0.8 "39 Basic Red 17 -- -- 1.0 "40 Basic Violet 26 -- -- 0.5 "41 Basic Orange 14/Disperse Blue Colloid of lithium 100/150 -- 1.0 Water/Acetone 66 (50/50) silicate (50/50)42 Disperse Brown 3 -- -- 0.7 Acetone43 Pigment Blue 25/Solvent Black 5 -- Polystyrene 100/20 0.7 Toluene (20/80)44 Solvent Red 21 Sodium metasilicate 100/60 -- 0.9 Methanol45 Basic Blue 21 -- -- 0.6 Water46 Vat Yellow 10 -- -- 0.4 Xylene47 Vat Red 16/Vat Brown 44 -- -- 0.5 "48 Solvent Black 7 Colloidal silica 100/100 -- 0.4 Water/Methanol (30/70)49 Disperse Blue 104 -- Polyindene 100/50 0.7 Trichloroethylene50 Vat Yellow 4 -- -- 0.9 Xylene51 Vat Orange 4 -- -- 0.5 Methanol52 Pigment Violet 122 -- Poly(4-chlorostyrene) 100/100 1.0 MEK53 Vat Red 1 -- -- 0.8 Xylene54 Pigment Green 38 -- Poly(4-methoxystyrene) 100/10 0.9 MEK55 Acid Black 2/Basic Red 9 -- -- 0.5 Water/n-Amyl alcohol (80/20)56 Basic Green 1 -- -- 0.6 Water57 Pigment Blue 1 -- Poly(vinyl methyl 100/40 0.9 Acetone ketone)58 Pigment Violet 23 -- Atactic polypropylene 100/70 0.7 Toluene59 Solvent Black 3/Basic Blue 24 -- -- 0.6 Methanol60 Basic Orange 22 Water glass -- 0.8 Water (100/50)61 Disperse Yellow 33 -- -- 1.5 Xylene62 Vat Orange 7 -- -- 0.7 Pyridine63 Sulfur Blue 4 Fe(OH).sub.3 sol 100/5 -- 0.6 Water64 Fluorescent Brightening -- -- 0.7 Pyridine Agent 174__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 10 30 50 100 150 200__________________________________________________________________________ 1* 100 l 10-13 60 H (1200) 2* 40 m.sup.3 7-8 " H (1100) 3* 100 l 0.8-1 30 H (900) 4* 130 m.sup.3 0.4-0.7 " E H (900) 5* 1 m.sup.3 0.2-0.3 " E H (800) 6* 2 m.sup.3 0.05-0.1 " B E H (700) 7* 40 m.sup.3 7-8 " B E H (400) 8* " " " B C F H (300) 9* 1 m.sup.3 0.2-0.3 " H (800) 10* 40 m.sup.3 7-8 " B C F H (450) 11* 1 m.sup.3 0.2-0.3 60 H (1100) 12 130 m.sup.3 0.4-0.7 10 A A A A A B (3) 13 " 0.4-0.7 " A A A A A A (0.2) 14 " " " A A A A A A (0.5) 15 2 m.sup.3 0.05-0.1 " A A A B C D (20) 16 " " " A A A A A A (0.9) 17 " " " A A A A A A (0.7) 18 " " " A A A A A A (0.8) 19 " " " A A A B C D (21) 20 " " " A A A B C D (18) 21 " " " A A A B C D (19) 22 " " " A A A B C D (15) 23 " " " A A A B C D (20) 24 " " " A A A A A A (0.5) 25 1 m.sup.3 0.2-0.3 " A A A B C D (16) 26 " " " A A A B C D (18) 27 " " " A A A A A A (0.9) 28 " " " A A A B C D (20) 29 " " " A A A B C D (22) 30 " " " A A A B C D (19) 31 " " " A A A A B C (10) 32 130 m.sup.3 0.4-0.7 " A A A A A A (0.8) 33 1 m.sup.3 0.2-0.3 " A A A B C D (18) 34 " " " A A A A B C (8) 35 " " " A A A A A B (3) 36 " " " A A A A B C (10) 37 " " " A A A B C D (20) 38 " " " A A A A B C (9) 39 " " " A A A B C D (18) 40 100 l 0.8-1 " A A A B C D (17) 41 " " " A A A A A A (0.7) 42 " " " A A A A A B (3) 43 " " " A A A A A B (2.5) 44 " " " A A A A A A (0.4) 45 " " " A A A B C D (19) 46 " " " A A A A A B (4) 47 " " " A A A A B C (9) 48 " " 15 A A A A A A (0.2) 49 2 m.sup.3 0.05-0.1 " A A A A A B (2.5) 50 " " " A A A A B C (7) 51 " " " A A A A B C (9) 52 " " " A A A A B C (10) 53 " " " A A A B C D (19) 54 " " " A A A A A B (2.3) 55 " " " A A A A A A (0.9) 56 " " " A A A A B C (8) 57 " " " A A A B C D (18) 58 1 m.sup.3 0.2-0.3 " A A A A A B (2.1) 59 " " " A A A A A A (0.7) 60 " " " A A A A A B (1.8) 61 " " " A A A A B C (10) 62 " " " A A A A B C (9) 63 " " " A A A A A A (0.6) 64 " " " A A A B C D__________________________________________________________________________ (7) Notes: (1) *comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 2
As shown in Table 2, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 2, a dye or a pigment was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of dye or pigment in the coating solution are also shown in Table 2. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 parts of vinyl chloride monomer, 200 parts of deionized water, 0.125 part of hydroxypropylmethyl cellulose, 0.125 part of sorbitan monolaurate and 0.025 part of .alpha.,.alpha.'-azobis-2,4-dimethylvaleronitrile, and polymerization was carried out at 52.degree. C. for 10 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 2. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
In the same manner as in Example 1, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 2.
In Table 2, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 65 and 66 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound. Also, the coating solution employed in Experiment Nos. 105 and 133 was prepared by dissolving one part of sodium sulfide in 100 parts of water and adding 0.5 part of a dye to the resultant solution, followed by heating at 80.degree. C. for 30 minutes.
TABLE 2__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Dye or pigment (a) compound weight compound weight conc. SolventNo. (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 65* -- -- -- -- 66* -- -- -- -- 67* Basic Black 2 -- -- 0.8 Water/n-Butyl alcohol (80/20) 68* " Colloidal silica 100/80 -- 0.8 Water/n-Butyl alcohol (80/20) 69* -- " 0/100 -- 0.8 Water 70* -- -- Polyindene 0/100 0.5 Dioxane 71* Basic Red 2 ZnCl.sub.2 100/5 -- 0.8 Water/n-Amyl alcohol (80/20) 72* Acid Blue 59 Water glass 100/80 -- 0.5 Water/Isobutyl alcohol (90/10) 73* Basic Orange 14 Mesotrisilicic acid 100/50 -- 0.7 Water 74* Acid Black 2 Manganese dioxide 100/5 -- Water/Butyl alcohol (85/15) 75 Basic Orange 14 -- -- 0.6 Water 76 " ZnCl.sub.2 -- " " 77 Basic Orange 14 Colloidal silica -- 0.6 " 78 " Colloid of sulfur -- " " 79 Direct Brown 44 -- -- 0.9 " 80 Acid Orange 33 -- -- 0.8 " 81 Basic Red 2 ZnCl.sub.2 100/5 -- 0.8 Water/n-Amyl alcohol (80/20) 82 Mordant Red 21 -- -- 0.5 Water 83 Solvent Red 30 -- -- 0.7 Methanol 84 Acid Black 110 -- -- 0.4 Water 85 Direct Blue 108 Mesotetrasilicic acid 100/40 -- 0.7 " 86 Acid Blue 59 Water glass 100/80 -- 0.5 Water/Isobutyl alcohol (90/10) 87 Solvent Orange 44 -- -- 0.9 Methanol 88 Solvent Black 5 -- -- 1.0 " 89 Basic Orange 14 Mesotrisilicic acid 100/50 -- 0.7 Water 90 Solvent Red 100 -- -- 0.6 Methanol 91 Basic Blue 22 Al(OH).sub.3 sol 100/2 -- 0.5 Water 92 Vat Yellow 20 -- -- 0.8 " 93 Vat Orange 13 -- -- 0.4 " 94 Disperse Violet 23 -- -- 0.9 Acetone 95 Solvent Black 3 -- -- 0.7 " 96 Pigment Red 35 -- Poly(vinyl n-butyl 100/80 1.0 Methylene ether) chloride 97 Vat Green 2 -- -- 0.5 -- 98 Pigment Red 88 -- Polyvinyl methyl 100/70 0.8 Dioxane ketone 99 Pigment Blue 16 -- Polyvinyl sulfonic 100/100 0.7 Water acid100 Basic Blue 19 Ce(NO.sub.3).sub.3 100/10 -- 0.7 "101 Solvent Blue 73/Pigment Blue 2 -- Polyindene 100/50 0.5 Dioxane (50/50)102 Solvent Black 49 Ni(NO.sub.3).sub.2 100/20 -- 1.0 Water103 Basic Black 2 Colloidal silica 100/80 -- 1.0 Water/n-Butyl alcohol (80/20)104 Disperse Violet 42 -- -- 0.7 Acetone105 Sulfur Blue 6 -- -- 0.9 Water106 Solubilized Sulfur Brown 1 -- -- 0.6 "107 Fluorescent Brightening -- -- 0.4 " Agent 22108 Disperse Red 113 -- -- 0.8 Acetone109 Pigment Red 2/Pigment -- Polyacenaphthylene 100/100 0.8 Toluene Green 10110 Pigment Yellow 13 -- Poly(4-vinylbiphenyl) 100/30 0.6 Benzene111 Basic Orange 2 MgCl.sub.2 100/15 -- 0.9 Water112 Basic Orange 33 -- -- 0.6 "113 Basic Yellow 36 -- -- 0.7 "114 Direct Violet 90 -- -- 0.5 "115 Direct Blue 168 -- -- 0.6 "116 Direct Black 22 Water glass 100/50 -- 0.6 Water/Isobutyl alcohol (90/10)117 Acid Yellow 42 -- -- 1.0 Water118 Acid Red 77/Food Yellow 4 -- -- 0.5 " (40/60)119 Pigment Brown 5 -- Polyacrylomorpholide 100/50 1.0 DMF120 Acid Black 115 Colloid of sulfur 100/20 -- 0.9 Water121 Direct Red 11 -- -- 0.6 "122 Mordant Blue 8 -- -- 0.8 "123 Pigment Violet 5 -- Polyacrolein 100/40 0.9 DMF124 Food Blue 1/Food Green 2 -- -- 0.7 Water125 Pigment Red 90 -- Poly(1,5-hexadiene- 100/80 0.8 Acetophenone sulfone)126 Acid Black 2 Colloid of manganese 100/5 -- 0.6 Water/n-Butyl dioxide alcohol (85/15)127 Acid Brown 103 -- -- 0.5 Water128 Acid Yellow 7/Solvent Back 7 CoCl.sub.2 100/2 -- 0.7 Water/Methanol (90/10) (30/70)129 Sulfur Green 2 -- -- 0.9 Water130 Fluorescent Brightening -- -- 0.4 " Agent 87131 Reactive Orange 20 -- -- 0.5 "132 Reactive Brown 7 -- -- 0.8 "133 Reactive Black 12 Sodium metasilicate 100/30 -- 1.0 Water/Amyl alcohol (80/20)134 Azoic Component 17 -- -- 0.6 Water135 Azoic Green 1 -- -- 0.8 "__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 10 30 50 100 150 200__________________________________________________________________________ 65* 100 l 10-13 60 H(1500) 66* 2 m.sup.3 0.05-0.1 45 H(1200) 67* 100 l 10-13 " G H(400) 68* " " " B C F H(300) 69* 1 m.sub.3 0.2-0.3 " H(700) 70* " " " H(800) 71* 100 l 10-13 " B C F H(350) 72* " " " B C F H(320) 73* " " " B C F H(300) 74* " " " B C F H(280) 75 1 m.sup.3 0.2-0.3 10 A A A B C D(20) 76 " " " A A A A A B(3) 77 1 m.sup.3 0.2-0.3 10 A A A A A B(2.5) 78 " " " A A A A A B(2.3) 79 2 m.sup.3 0.05-0.1 " A A B C D F(60) 80 " " " A A B C D F(58) 81 " " " A A A A A B(3) 82 " " " A A B C D F(57) 83 " " " A A B C D F(61) 84 " " " A A B C D F(55) 85 " " " A A A A A B(2.5) 86 100 l 0.3-0.5 20 A A A A A B(2.0) 87 " " " A A B C D F(61) 88 " " " A A A A B C(9) 89 100 l 0.3-0.5 20 A A A A A B(2.1) 90 " " " A A B C D F(60) 91 " " " A A A A A B(59) 92 " " " A A B C D F(60) 93 " " 15 A A B C D F(80) 94 1 m.sup.3 0.2-0.3 " A A B C D F(62) 95 " " " A A B C D F(57) 96 " " " A A A B C D(58) 97 " " " A A B C D F(59) 98 " " " A A A B C D(18) 99 " " " A A A B C D(20) 100 " " " A A A A A B(1.9) 101 1 m.sup.3 0.2-0.3 15 A A B C D F(60) 102 " " 10 A A A A A B(2.5) 103 " " " A A A A A B(2.0) 104 " " " A A B C D F(56) 105 100 l 0.3-0.5 " A A B C D F(57) 106 " " " A A B C D F(59) 107 " " " A A B C D F(60) 108 " " " A A B C D F(57) 109 " " " A A A B C D(20) 110 " " " A A A A B C(11) 111 " 0.8-1 15 A A A A A B(3) 112 " " " A A B C D F(60) 113 100 l 0.8-1 15 A A B C D F(58) 114 " " " A A B C D F(57) 115 " " " A A B C D F(58) 116 " " " A A A A A B(2) 117 " " " A A B C D F(60) 118 " " " A A B C D F(56) 119 " " " A A A B C D(20) 120 " " " A A A A A B(1.9) 121 1 m.sup.3 0.2-0.3 " A A B C D F(57) 122 " " " A A B C D F(58) 123 " " " A A A B C D(20) 124 " " " A A B C D F(59) 125 1 m.sup.3 0.2-0.3 15 A A A B C D(20) 126 " " 10 A A A A A B(3) 127 " " " A A B C D F(57) 128 " " " A A A A A B(1.8) 129 " " " A A A B C D(21) 130 " " " A A B C D F(59) 131 2 m.sup.3 0.05-0.1 " A A B C D F(60) 132 " " " A A B C D F(62) 133 " " " A A A A A B(3) 134 " " " A A B C D F(60) 135 " " " A A B C D F(59)__________________________________________________________________________ Notes: (1) *comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 3
As shown in Table 3, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 3, a dye or a pigment was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of dye or pigment in the coating solution are also shown in Table 3. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 80 parts of vinyl chloride monomer, 20 parts of vinyl acetate monomer, 200 parts of deionized water, 0.3 part of gelatin, 1 part of trichlene and 0.175 part of lauroyl peroxide, and polymerization was carried out at 70.degree. C. for 6 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 3. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
In the same manner as in Example 1, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 3.
In Table 3, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 136 and 137 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound. Also, the coating solution employed in Experiment Nos. 177 and 178 was prepared by dissolving one part of sodium sulfide in 100 parts of water and adding 0.5 part of a dye to the resultant solution, followed by heating at 80.degree. C. for 30 minutes.
TABLE 3__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Dye or pigment (a) compound weight compound weight conc. SolventNo. (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 136* -- -- -- -- 137* -- -- -- -- 138* Solvent Black 5 -- -- 0.5 Methanol 139* " Colloidal silica 100/50 -- 0.8 " 140* -- " 0/100 -- 1.0 Water 141* Solvent Black 5 -- Polystyrene 100/50 0.7 Toluene 142* Basic Black 2 Water glass 100/50 -- 0.9 Water/Isobutyl alcohol (90/10) 143* Disperse Blue 98 BaCl.sub.2 100/5 -- 0.8 Water/Acetone (50/50) 144* Basic Blue 65/Basic Red 34 CuSO.sub.4 100/20 -- 0.9 Water (70/30)145 Acid Violet 41 -- -- 0.5 Methanol146 " Colloidal silica 100/150 -- 0.8 "147 " Al(OH).sub.3 sol 100/2 -- 0.5 "148 Acid Violet 41 FeCl.sub.2 100/5 -- 0.5 Methanol149 Direct Red 13 -- -- " Water150 Direct Green 31 NiCl.sub.2 100/3 -- 0.8 "151 Basic Black 2 Water glass 100/50 -- 0.9 Water/Isobutyl alcohol (90/10)152 Basic Red 18 -- -- 0.5 Water153 Basic Red 22 -- -- 0.4 "154 Basic Red 24 -- -- 0.7 "155 Basic Blue 65/Basic Red 34 CuSO.sub.4 100/20 -- 0.9 " (70/30)156 Azoic Diazo Component 21 -- -- 0.6 Methanol157 Azoic Diazo Component 27 -- -- 0.6 Ethanol158 Disperse Yellow 8 -- Polyglutardialdehyde 100/100 0.8 Ethyl ether159 Disperse Orange 45 -- -- 0.6 Acetone160 Disperse Red 58 -- -- 0.4 Acetone161 Disperse Violet 24 Colloidal silica 100/40 -- 1.0 Water/Acetone (50/50)162 Disperse Yellow 23 -- -- 0.8 Acetone163 Disperse Red 74 -- -- 0.9 "164 Solvent Orange 31 -- -- 0.7 Methanol165 Solvent Orange 16 -- -- 0.8 "166 Solvent Brown 5 Colloid of lithium 100/10 -- 0.8 Water/Methanol silicate (30/70)167 Solvent Black 3 Colloidal silica 100/50 -- 1.0 Water/Acetone (50/50)168 Disperse Black 10 -- -- 0.5 Acetone169 Solvent Yellow 16/Solvent -- -- 0.7 Methanol Orange 45 (60/40)170 Pigment Brown 2 -- Polyvinyl n-butyl 100/40 2.0 Methylene ether chloride171 Pigment Black 1 -- Polycyclopentene 100/70 1.0 Toluene172 Vat Green 8 -- -- 0.5 Xylene173 Disperse Blue 98 BaCl.sub.2 100/5 -- 0.8 Water/Acetone (40/60)174 Vat Violet 10 -- -- 0.7 Xylene175 Vat Red 2/Basic Blue 26 -- -- 0.9 Water/n-Amyl alcohol (90/10)176 Basic Violet 7 -- -- 0.6 Water177 Sulfur Black 6 -- -- 0.8 "178 Sulfur Black 11 -- -- 0.5 "179 Azoic Diazo Component 47 -- -- 0.8 "180 Basic Red 40 -- -- 0.7 "__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 10 30 50 100 150 200__________________________________________________________________________ 136* 100 l 10-13 60 H(1200) 137* 1 m.sup.3 0.2-0.3 " H(800) 138* 40 m.sup.3 7-8 45 B F H(400) 139* " " " B C F H(300) 140* 2 m.sup.3 0.05-0.1 " H(600) 141* 100 l 10-13 " B C F H(400) 142* " " " B C F H(280) 143* " " " B C F H(250) 144* " " " B C F H(310) 145 1 m.sup.3 0.2-0.3 10 A A A B C D(20) 146 " " " A A A A A A(0.5) 147 " " " A A A A A A(0.7) 148 1 m.sup.3 0.2-0.3 10 A A A A A A(0.9) 149 2 m.sup.3 0.05-0.1 15 A A A A B C(10) 150 " " " A A A A A A(0.5) 151 " " " A A A A A A(0.6) 152 " " " A A A A B C(12) 153 " " " A A A B C D(20) 154 " " " A A A B C D(25) 155 " " " A A A A A A(0.5) 156 " " " A A A B C D(19) 157 " " " A A A B C D(20) 158 " " " A A A A B C(10) 159 1 m.sup.3 0.2-0.4 10 A A A B C D(18) 160 1 m.sup.3 0.2-0.4 10 A A A B C D(17) 161 " " " A A A A A A(0.7) 162 " " " A A A B C D(18) 163 " " " A A A B C D(17) 164 " " " A A A B C D(18) 165 " " " A A A B C D(19) 166 130 m.sup.3 0.4-0.7 20 A A A A A A(0.5) 167 " " " A A A A A A(0.6) 168 1 m.sup.3 0.2-0.4 " A A A B C D(20) 169 " " " A A A A A B(3) 170 100 l 0.8-1.0 10 A A A A A B(2.8) 171 " " " A A A A A B(2.9) 172 100 l 0.8-1.0 10 A A A B C D(21) 173 " " " A A A A A A(0.8) 174 " " " A A A B C D(21) 175 " " " A A A B C D(15) 176 " " " A A A B C D(18) 177 " " " A A A A B C(17) 178 " " " A A A B C D(20) 179 " " " A A A B C D(21) 180 " " " A A A B C D(18)__________________________________________________________________________ Notes: (1) *comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 4
As shown in Table 4, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 4, a dye or a pigment was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of dye or pigment in the coating solution are also shown in Table 4. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 parts of vinyl chloride monomer, 200 parts of deionized water, 0.02 part of partially saponified polyvinyl alcohol, 0.03 part of hydroxymethyl cellulose and 0.04 part of di-2-ethylhexyl peroxydicarbonate, and polymerization was carried out at 57.degree. C. for 7 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 4. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
In the same manner as in Example 1, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch.
The numbers of fish eyes in the products obtained from the polymers produced in the 10th, 30th, 50th, 100th, 150th and 200th batches in each experiment were measured as follows. A mixture of 100 parts by weight of a polymer obtained by dehydrating and drying the slurry after polymerization, 50 parts by weight of DOP, 1 part by weight of dibutyltin laurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of titanium oxide and 0.05 part by weight of carbon black was kneaded between two rolls at 150.degree. C. for 7 minutes and then formed into a sheet with a thickness of 0.2 mm. The number of fish eyes per 100 cm.sup.2 contained in the sheet was examined according to the light transmission method. The results are shown in Table 4.
In Table 4, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 181 and 182 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 4__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Dye or pigment (a) compound weight compound weight conc. SolventNo. (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio)181* -- -- -- --182* -- -- -- --183 Solvent Yellow 16/Solvent Colloidal silica 100/100 0.5 Methanol Orange 45 (50/50)184 Solvent Brown 5 Fe(OH).sub.3 sol 100/10 -- 0.9 Acetone185 Acid Yellow 7/Solvent Black Colloidal silica 100/40 -- 1.0 Methanol 7 (20/80)186 Solvent Black 3 Colloid of sulfur 100/20 -- 0.4 "187 Solvent Black 5 CaCl.sub.2 100/5 -- 0.9 "188 Solvent Black 7 Al(OH).sub.3 sol 100/10 -- 0.8 "189 " -- -- 0.8 "__________________________________________________________________________ (3) Surface (4) roughness of Time for washing Scaling(1) Capacity inner wall with water after Visual evaluation (Amount attached Fish eyes (number)Exp. of Poly- surface, etc. completion Batch No. Batch No.No. merizer (Rmax) .mu.m min. 10 30 50 100 150 200 10 30 50 100 150 200__________________________________________________________________________181* 100 l 10-13 60 H(1100) 350182* 1 m.sup.3 0.2-0.3 " C D F H(950) 20 50 100 320183 2 m.sup.3 0.05-0.1 10 A A A A A B(1.5) 0 0 0 0 7 10184 100 l 0.8-1 " A A A A A B(2.0) 0 0 0 0 9 15185 1 m.sup.3 0.2-0.3 " A A A A A A(0.3) 0 0 0 0 0 2186 " " " A A A A A B(2.0) 0 0 0 0 6 11187 130 m.sup.3 0.4-0.7 " A A A A A A(0.5) 0 0 0 0 3 5188 " " " A A A A A A(0.5) 0 0 0 0 2 3189 " " " A A A A A B(3.0) 0 0 0 0 5 10__________________________________________________________________________ Notes: (1) *comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 5
As shown in Table 5, for each experiment, a 5-l, 20-l, or 100-l stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 5, a dye or a pigment was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of dye or pigment in the coating solution are also shown in Table 5. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 75 parts of styrene, 25 parts of acrylonitrile, 120 parts of deionized water, 0.5 part of tricalcium phosphate, 0.01 part of sodium dodecylbenzenesulfonate and 0.4 part of lauroyl peroxide, and polymerization was carried out at 90.degree. C. for 8 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 5. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 10 batches.
In the same manner as in Example 1, scaling after completion of each of the 1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 5.
In Table 5, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 190 and 191 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound. Also, the coating solution employed in Experiment No. 215 was prepared by dissolving one part of sodium sulfide in 100 parts of water and adding 0.5 part of a dye to the resultant solution, followed by heating at 80.degree. C. for 30 minutes.
TABLE 5__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Dye or pigment (a) compound weight compound weight conc. SolventNo. (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio)190* -- -- -- --191* -- -- -- --192* Direct Black 51 -- -- --193* " Cu(NO.sub.3).sub.2 100/10 -- 0.5 Water194* -- " 0/100 -- 0.5 "195* Solvent Black 5 Fe(OH).sub.3 sol 100/20 -- 0.5 Water/Methanol (30/70)196* Basic Red 37 CuCl.sub.2 100/5 -- 0.8 Water197* Direct Black 51 -- -- 0.5 "198* " Cu(NO.sub.3).sub.2 100/10 -- 0.5 "199* " Colloidal silica 100/200 -- 0.8 "200 " Colloid of sulfur 100/20 -- 0.5 "201 " Metadisilicic acid 100/100 -- 0.7 "202 Basic Violet 28 -- -- 0.4 Water203 Basic Blue 67 -- -- 0.9 "204 Disperse Violet 41 -- -- 0.8 Acetone205 Disperse Red 82 -- -- 0.6 "206 Pigment Red 10 -- Polyacetaldehyde 100/30 0.8 Methanol207 Solvent Black 5 Fe(OH).sub.3 sol 100/20 -- 0.5 Water/Methanol (30/70)208 Solvent Red 83 -- -- 1.0 Methanol209 Direct Black 112 Cu(NO.sub.3).sub.2 100/10 -- 0.5 Water210 Vat Black 29 -- Polyvinyl alcohol 100/20 0.8 "211 Basic Violet 14 -- -- 0.5 "212 Basic Blue 41/Solvent Blue 2 Colloidal silica 100/50 -- 0.9 Water/Methanol (40/60) (50/50)213 Acid Orange 19 -- -- 0.4 Water214 Basic Red 37 CuCl.sub.2 100/5 -- 0.6 Water215 Sulfur Brown 12 -- -- 0.8 Water/Isobutyl alcohol (80/20)216 Fluorescent Brightening -- -- 0.6 Water Agent 121217 Azoic Diazo Component 14 -- -- 0.7 "218 Acid Blue 59 Metadisilicic acid 100/100 -- 0.5 Water/n-Amyl alcohol__________________________________________________________________________ (90/10) (3) (4) Surface roughness of Time for washing Scaling(1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2)Exp. Capacity of (Rmax) completion Batch No.No. Polymerizer .mu.m min. 1 2 3 5 7 10__________________________________________________________________________190* 5 l 10-13 20 H(2000)191* 20 l 0.1-0.3 " H(1900)192* 5 l 10-13 " G H(500)193* " " " B E H(200)194* " 0.05-0.1 " H(1800)195* " 10-13 " B E H(210)196* " " " B E H(250)197* 100 l 0.8-1.0 5 A A A B C D(20)198* " " " A A A A A A(0.9)199* " " " A A A A A A(0.8)200 " " " A A A A A A(0.5)201 " " " A A A A A A(0.4)202 5 l 0.05-0.1 " A A A B C D(21)203 " " " A A A B C D(19)204 " " " A A A B C D(18)205 " " " A A A B C D(17)206 " " " A A A A A B(3)207 " " " A A A A A A(0.4)208 " 0.4-0.7 " A A A B C D(20)209 " " 10 A A A A A A(0.9)210 " " " A A A A B C(12)211 " " " A A A B C D(20)212 " " " A A A A A A(0.5)213 20 l 0.1-0.3 " A A A B C D(20)214 " " " A A A A A A(0.8)215 " " " A A A B C D(21)216 " " " A A A B C D(17)217 " " " A A A B C D(18)218 " " " A A A A A A(25)__________________________________________________________________________ Notes: (1) *comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 6
As shown in Table 6, for each experiment, a 5-l, 20-l, or 100-l stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 6, a dye or a pigment was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of dye or pigment in the coating solution are also shown in Table 6. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 parts of styrene monomer, 250 parts of deionized water, 0.2 part of polyvinyl alcohol, 0.75 part of t-dodecyl mercaptan and 0.5 part of lauroyl peroxide, and polymerization was carried out under stirring at 70.degree. C. for 5 hours. Thereafter, the reaction mixture was heated from 70.degree. C. to 80.degree. C. over 2 hours, and polymerization was further conducted at 80.degree. C. for 1 hour. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 6. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 10 batches.
In the same manner as in Example 1, scaling after completion of each of the 1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 6.
In Table 6, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 219 and 220 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 6__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Dye or pigment (a) compound weight compound weight conc. SolventNo. (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 219* -- -- -- -- 220* -- -- -- -- 221* -- Colloidal silica 0/100 -- 0.5 Water 222* -- -- Polyvinyl alcohol 0/100 0.8 " 223* Basic Blue 25 Colloidal silica 100/20 -- 0.6 Water/n-Amyl alcohol (80/20) 224* Solvent Black 5 CoCl.sub.3 100/10 -- 0.7 Water/Methanol (50/50)225 Disperse Yellow 7 -- -- 0.8 Acetone226 Solvent Black 5 CoCl.sub.3 100/10 -- 0.7 Water/Methanol (50/50)227 Solvent Black 5 -- -- 0.5 Methanol228 Solvent Blue 35 -- -- 0.5 "229 Disperse Violet 1 -- -- 0.6 Acetone230 Direct Black 113/Acid Brown Orthosilicic acid 100/50 -- 1.0 Water/Isobutyl 14 (60/40) alcohol (90/10)231 Pigment Blue 3 -- Polyvinyl alcohol 100/50 0.7 Water232 Pigment Violet 3 -- Polyphenylacetylene 100/80 0.8 Methanol233 Basic Orange 2 Water glass 100/100 -- 0.8 Water234 Basic Blue 25 Colloidal silica 100/20 -- 0.6 Water/n-Amyl alcohol (80/20)235 Disperse Orange 20 -- -- 0.5 Acetone236 Solvent Red 24 -- -- 0.5 Methanol237 Basic Blue 54 -- -- 0.7 Water238 Disperse Red 65 -- -- 1.0 Acetone239 Disperse Blue 91 -- -- 0.6 "240 Vat Green 9 -- -- 0.5 Xylene241 Basic Blue 5 Fe(OH).sub.3 sol 100/5 -- 0.8 Water242 Acid Black 2 Sodium metasilicate 100/60 -- 0.6 Water/n-Butyl alcohol (85/15)243 Basic Red 12 -- -- 0.4 Water244 Fluorescent Brightening -- -- 0.7 " Agent 175245 Disperse Orange 30 -- -- 0.9 Acetone246 Pigment Red 7 -- Polyvinyl butyral 100/100 1.0 Ethanol247 Basic Red 38 -- -- 0.5 Water__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached Exp. Capacity of (Rmax) completion g/m.sup.2) Batch No. No. Polymerizer .mu.m min. 1 2 3 5 7 10__________________________________________________________________________ 219* 5 l 10-13 30 H(800) 220* 20 l 0.1-0.3 " G H(750) 221* 5 l 0.05-0.1 " G H(780) 222* " " " G H(800) 223* " 10-13 " B E H(300) 224* " " " B E H(280) 225 100 l 0.8-1.0 15 A A A B C D(20) 226 " " " A A A A A A(0.3) 227 " " " A A A A A B(3) 228 " " " A A A B C D(18) 229 " " " A A A B C D(17) 230 " " 10 A A A A A A(0.5) 231 5 l 0.05-0.1 10 A A A A A B(3) 232 " " " A A A A A B(3.5) 233 " " " A A A A A A(0.7) 234 " " " A A A A A A(0.6) 235 " " " A A A B C D(20) 236 " " " A A A B C D(18) 237 " " " A A A B C D(19) 238 20 l 0.1-0.3 " A A A B C D(21) 239 " " " A A A B C D(18) 240 " " 15 A A A B C D(19) 241 " " " A A A A A A(0.9) 242 " " " A A A A A A(0.5) 243 5 l 0.4-0.7 15 A A A B C D(20) 244 " " " A A A B C D(25) 245 " " " A A A B C D(20) 246 " " " A A A A A B(4) 247 " " " A A A B C D(18)__________________________________________________________________________ Notes: (1) *comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 7
As shown in Table 7, for each experiment, a 5-l, 20-l, or 100-l stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 7, a dye or a pigment was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of dye or pigment in the coating solution are also shown in Table 7. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 148 parts of water, 1.85 parts of sodium oleate, 48 parts of polybutadiene latex (solid content: 45%), 33 parts of styrene monomer, 19 parts of acrylonitrile monomer, 0.15 part of t-dodecyl mercaptan and 0.5 part of cumene hydroperoxide. After the temperature of the mixture was raised to 65.degree. C., the polymerizer was further charged with 0.74 part of glucose, 0.0074 part of ferrous sulfate and 0.37 part of sodium pyrophosphate, and polymerization was carried out under stirring at 65.degree. C. for 5 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 7. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 10 batches.
In the same manner as in Example 1, scaling after completion of each of the 1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 7.
In Table 7, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 248 and 249 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 7__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Dye or pigment (a) compound weight compound weight conc. SolventNo. (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 248* -- -- -- -- 249* -- -- -- -- 250* -- Sodium metasilicate -- 0.5 Water 251* -- Polyvinyl sulfonic acid 0.7 " 252* Solvent Black 5 Colloidal silica 100/50 -- 0.7 Water/Methanol (30/70) 253* Basic Orange 2 Sodium metasilicate 100/100 -- 0.8 Water254 Solvent Red 23 -- -- 0.4 Methanol255 Solvent Yellow 6/Direct -- -- 1.0 Water/Methanol Black 107 (40/60) (50/50)256 Disperse Blue 7 -- -- 0.5 Acetone257 Disperse Violet 37 -- -- 0.8 "258 Acid Black 2/Solvent -- -- 0.6 Water/Methanol Yellow 14 (90/10) (60/40)259 Pigment Red 14 -- Polyvinyl acetate 100/100 0.8 Toluene260 Pigment Brown 1 -- Polyvinyl ethyl ether 100/30 0.9 Methylene chloride261 Solvent Black 5 Colloidal silica 100/50 -- 0.7 Water/Methanol (30/70)262 Basic Blue 45 -- -- 0.5 Water263 Vat Brown 25 -- Polyvinyl sulfonic 100/50 0.6 " acid264 Disperse Blue 79 -- -- 0.3 Acetone265 Acid Yellow 29 -- -- 0.5 Water266 Basic Orange 2 Sodium metasilicate 100/100 -- 0.8 "267 Disperse Blue 90 Lithium orthosilicate 100/40 -- 0.8 Water/Acetone (40/60)268 Basic Violet 1 -- -- 0.7 Water269 Disperse Yellow 4 -- -- 0.5 Acetone270 Disperse Red 52 -- -- 0.6 "271 Solvent Black 3 -- -- 0.5 "272 Acid Red 303 Colloidal silica 100/60 -- 0.6 Water273 Fluorescent Brightening -- -- 0.4 " Agent 153274 Disperse Red 17 -- -- 0.5 Acetone275 Basic Red 2 ZnCl.sub.3 100/10 -- 0.8 Water/Isobutyl alcohol (80/20)276 Disperse Yellow 3 -- -- 0.5 Acetone__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 1 2 3 5 7 10__________________________________________________________________________ 248* 5 l 10- 13 45 H(1500) 249* 20 l 0.1-0.3 " G H(800) 250* " " " G H(1100) 251* " " " G H(1200) 252* 5 l 0.05-0.1 " B E H(700) 253* " " 15 B E H(650) 254 " 0.4-0.7 " A A B C D H(200) 255 " " " A A A B C D(20) 256 " " " A A A B C D(25) 257 " " " A A A B C D(18) 258 " " " A A A A A A(0.5) 259 " " " A A A A A B(3) 260 100 l 0.8-1.0 10 A A A A A B(4) 261 " " " A A A A A A(0.4) 262 " " " A A A B C D(19) 263 " " " A A A A A B(2.5) 264 5 l 0.05-0.1 " A A A B C D(18) 265 " " " A A B C D H(100) 266 " " " A A A A A A(0.9) 267 " " " A A A A A A(0.7) 268 " " " A A A B C D(20) 269 " " " A A A B C D(21) 270 " " " A A A B C D(19) 271 20 l 0.1-0.3 " A A A A A B(3) 272 20 l 0.1-0.3 10 A A A A A A(0.9) 273 " " " A A A B C D(20) 274 " " " A A A B C D(21) 275 " " " A A A A A A(0.5) 276 " " " A A A B C D(20)__________________________________________________________________________ Notes: (1) *comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 8
As shown in Table 8, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 8, a conjugated .pi. bond compound was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound or the polymeric compound and the concentration of the conjugated .pi. bond compound in the coating solution are also shown in Table 8. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 parts of vinyl chloride monomer, 200 parts of deionized water, 0.022 part of partially saponified polyvinyl alcohol, 0.028 part of hydroxyethyl cellulose and 0.03 part of t-butyl peroxyneodecanate, and polymerization was carried out at 52.degree. C. for 7 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 8. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
In the same manner as in Example 1, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 8.
In Table 8, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 301 to 306 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 8__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Conjugated .pi. bond compound (a) compound weight compound weight conc. SolventNo. Kind (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio)301* -- -- --302* -- -- --303* Quinalizarin -- -- 0.5 Methanol304* Quinalizarin Colloidal silica 100/50 0.8 "305* -- " 0/100 -- 0.5 Water306* Aurine Colloid of sulfur 100/30 -- 0.8 Water/Methanol (30/70)307* Azotoluene/ -- Poly(N--vinylbenzo- 100/30 0.6 DMF Phenazoxide triazole) (60/40)308* 1,2-Dichloro- Metasilicic acid 100/50 -- 0.6 Water/Methanol naphthalene (30/70)309* Azoxyanthraquinone Colloid of sulfur 100/10 -- 0.7 Water/Methanol (50/50)310 Quinalizarin Fe(OH).sub.3 sol 100/5 -- 0.5 Water/Methanol (50/50)311 " Al(OH).sub.3 sol 100/2 -- 0.4 Water/Methanol (50/50)312 " CuCl.sub.2 100/10 -- 0.6 Water/Methanol (50/50)313 Quinalizarin FeCl.sub.3 100/15 -- 0.5 Water/Methanol (50/50)314 Phenylazo-2- Fe(OH).sub.3 sol 100/5 -- 0.5 Water/Methanol naphthol (50/50)315 Succinic acid -- -- 0.7 Methanol bis(.beta.-phenyl- hydrazine)316 Bisphenylhydrazone -- -- 0.6 "317 Benzophenone -- -- 0.5 " potassium318 Disalicylaldehyde Colloidal silica 100/30 -- 0.8 Water/Methanol (80/20)319 Aurin Colloid of sulfur 100/20 -- 0.8 Water/Methanol (30/70)320 Fluorene -- -- 0.6 Methanol321 Chlorobenzophenone -- -- 0.8 "322 6-Chloro-3- -- -- 0.5 " benzoylflavone323 Azotoluene/ (60/40) -- Poly(N-vinylbenzo- 100/30 0.6 DMF Phenazoxide triazole)324 2-Aminostilbene -- -- 0.9 Methanol325 2-Aminostilbene Al(OH).sub.3 sol 100/10 -- 0.8 Water/Methanol (20/80)326 Terphenyl -- -- 0.5 Methanol327 N--Methylnaph- -- -- 0.5 " thylamine328 1,2-Dichloro- -- -- 0.7 Water/Methanol naphthalene (30/70)329 1,2-Dichloro- Metasilicic acid 100/50 -- 0.6 Water/Methanol naphthalene (30/70)330 1-Phenoxynaph- -- -- 0.8 Methanol thalene331 Dinaphthoquinone -- -- 0.5 "332 Imide chloride -- -- 0.5 "333 4-Oxybenzanthrone -- -- 0.6 "334 1-Aminoanthracene Orthosilicic acid 100/30 -- 0.8 Water/Methanol (50/50)335 1,4-Diamino- Metasilicic acid 100/50 -- 0.8 Water/Methanol anthracene (20/80)336 1,1'-Bianthryl -- -- 0.5 Methanol337 Estrone/3- (50/50) -- -- 0.5 " Acetylretene338 2,7-Dibromophenan- -- -- 0.8 " threnequinone339 2-Oxyretenequinone -- -- 0.9 "340 Benzo[a]pyrene- -- -- 0.6 " 1,6-quinone341 1,4-naphthoquinone -- -- 0.6 " phenoxathine342 2-Methyl-3-phytil-1,4- -- Polyacetaldehyde 100/30 1.0 " naphthoquinone343 Di-(3-oxy-1,4- -- 0.7 " naphthoquinonyl- 2-)methane344 Quinalizarin -- -- 0.5 "345 Azoxyanthraquinone -- -- 0.7 Water/Methanol (50/50)346 Azoxyanthraquinone Colloid of sulfur 100/10 -- 0.7 Water/Methanol (50/50)347 Benzopyran/6- (40/60) -- -- 0.7 Methanol Phenylcumalin348 Dracorhodin/ (50/50) -- -- 0.6 " Petunidin349 Fukugetin -- -- 0.8 "350 Xanthotoxin -- -- 0.9 "351 Bilirubin -- -- 0.7 "352 3-Triphenyl- -- -- 0.7 " methylindole353 Tryptophan/ -- -- 0.5 " Violasein (70/30)354 2,2'-Diaminodiphenyl Colloidal silica 100/100 -- 0.8 Water/Methanol (40/60)355 5-Amino-3-methyl-4- -- 0.7 Methanol phenylisoxazole356 2-Phenylimidazole -- Poly(1,5-hexane- 100/50 1.0 Acetophenone dienesulfone)357 5-Amino-3- -- -- 0.7 Methanol phenylpyrazole358 3,4-Diphenylfurazane -- -- 0.6 "359 Quinaldine/ (0/60) -- -- 0.9 " Naphthocyanol360 6-Aminomethyl- -- -- 0.4 " phenanthridine361 Quinazoline/ (50/50) -- -- 0.5 " 2,3-Dimethyl- quinoxaline362 Quinazoline (50/50) Fe(OH).sub.3 sol 100/5 -- 0.9 " 2,3-Dimethyl- quinoxaline363 .alpha.-Sexithienyl -- -- 0.6 "364 2,3-Thiophan- -- -- 0.8 " thraquinone365 8,9-Benzothio- -- -- 0.8 " phanthrene366 Thiaxanthone -- -- 0.6 "367 Thianthrene -- -- 0.9 "368 3-Ethyl-2-phenyl- Colloidal silica 100/200 -- 0.5 Water/Methanol pyrrocoline (50/50)369 Canadine methiodide -- -- 0.7 Methanol370 Codamine -- -- 1.0 "371 Flindersine -- -- 0.7 "372 Laudanine/ (50/50) Colloid of vanadium 100/50 -- 1.0 Water/Methanol Corpaverine pentoxide (20/80)373 o-Methylberbamine -- -- 0.5 Methanol374 Angelicin -- -- 0.5 "375 Pimpinellin -- -- 0.3 "376 Medakenine -- -- 0.5 "377 Xanthoxylene -- -- 0.6 "378 Nodakenetin -- Polyethylene 100/50 0.8 " terephthalate379 Seselin -- -- 0.7 "380 Oroselole -- -- 0.6 "381 Psoralen -- -- 0.5 "382 Dixanthylene -- -- 0.5 "383 9,9-Diphenylxanthene -- -- 0.7 "384 2,5-Diphenylisoindole -- -- 0.4 "385 Naphtho[1,2] CuCl.sub.2 100/10 -- 0.8 Water/Methanol thiazole (30/70)386 2-Fluoroquinoline/ Al(OH).sub.3 sol 100/20 -- 0.7 Water/Methanol Quinoxaline (50/50)387 1,5-Diphenyltetrazole -- -- 0.5 Methanol__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 10 30 50 100 150 200__________________________________________________________________________ 301* 100 l 10-13 60 H (1200) 302* 1 m.sup.3 0.2-0.3 " E H (800) 303* 40 m.sup.3 7-8 " E H (700) 304* " " " B E H (250) 305* 1 m.sup.3 0.2-0.3 " H (800) 306* 100 l 10-13 " B E H (400) 307* " " " E H (400) 308* " " " B E H (300) 309* " " " B E H (280) 310 2 m.sup.3 0.05-0.1 15 A A A A A B (2.1) 311 " " " A (1.8) A A A A B (1.8) 312 " " " A A A A A B (2.0) 313 " " " A A A A A B (2.5) 314 " " " A A A A A B (3) 315 " " " A A A B C D (20) 316 " " " A A A B C D (15) 317 " " " A A A B C D (18) 318 " " " A A A A A B (1.8) 319 " " " A A A A A B (3) 320 " " " A A A B C D (20) 321 " " " A A B C D F (60) 322 100 l 0.8-1.0 " A A A B C D (21) 323 " " 10 A A A A B B (2.6) 324 " " " A A A B C D (21) 325 " " " A A A A A B (2.8) 326 " " " A A A B C D (20) 327 " " " A A A B C D (23) 328 " " " A A A B C D (19) 329 " " " A A A A A B (3) 330 " " " A A A B C D (18) 331 " " " A A B C D F (60) 332 " " " A A B C D F (59) 333 " " 15 A A A B C D (20) 334 130 m.sup.3 0.4-0.7 20 A A A A A B (3) 335 " " " A A A A A B (2.5) 336 1 m.sup.3 0.2-0.3 " A A A B C D (21) 337 " " " A A B C D F (55) 338 " " " A A A B C D (15) 339 " " " A A A B C D (17) 340 " " " A A B C D F (58) 341 " " " A A A B C D (15) 342 " " " A A A B B C (8) 343 " " " A A A B C D (14) 344 " " " A A A B C D (17) 345 " " " A A A B C D (19) 346 " " " A A A A A B (2.2) 347 " " " A A A B C D (18) 348 " " " A A A B C D (13) 349 " " " A A A B C D (19) 350 " " " A A A B C D (20) 351 " " " A A B C D F (60) 352 " " " A A A B C D (20) 353 130 m.sup.3 0.4-0.7 15 A A A B C D (18) 354 100 l 0.8-1.0 " A A A A A B (2.6) 355 " " " A A A B C D (19) 356 " " " A A A B B C (5) 357 " " " A A A B C D (13) 358 " " " A A A B C D (19) 359 " " " A A A B C D (16) 360 " " " A A A B C D (18) 361 " " " A A A B C D (15) 362 " " " A A A A A B (1.9) 363 " " " A A B C D F (60) 364 " " " A A A B C D (20) 365 2 m.sup.3 0.05-0.1 10 A A A B C D (20) 366 " " " A A B C D F (60) 367 " " " A A A B C D (21) 368 " " " A A A A A B (2) 369 " " " A A A B C D (18) 370 " " " A A A B C D (17) 371 " " " A A A B C D (20) 372 " " " A A A A A B (1.9) 373 " " " A A B C D F (61) 374 " " " A A B C D F (60) 375 100 l 0.8-1.0 " A A A B C D (18) 376 " " " A A A B C D (17) 377 " " " A A A B C D (15) 378 " " " A A A A B C (8) 379 " " " A A B C D F (60) 380 " " " A A B C D F (58) 381 " " " A A B C D F (57) 382 100 l " " A A B C D F (60) 383 " " " A A A B C D (20) 384 130 m.sup.3 0.4-0.7 15 A A A B C D (20) 385 " " " A A A A A B (2.7) 386 1 m.sup.3 0.2-0.3 " A A A A A B (2.5) 387 " " " A A A B C D__________________________________________________________________________ (18) Notes: (1) *comparative examples (2) Conjugated .pi. bond compound concentration in coating solution. (3) Surface roughness of the inner wall surfacce of the polymerizer and the portions of the equipment therof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 9
As shown in Table 9, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 9, a conjugated .pi. bond compound was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound or the polymeric compound and the concentration of the conjugated .pi. bond compound in the coating solution are also shown in Table 9. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 parts of vinyl chloride monomer, 200 parts of deionized water, 0.125 part of hydroxypropylmethyl cellulose, 0.125 part of sorbitan monolaurate and 0.025 part of a .alpha.,.alpha.'-azobis-2,4-dimethylvalelonitrile, and polymerization was carried out at 52.degree. C. for 10 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 9. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
In the same manner as in Example 1, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 9.
In Table 9, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 388 and 389 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 9__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Conjugated .pi. bond compound (a) compound weight compound weight conc. SolventNo. Kind (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio)388* -- -- --389* -- -- --390* 2,4-Dinitrophenoxazine -- -- 0.5 Methanol391* " Silicomolybdic acid 100/50 -- 1.0 Water/Methanol (30/70)392* -- Silicomolybdic acid 0/100 -- 0.5 Water393* 1-Aminoacetylnaphthalene Fe(OH).sub.3 sol 100/20 -- 0.8 Water/Methanol (10/90)394 2,4-Dinitrophenoxazine -- -- 0.5 Water/Methanol (30/70)395 2,4-Dinitrophenoxazine Silicomolybdic acid 100/50 -- 1.0 Water/Methanol (30/70)396 Triphenylenedioxazine -- -- 0.6 Methanol397 Bis(4-nitrophenylhydrazine) -- -- 0.5 "398 Dinitrobenzyl -- -- 0.7 "399 Phlorchinyl -- -- 0.8 "400 2-Oxy-4-methylquinone -- -- 0.6 Methanol401 2,2'-Diaminostilbene -- -- 0.5 "402 Di-.alpha.-naphthylmethane -- Polyindene 100/50 0.8 Benzene403 Naphthazarin/Perimidone -- -- 1.0 Methanol (70/30)404 Diaminotetralin Colloidal silica 100/100 -- 0.7 Water/Methanol (50/50)405 2,3-Dihydrazinonaphthalene -- Polyvinyl ethyl ether 100/100 0.9 Chloroform406 3-Acetyl-6,7-benzocumarin -- -- 0.6 Methanol407 1,2-Benzoxanthone -- -- 0.5 "408 1-Aminoacetylnaphthalene Fe(OH).sub.3 sol 100/20 0.8 Water/Methanol (10/90)409 9-Isopropylanthracene -- -- 0.6 Methanol410 Anthrone/6-Acylaminoretene -- -- 0.9 " (50/50)411 2,7-Diaminophenanthrenequinone ZnCl.sub.2 100/5 -- 0.7 Water/Methanol (20/80)412 Nitrosaminonaphthoquinone -- -- 0.6 Water/Methanol (50/50)413 Nitrosaminonaphthoquinone Orthosilicic acid 100/100 -- 0.7 Water/Methanol (50/50)414 Azoxyanthraquinone Mesotrisilicic acid 100/50 -- 0.4 Water/Methanol (40/60)415 Alizarinquinone/Pyridoxine -- -- 0.9 Methanol (80/20)416 Stercobilin -- -- 0.6 "417 2-Methyl[1,2]thiazole -- -- 0.4 "418 Azacyanine -- -- 0.9 "419 Acriflavine -- -- 0.6 "__________________________________________________________________________ (3) (4) Scaling (1) Surface roughness of Time for washing Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of inner wall surface, etc. with water after Batch No. No. Polymerizer (Rmax) .mu.m completion min. 10 30 50 100 150 200__________________________________________________________________________ 388* 100 l 10-13 45 H(1500) 389* 2 m.sup.3 0.05-0.1 " H(1200) 390* 40 m.sup.3 7-8 " G H(700) 391* " " 30 B E H(500) 392* 2 m.sup.3 0.05-0.1 " H(900) 393* 100 l 10-13 " B C F H(400) 394 2 m.sup.3 0.05-0.1 " A A B C D F(60) 395 " " " A A A A B C(10) 396 " " " A A B C D F(59) 397 " " " A A B B C D(20) 398 " " " A A B C D E(31) 399 " " " A A B C D F(61) 400 " " " A A B C D E(29) 401 " " " A A B C D F(60) 402 " " " A A A B C D(23) 403 " " " A A B C D E(30) 404 " " " A A A A B C(10) 405 " " " A A A B C D(21) 406 " " " A A B C D F(60) 407 1 m.sup.3 0.2-0.3 " A A B C D F(58) 408 " " " A A A A B C(9) 409 " " " A A B C D F(60) 410 " " " A B B C D F(65) 411 " " " A A A A B C(8) 412 " " " A A B C D F(60) 413 " " " A A A A B C(20) 414 " " " A A A A B C(21) 415 " " " A A B C D E(30) 416 " " " A B B C D F(62) 417 " " " A A B C D F(60) 418 " " " A A B C D E(30) 419 " " " A A B C D E(29)__________________________________________________________________________ Notes: (1) *comparative examples (2) Conjugated .pi. bond compound concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 10
As shown in Table 10, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 10, a conjugated .pi. bond compound was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound or the polymeric compound and the concentration of the conjugated .pi. bond compound in the coating solution are also shown in Table 10. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 80 parts of vinyl chloride monomer, 20 parts of vinyl acetate monomer, 200 parts of deionized water, 0.3 part of gelatin, 1 part of trichlene and 0.175 part of lauroyl peroxide, and polymerization was carried out at 70.degree. C. for 6 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 10. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
In the same manner as in Example 1, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 10.
In Table 10, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 420 and 421 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 10__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Conjugated .pi. bond compound (a) compound weight compound weight conc. SolventNo. Kind (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio)420* -- -- --421* -- -- --422* 9,9-Azoxyphenanthrene -- -- Methanol423* " Fe(OH).sub.3 sol 100/5 -- 0.8 "424* -- Fe(OH).sub.3 sol 0/100 -- 0.5 Water425* 4-Aminoacridine Water glass 100/50 -- 0.6 Water/Methanol (80/20)426 Egonol -- -- 1.0 Methanol427 Dibenzofuran -- -- 0.9 "428 Euparin -- -- 0.5 "429 Dracorubin/Pelargonidin -- -- 1.0 " (50/50)430 Isopimpinellin Colloidal silica 100/200 -- 1.0 Water/Methanol (20/80)431 2,3,4,5-Tetraphenylpyrrole -- -- 0.5 Methanol432 1,3-Diphenylpyrazole -- -- 0.7 Methanol433 4-Aminoacridine -- -- 0.6 Water/Methanol (80/20)434 4-Aminoacridine Water glass 100/50 -- 0.6 Water Methanol (80/20)435 3-Bromocinnoline -- -- 0.7 Methanol436 Cyclo[3.2.2]azine MgCl.sub.2 100/10 -- 0.7 Water/Methanol437 Heteroquinine/Quinotoxine -- -- 0.9 Methanol (70/30)438 Naphthotropone Colloid of lithium 100/50 -- 1.0 Water/Methanol silicate (50/50)439 N--Naphthylglycine -- Polycyclohexane 100/70 1.5 Benzene oxide440 .alpha.-Naphthylhydrazine -- -- 0.7 Methanol441 4-Amino-1-naphthaldehyde -- -- 0.6 "442 4-Amino-1-naphthaldehyde Orthosilicic acid 100/30 -- 0.8 Water/Methanol (70/30)443 2-Aminobenzoylnaphthalene -- -- 0.7 Water/Methanol (10/90)444 9,9'-Azoxyphenanthrene Fe(OH).sub.3 sol 100/5 -- 0.8 Methanol445 Mesonaphthodianthrene -- -- 0.4 "446 Triphthaloylbenzene -- -- 0.7 "447 Anthraquinoneacridone -- -- 0.6 "448 Anthraquinoneacridone CaCl.sub.2 100/5 -- 0.6 "449 Mesonaphthodianthrone -- -- 0.8 "450 Phenazine -- -- 0.4 "451 2-Methylquinazoline -- -- 0.9 "__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 10 30 50 100 150 200__________________________________________________________________________ 420* 100 l 10-13 45 H(1100) 421* 2 m.sup.3 0.05-0.1 " H(700) 422* 40 m.sup.3 7-8 " B E H(500) 423* " " " B C F H(400) 424* 2 m.sup.3 0.05-0.1 " H(800) 425* 100 l 10-13 " B C F H(500) 426 1 m.sup.3 0.2-0.3 15 A A A B C D(20) 427 " " " A A B C D F(60) 428 " " " A A B C D F(61) 429 " " " A A B C D F(58) 430 " " " A A A A A B(2.5) 431 " " " A A B C D F(58) 432 1 m.sup.3 0.2-0.3 15 A A A B C D(20) 433 " " " A A A B C D(18) 434 " " " A A A A A B(2.3) 435 " " " A A B C D F(59) 436 " " " A A A A B C(10) 437 100 l 0.8-1.0 10 A A A B C D(21) 438 " " " A A A A B C(9) 439 " " " A A A B B C(8) 440 " " " A A B C D F(60) 441 " " " A A A B C D(21) 442 " " " A A A A B C(10) 443 " " " A A A B C D(23) 444 100 l 0.8-1.0 10 A A A A B C(9) 445 " " " A A A B C D(21) 446 " " " A A A B C D(20) 447 2 m.sup.3 0.05-0.1 " A A A B C D(18) 448 " " " A A A A B C(9) 449 " " " A A B C D F(50) 450 " " " A A A B C D(21) 451 " " " A A A B C D(19)__________________________________________________________________________ Notes: (1) *comparative examples (2) Conjugated .pi. bond compound concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 11
As shown in Table 11, for each experiment, a 100-l, 1000-l, 2000-l, 40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table II, a conjugated .pi. bond compound was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound or the polymeric compound and the concentration of the conjugated .pi. bond compound in the coating solution are also shown in Table 11. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 part of vinyl chloride monomer, 200 parts of deionized water, 0.02 part of partially saponified polyvinyl alcohol, 0.03 part of hydroxymethyl cellulose and 0.04 part of di-2-ethylhexyl peroxydicarbonate, and polymerization was carried out at 57.degree. C. for 7 hours After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 11. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 200 batches.
In the same manner as in Example 1, scaling after completion of each of the 10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch.
The numbers of fish eyes in the products obtained from the polymers produced in the 10th, 30th, 50th, 100th, 150th and 200th batches in each experiment were measured in the same manner as in Example 4. The results are shown in Table 11.
In Table 11, the Experimental numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 452 and 453 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 11__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Conjugated .pi. bond compound (a) compound weight compound weight conc. SolventNo. Kind (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio)452* -- -- --453* -- -- --454 Quinalizarin Colloidal silica 100/100 -- 0.8 Methanol455 Disalicylaldehyde Fe(OH).sub.3 sol 100/10 -- 0.9 "456 1-Phenoxynaphthalene CaCl.sub.2 100/5 -- 0.5 "457 Azoxyanthraquinone Colloid of sulfur 100/40 -- 0.6 "458 Quinaldine/Naphthocyanol CuCl.sub.2 100/20 -- 1.0 " (50/50)459 2,5-Diphenylisoindole Al(OH).sub.3 sol 100/10 -- 0.7 "460 2,2'-Diaminostilbene Ni(NO.sub.3).sub.2 100/5 -- 0.8 "461 Naphthazarin/Perimidone Fe(OH).sub.3 sol 100/10 -- 0.7 " (60/40)462 Azacyanine Colloidal silica 100/100 -- 0.9 Methanol463 Azacyanine -- -- 0.9 "__________________________________________________________________________ (3) (4) Surface roughness Time for washing Scaling(1) of inner wall with water after Visual evaluation (Amount attached Fish eyes(number)Exp. Capacity of surface, etc. completion g/m.sup.2) Batch No. Batch No.No. Polymerizer (Rmax) .mu.m min. 10 30 50 100 150 200 10 30 50 100 150 200__________________________________________________________________________452* 100 l 10-13 60 H(1000) 300453* 40 m.sup.3 7-8 " H(950) 280454 100 l 0.8-1.0 15 A A A A B C(10) 0 0 0 0 30 55455 " " " A A A A B C(9) 0 0 0 0 25 50456 " " " A A A A B C(7) 0 0 0 0 13 30457 " " " A A A A B C(9) 0 0 0 0 15 35458 130 m.sup.3 0.4-0.7 " A A A A B C(8) 0 0 0 0 20 40459 1 m.sup.3 0.2-0.3 " A A A A B C(10) 0 0 0 0 35 70460 " " " A A A A B C(7) 0 0 0 0 12 20461 " " " A A A A B C(8) 0 0 0 0 21 40462 1 m.sup.3 0.2-0.3 15 A A A A B C(10) 0 0 0 0 32 60463 " " " A A A B C D(18) 0 0 0 15 40 70__________________________________________________________________________ Notes: (1) *comparative examples (2) Conjugated .pi. bond compound concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 12
As shown in Table 12, for each experiment, a 5-l, 20-l, or 100-l stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 12, a conjugated .pi. bond compound was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound or the polymeric compound and the concentration of the conjugated .pi. bond compound in the coating solution are also shown in Table 12. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 75 parts of styrene, 25 parts of acrylonitrile, 120 parts of deionized water, 0.5 part of tricalcium phosphate, 0.01 part of sodium dodecylbenzenesulfonate and 0.4 part of lauroyl peroxide, and polymerization was carried out at 90.degree. C. for 8 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 12. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 10 batches.
In the same manner as in Example 1, scaling after completion of each of the 1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 12.
In Table 12, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 464 and 465 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 12__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Conjugated .pi. bond compound (a) compound weight compound weight conc. SolventNo. Kind (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 464* -- -- -- 465* -- -- -- 466* Diaminonaphthalene -- -- 0.6 Methanol 467* " Colloidal silica 100/50 -- 0.6 " 468* -- Colloidal silica 0/100 -- 0.5 Water 469* N--Benzylnaphthylamine CaCl.sub.3 100/5 -- 0.7 Methanol 470* 1-Benzoylphenanthrene Fe(OH).sub.3 sol 100/20 -- 0.5 " 471* Isoxazole Mesotetrasilicic acid 100/100 -- 0.6 Water/Methanol (50/50)472 Diaminonaphthalene -- -- 0.6 Methanol473 " Colloidal silica 100/50 -- 0.6 "474 Tetraaminonaphthalene -- -- 0.8 "475 N--Methylnaphthylamine -- -- 1.0 "476 N--Benzylnaphthylamine CoCl.sub. 3 100/5 -- 0.7 Methanol477 N--Phthaloylnaphthylamine -- Polyvinyl alcohol 100/30 0.6 Water/Isobutyl alcohol (90/10)478 Aminotetralin -- -- 0.4 Methanol479 Acenaphthene/Dinaphthopyran -- -- 0.7 "480 1-Benzoylphenanthrene -- -- 0.5 "481 1-Benzoylphenanthrene Fe(OH).sub.3 sol 100/20 -- 0.5 "482 4,4'-Diphenoquinone -- Polypyridylacetylene 100/80 0.8 "483 Phenanthrophenazine -- -- 0.6 "484 Calchonphenylhydrazone -- -- 0.7 "485 Apigeninidin -- -- 0.5 "486 Apigeninidin Colloidal silica 100/150 -- 0.8 Water/Methanol (30/70)487 Ostruthol/Bergapten -- -- 0.7 Methanol488 Prodigiosin -- -- 0.5 Methanol489 Isoxazole Mesotetrasilicic acid 100/100 -- 0.6 Water/Methanol (50/50)490 2-Aminonaphtho[2,1]thiazole -- -- 0.6 Methanol__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling(1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2)Exp. Capacity of (Rmax) completion Batch No.No. Polymerizer .mu.m min. 1 2 3 5 7 10__________________________________________________________________________ 464* 5 l 10-13 20 H(1200) 465* 20 l 0.1-0.3 " H(1950) 466* 5 l 10-13 " G H(700) 467* " " " B E H(280) 468* " 0.05-0.1 " G H(1000) 469* " 10-13 " B E H(600) 470* " " " B E H(400) 471* " " " B E H(300)472 100 l 0.8-1.0 10 A A A B C D(20)473 " " " A A A A A B(3)474 " " " A A A B C D(21)475 " " " A A A B C D(18)476 20 l 0.1-0.3 10 A A A A A B(2.5)477 " " " A A A A B C(10)478 " " " A A A B C D(22)479 " " " A A A B C D(25)480 5 l 0.05-0.1 " A A A B C D(19)481 " " " A A A A A B(2.1)482 " " " A A A A B C(12)483 " " " A A A B C D(20)484 " " 5 A A A B C D(18)485 " " " A A A B C D(15)486 " 0.4-0.7 " A A A A A B(2.5)487 " " " A A A B C D(20)488 5 l 0.4-0.7 5 A A A B C D(17)489 " " " A A A A A B(2.8)490 " " " A A A B C D(25)__________________________________________________________________________ Notes: (1) *comparative examples (2) Conjugated .pi. bond compound concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 13
As shown in Table 13, for each experiment, a 5-l, 20-l, or 100-l stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 13, a conjugated .pi. bond compound was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of the conjugated .pi. bond compound in the coating solution are also shown in Table 13. The coating solution was applied on the polished inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 100 parts of styrene monomer, 250 parts of deionized water, 0.2 part of polyvinyl alcohol, 0.75 part of t-dodecyl mercaptan and 0.5 part of lauroyl peroxide, and polymerization was carried out at 70.degree. C. for 5 hours. Thereafter, the temperature of the mixture was raised from 70.degree. C. to 80.degree. C. over 2 hours, and polymerization was conducted at 80.degree. C. for another one hour. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for a period of time shown in Table 13. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 10 batches.
In the same manner as in Example 1, scaling after completion of each of the 1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 13.
In Table 13, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 491 and 492 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 13__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Conjugated .pi. bond compound (a) compound weight compound weight conc. SolventNo. Kind (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 491* -- -- -- 492* -- -- -- 493* -- Colloidal silica 0/100 -- 494* -- -- Poly(3-phenoxylene) 0/100 0.5 Methanol 495* Pararosaniline Colloidal silica 100/20 -- Water/Methanol (40/60) 496* 3-Nitro-2-phenylindole/Acid Colloidal silica 100/50 -- 0.8 Water/Methanol Red 274 (50/50)497 Benzoic acid toluidide -- -- 0.4 Methanol498 2-Phenylbenzoxazole -- -- 0.8 "499 3-Nitro-2-phenylindole -- -- 0.3 "500 Pararosaniline Colloidal silica 100/20 -- 0.6 Water/Methanol (40/60)501 Pyrrole-polymethine dye -- -- 0.4 Methanol502 9-Benzylacridine -- Poly(3-phenoxylene) 100/30 0.5 "503 5-Phenylthiazole -- -- 0.5 Methanol504 2-(o-Aminophenyl)benzimidazole -- -- 0.3 "505 Indigo/Carbazole Fe(OH).sub.3 sol 100/10 -- 0.5 Water/Methanol (70/30) (10/90)506 3-Nitro-2-phenylindole/Acid Colloidal silica 100/50 -- 0.8 Water/Methanol Red 274 (40/60) (50/50)507 1-Chloroisoquinoline -- -- 0.9 Methanol508 1-Aminoacridine -- -- 0.5 "509 8-Methyl-1,7-phenanthroline -- -- 0.4 "510 5-Phenyltetrazole Colloidal silica 100/100 -- 0.7 Water/Methanol (40/60)511 2-Methylquinoxaline -- -- 0.5 Methanol512 1-Phenazinol -- -- 0.3 "513 Bis(3-dibenzofuryl) Metasilicic acid 100/20 -- 0.5 Water/Methanol (20/80)514 2-Iodobenzothiophene -- -- 0.9 Methanol515 Naphtho[1,2-b]thiophene -- -- 0.8 Methanol516 2,3-Diaminophenazine/Direct -- -- 0.8 Water/Methanol Green 6 (50/50) (40/60)517 Benzo[b] quinolizinium salt Colloidal silica 100/100 -- 0.6 Water518 Acronycidine -- -- 0.4 Methanol__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 1 2 3 5 7 10__________________________________________________________________________ 491* 5 l 10-13 30 H(800) 492* 20 l 0.1-0.3 " G H(750) 493* 5 l 0.05-0.1 " G H(780) 494* " " " G H(820) 495* " 10-13 " B E H(400) 496* " " 10 B E H(300) 497 " 0.4-0.7 " A A A B C D(20) 498 " " " A A B C D E(30) 499 " " " A A B B C D(21) 500 " " 15 A A A A A B(2.3) 501 " " " A A A B C D(23) 502 " " " A A A A A B(2.5) 503 5 l 0.4-0.7 15 A A A B C D(19) 504 " " " A A A B C D(20) 505 100 l 0.8-1.0 " A A A A A B(2.0) 506 " " " A A A A A A(0.9) 507 " " 10 A A B C D E(30) 508 5 l 0.05-0.1 " A A B C C D(21) 509 " " " A A B B C D(17) 510 " " " A A A A A B(2.8) 511 " " " A A A B C D(22) 512 " " " A A B C D E(29) 513 " " " A A A A A B(2.8) 514 20 l 0.1-0.3 " A A B B C D(20) 515 20 l 0.1-0.3 10 A A B C D E(30) 516 " " " A A A A A B(1.2) 517 " " " A A A A A B(3) 518 " " " A A A B C D(20)__________________________________________________________________________ Notes: (1) *comparative examples (2) Conjugated .pi. bond compound concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h
EXAMPLE 14
As shown in Table 14, for each experiment, a 5-l, 20-l, or 100-l stainless steel polymerizer was selected, and the inner wall surface of the polymerizer and the portions of the auxiliary equipment such as the stirrers which may come into contact with monomer were treated to have the surface roughness (Rmax) shown in the Table. For each experiment, as shown in Table 14, a conjugated .pi. bond compound was dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound as shown in the Table to prepare a coating solution. The formulation ratio of the inorganic compound and the polymeric compound and the concentration of the conjugated .pi. bond compound in the coating solution are also shown in Table 14. The coating solution was applied on the inner wall surface of the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. for 10 minutes and then thoroughly washed with water.
Next, the thus coated polymerizer was charged with 148 parts of water, 1.85 parts of sodium oleate, 48 parts of polybutadiene latex (solid content: 45%), 33 parts of styrene monomer, 19 parts of acrylonitrile monomer, 0.15 part of t-dodecyl mercaptan and 0.5 part of cumene hydroperoxide. After the mixture was heated to 65.degree. C., the polymerizer was further charged with 0.74 part of glucose, 0.0074 part of ferrous sulfate and 0.37 part of sodium pyrophosphate, and polymerization was carried out under stirring at 65.degree. C. for 5 hours. After completion of polymerization, the polymer was taken out and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for a period of time shown in Table 14. The above operations from coating and charging to washing with water were conducted for each batch and this was repeated for a maximum of 10 batches.
In the same manner as in Example 1, scaling after completion of each of the 1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount of scales adhering (g/m.sup.2) was also measured after completion of the final batch. The results are also shown in Table 14.
In Table 14, the Experiment numbers marked with an asterisk (*) indicate Comparative examples. In particular, Experiment Nos. 519 and 520 are examples in which the inner wall surface of the polymerizer was subjected to no treatment with any compound.
TABLE 14__________________________________________________________________________Coating Solution(1) Inorganic (a)/(b) Polymeric (a)/(c) (2)Exp. Conjugated .pi. bond compound (a) compound weight compound weight conc. SolventNo. Kind (Mixing ratio) (b) ratio (c) ratio % (Mixing__________________________________________________________________________ ratio) 519* -- -- -- 520* -- -- -- 521* -- Fe(OH).sub.3 sol 0/100 -- 0.5 Water 522* -- -- Nitrocellulose 0/100 0.5 Methanol 523* 4,5'-Biquinoline Fe(OH).sub.3 sol 100/2 -- 0.5 Water/Methanol (20/80) 524* Naphthol[1,2]furazane Colloidal silica 100/100 -- 0.5 Water/Methanol (50/50)525 4,5'-Biquinoline Fe(OH).sub.3 sol 100/2 -- 0.5 Water/Methanol (20/80)526 Aminocinnoline -- -- 0.5 Methanol527 2,3-Diphenyl-4-quinazoline -- -- 0.7 Methanol528 Meldola's Blue/Chloropromazine Colloidal silica 100/30 -- 0.8 Water/Methanol (30/70) (10/90)529 5,10-Dihydrophenazine -- -- 0.5 Methanol530 Chlorothen citrate -- -- 0.7 Methanol531 Acronycin -- -- 0.9 Methanol532 .alpha.-Hydridone/Disperse Red 5 -- -- 0.4 Acetone (50/50)533 2,3-Diphenylindole -- -- 1.0 Methanol534 Resazurin/1,3-Dioxyacridine -- Nitrocellulose 100/30 0.6 Methanol (20/80)535 Phthalazine -- -- 0.7 Methanol536 2,3-Diaminoquinoxaline -- -- 0.4 Methanol537 2,4-Diphenylthiophene -- -- 0.5 Methanol538 10,10-Diphenylphenoxathine -- -- " 0.9 Methanol539 Dimethylimino-.beta.-isoindigo Colloidal silica 100/100 -- 1.0 Water/Methanol (50/50)540 Naphtho[1,2]furazane Colloidal silica 100/200 -- 0.5 Water/Methanol (20/80)541 3-Chloro-10-ethylphenothiazine Fe(OH).sub.3 sol 100/50 -- 0.8 Water/Methanol (5/95)542 Allomycin/Solvent Black 5 -- Polyvinyl acetate 100/50 0.5 Ethanol (50/50)543 Naphtho[2,3-c]thiophene -- -- 0.5 Methanol544 4,5-Diphenyloxazole -- -- 0.4 Methanol__________________________________________________________________________ (3) (4) Surface roughness of Time for washing Scaling (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m.sup.2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer .mu.m min. 1 2 3 5 7 10__________________________________________________________________________ 519* 5 l 10-13 45 H(1500) 520* " 0.1-0.3 " H(800) 521* " " " H(780) 522* " " " H(750) 523* " 10-13 " B E H(750) 524* " " " B E H(700) 525 100 l 0.8-1.0 10 A A A A A B(3) 526 " " " A A A B C D(20) 527 " " " A A B C D H(100) 528 " " " A A A A A B(3) 529 5 l 0.05-0.1 " A A B B C D(21) 530 " " " A A B C D H(120) 531 5 l " " A A B B C D(17) 532 " " " A A A A B C(10) 533 " " 15 A A B C D E(30) 534 " " " A A A A A B(2.5) 535 " 0.4-0.7 " A A A B C D(22) 536 " " " A A B C D H(100) 537 " " " A A A B C D(20) 538 " " " A A A B C D(19) 539 20 l 0.1-0.3 5 A A A A A B(2.8) 540 " " " A A A A A B(2.5) 541 " " " A A A A A B(2.1) 542 " " " A A A A A B(2.3) 543 " " " A A B C D H(150) 544 " " " A A B B C D(20)__________________________________________________________________________ Notes: (1) *comparative examples (2) Conjugated .pi. bond compound concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and th portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h

Number	Date	Country	Kind
59-171045	Aug 1984	JPX
59-171046	Aug 1984	JPX

Number	Name	Date
3923765	Goetze et al.	Dec 1975
4049895	McOnie et al.	Sep 1977
4539230	Shimizu et al.	Sep 1985

Process for production of vinyl polymer

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