JPH0430405B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing vinyl chloride polymers.
In particular, polymerization vessels used in the polymerization process of vinyl chloride, etc.
Concerning improvements in preventing scale from adhering to internal walls, etc. [Prior art and its problems] Vinyl chloride monomer or vinyl chloride monomer and its
in the presence of a polymerization catalyst.
Suspension polymerization or emulsion polymerization in an aqueous medium
In this method, the inner wall surface of the polymerization vessel or the stirrer during the polymerization process
Do not put heavy
There is a problem with the adhesion of coalesced scale. this
If scale adheres to the inner walls of the polymerization vessel, it may cause damage to the polymer.
In addition to decreasing the yield and cooling capacity of the polymerization vessel, it also causes adhesion.
The kale is separated from the polymerization vessel and mixed into the product.
The quality of the product may be affected, such as causing so-called "fish eyes".
lower. Furthermore, this adhering scale is removed.
It takes too much effort and time to
However, unreacted monomers are adsorbed in this scale.
This has recently become a very serious problem.
Human damage caused by monomers (vinyl chloride, etc.)
It has the disadvantage of being dangerous. How to prevent the adhesion of such polymer scales
As a method, a chemical (hereinafter referred to as "scale") is applied to the inner wall surface of the polymerization vessel.
There is a known method of applying an anti-adhesive agent.
Various scale adhesion inhibitors have been proposed and
Some of them have achieved certain results.
However, the reliability of the scale adhesion prevention effect is not necessarily guaranteed.
It wasn't expensive. In other words, changes in polymerization conditions, etc.
can sufficiently prevent scale adhesion.
The effect may not always be satisfactory.
It was nothing like that. [Object of the Invention] The object of the present invention is to solve the problems of the prior art described above.
with vinyl chloride monomer or vinyl chloride monomer.
In the polymerization process of mixtures with other vinyl monomers
Salt that can reliably prevent scale adhesion
An object of the present invention is to provide a method for producing a vinyl chloride polymer. The present inventors have discovered that conjugated
Adopting a specific compound having 5 or more π bonds,
and chloride ions in the reaction mixture during the polymerization process.
(Cl ^- ) effective and reliable by controlling the concentration
It has been found that scale adhesion can be prevented. [Structure of the present invention - means for solving problems] That is, according to the present invention, vinyl chloride monomer or vinyl chloride monomer and
Mixture of monomer and vinyl monomer that can be copolymerized
A method of suspension or emulsion polymerization in an aqueous medium.
In, the monomer on the inner wall surface of the polymerization vessel and the equipment attached to the polymerization vessel
aromatic having 5 or more conjugated π bonds in the contact area
Aromatic compounds and heterocyclic compounds (but dyes
and pigments) (hereinafter referred to as “conjugated π-bonds”)
At least one compound selected from
Seeds are applied to reduce the concentration of chloride ions in the reaction mixture during the polymerization process.
Control the temperature below 100ppm, preferably below 50ppm
A method for polymerizing a vinyl chloride polymer, characterized by:
is provided. Vinyl chloride monomer or vinyl monomer containing it
Chlorine ion in the reaction mixture in the polymerization of polymer mixtures
The on concentration generally increases rapidly during the early stages of polymerization.
and then continues to rise slightly until the end of polymerization.
Or it shows a flat trend. This chlorine ion
The concentration includes the amount of vinyl chloride used as a raw material.
The amount and preparation of methyl chloride and hydrochloric acid contained in the body
The temperature of the water used for brewing, the degree of vacuum after preparation, etc.
This is thought to be influenced by various factors. Inventor
et al., the chlorine ion in the reaction mixture through the polymerization process.
By controlling the on-concentration to 100ppm or less,
The scale adhesion prevention effect of conjugated π-bond compounds
I found out that it was possible to withdraw the book reliably, and as described above,
Completed the invention. Reaction mixture in this polymerization process
If the chlorine ion concentration in the substance exceeds 100ppm,
Even if the π-bonded compound is applied to the inner wall of the polymerization vessel, etc.
It is not effective as a scale adhesion preventive agent even if
Effectively prevents scale adhesion.
I can't do it. In the method of the present invention, the reaction in the polymerization process
The concentration of chloride ions in the mixture, e.g.
Keep the water temperature between 10 and 80℃, and prepare water or suspension.
The degree of vacuum in the polymerization vessel after charging agents, etc. is -750 to 100.
It can be adjusted by changing it within the mmHg range.
can. That is, in general, the temperature of the feed water is increased.
the higher the degree of vacuum after adding water, etc.
As the temperature increases, the chloride ion concentration in the reaction mixture decreases.
Therefore, the chloride ion concentration in the reaction mixture is
Methylchlora contained in the vinyl chloride monomer raw material
The content of hydrochloric acid and hydrochloric acid also has an effect, but usually industrial
For vinyl chloride monomers used in
Adjust the temperature of the preparation water and the degree of vacuum after preparation.
This reduces the chloride ion concentration in the reaction mixture.
Can be controlled to below 100ppm. for example,
Methyl chloride content as vinyl chloride monomer
60ppm or less, hydrogen chloride content 0.03ppm or less
When using, generally the temperature of the preparation water is
After adjusting the temperature to 40℃ and adding the water, the inside of the polymerization vessel was heated to -500℃.
Evacuate to a vacuum level of mmHg or less and remove vinyl chloride monomer.
By charging chloride ions in the reaction mixture,
The concentration can be controlled to 100 ppm or less. Used as a scale adhesion prevention agent in the method of the present invention
"Conjugated π bond" possessed by conjugated π bond compound
In this specification, 2 or more in a conjugate relationship
double and/or triple bonds.
Then, five or more conjugated π bonds used in the present invention are
Examples of the above aromatic compound include benzene.
Naphthalene derivatives, naphthalene derivatives, polynuclear aromatic compounds
substances, quinones, non-benzene aromatic compounds, etc.
Also, a complex having five or more conjugated π bonds
As a cyclic compound, for example, an oxygen-containing heterocyclic compound
compound, nitrogen-containing heterocyclic compound, sulfur-containing heterocyclic compound
compounds and other bicyclic compounds that share a nitrogen atom
Examples include substances, alkaloids, etc. These compounds
More specific examples include the following:
Ru. Aromatic compounds having 5 or more conjugated π bonds and
The following can be mentioned: First, benzene derivatives include phenols and their derivatives, such as
2,6-di-tert-butylphenylphenol,
Catecholphthalein, 2,2-diphenyrol
Propane, 3,7-dioxy-10-methylxane
Thene, phenolphthalein, 7-oxy-2,
4-dimethylbenzopyrooxonium chloride
Oxyanthraquinone, Purpurogalin, Ga
rhein, diphenyl ether, α-methoxyphene
nadine, chloroglucide, 2,3-dioxyane
Traquinone, 5,7-dioxy-4-methylcoumar
Phosphorus, dioxyacridone, salicylic acid, alpha-hydrogen
Dorindon, β-phenylbutylphenyl, N-
2,4-dinitrophenyl-N-phenylhydro
xylamine, acetophenone, 1-(4-nito
Lofenyl)-3,5-dimethylpyrazole, 9,
10-diphenylphenanthrene; aromatic amines and their derivatives, e.g.
For example, N-phenyl-p-benzoquinone diimine,
Quinoline, Safranin B, Rosaniline, Indi
Yurin Spirit Soluble, Aniline Bratu
Pararosaniline, Methyl Violet, Methyl
chill orange, methyl red, indigo, carva
sol, methylene blue, o-phenantroli
p-phenanthroline, 3,6-diaminoa
Kurijin, Indance Lens Scarlet 2G, 4
-Aminodiphenylamine, acridine yellow
-, 3-aminophenothiazine, N'-dipheni
Le-p-phenylenediamine, rhodamine, 7-
Amino-4-methylcoumarin, 2-aminophena
zine, phenothiazine, diphenylamine, N-
Methyldiphenylamine, N-phenyltrilua
amine, ditolylamine, 2-oxy-4-methyl
Quinoline, Hyza Yellow G, N,N'-diphene
Nylformamidine, phenantrophenazine,
Bismarck Brown G, 2,3-diaminophena
gin, 2-aminodiphenylamine, chrysodine
R, 2,3,7,8-tetraminophenazine,
aminophenoxazone, oxyphenoxazone,
Triphene dioxazine, 2,4-dinitrophe
Noxazine, 2',4'-dinitro-4-oxy-3
-aminophenylamine; nitro and nitroso derivatives, e.g. p-nitro
Trosodiphenylhydroxylamine, phenazi
phenazine oxide, 1-phenylazo-2
- Naphthol, triphenedioxazine, 4-di
Troxanthone, 4'-nitroso-2-nitrodif
enylamine; phenylhydroxylamine derivatives, e.g.
4,4'-dinitrodiphenylamine, divinyl oxalate
(β-phenylhydrazine), bismalonate
(β-phenylhydrazine), bissuccinate (β-
phenylhydrazine), bisphthalate (β-phthalate)
nylhydrazine); aromatic halides, such as biphenyl chloride
Ride; aromatic aldehyde, e.g. 2-phenyl-1
-Benzylbenzimidazole, leucomalachi
green, malachite green, tetrachlor
Hydroquinone monobenzoate, benzoflavi
2-phenylbenzthiazole, 4-benz
hydrylbenzaldehyde, bisphenylhydra
zon, bis(4-nitrophenylhydrazone); aromatic ketones, e.g.
Sasol, benzophenone potassium, 4-methyl
Benzophenone, P-toluic acid anilide, rest
Toluidide fragrant, diuryl phenyl ketone,
2,4,2',4'-tetramethylbenzophenone,
Chalcone phenylhydrazone, 1,3,5-tri
Phenylpyrazoline, dinitrobenzyl; benzoic acids, phthalates and their derivatives
body, e.g. quinizarin, nitrodiphenyl ether
Ter: has one type of substituent in addition to the aldehyde group
benzene derivatives such as disaltyaldehyde
coumarin, 2-benzoyl coumaron, 1-o
xy-2,4-dimethylfluorone, 3-phenylene
Lucumaron, coumarin-3-carboxylic acid ethyl ester
Stell, 3-acetylcoumarin, hydrovanilloi
4-oxy-3-methoxy-ω-nitrostylene
Ren, α-(nitrophenyl)-β-benzoyle
tyrene oxide, dinitrophenyl indazole
5-chloro-3-(4-oxyphenyl)a
ntranil, 3-nitroacridone, 6-nitro
-3-phenylanthranyl, 2,8-dimethyl
-1,9-anthrazoline, carbostyril,
1,3-dioxyacridine, oxyquinacridine
N, florkynil, 2-methylquinazoline, 3
-acetyl-2-methylquinoline, 2-oxy-
3-phenylquinoline, 3-nitroquinoline, quinoline
Norin-2,3-dicarboxylic acid ester; base having one type of substituent in addition to the acyl group
derivatives such as 7-oxyflavanone,
7-oxyflavone, 7,8-dioxyflavone
7-acetoxy-4-methyl-3-phenyl
Coumarin, 7,8-diacetoxy-4-methyl-
3-phenylcoumarin, o-oxybenzopheno
xanthone, 2-phenylbenzoxazole
m-oxybenzophenone, p-oxyben
Zophenone, 2-benzoylxanthone, 2,4
-dioxybenzophenone, 2,5-dioxybene
ndzophenone, 2,2'-dioxybenzophenone
xanthene, aurin, trioxybenzof
enone, 6,7-dimethoxy-3-phenyl bear
Ron, o-nitrobenzophenone, m-nitroben
Nzophenone, 4,4'-dibenzoylazoxibe
2-(2-aminophenyl)-4-methyl
Quinone, 2-oxy-4-methylquinone, acrylic
Don, 2,4-dimethylquinazoline, 3-cyan
-2-oxy-4-methylquinoline, fluorene
Anhydro(2-aminobenzophenone)
Imer, 2-oxy-3-phenylindazoe
3-phenylindazole, 2-phenylbenzole, 3-phenylindazole,
zuimidazole, 2-methyl-8-benzoyl
Quinoline, 2-methyl-4-phenylquinoline,
4-phenyl-2-quinazolone, aminobenzof
enone, chlorbenzophenone, 4-phenylben
1,2,3-triazine-3-oxide,
Diaminobenzophenone, 7-methyl-3-phene
Nyl-4,5-benzo-1,2,6-oxydia
gin, 4,4'-bisdimethylaminobenzopheno
4,4'-bisdimethylaminobenzophenone
imide, 2,4-dinitro-9-phenylacrylate
Benzene, 4,4'-dibenzoyldiphenyl; benzene having three or more different substituents
toluene derivatives, such as tetramethoxy
5,6,5′,6′-bismethylenedioxy
Indigo, 7-acetoxy-8-methoxy-3-
(2-nitrophenyl)carbostyryl, 2,
2'-dinitrodiphenyl disulfide-4,4'-
Dialdehyde, 6-chloro-3-benzoylfura
Bon, 1,3,8-trinitrophenoxazine; aralkyl compounds, such as 9-benzylac
Lysine; diazo and azo compounds, e.g. azo
Benzene, azotoluene, 2,2-dimethoxya
Zobenzene, 4,4'-dichloroazobenzene,
1,1'-azonaphthalene, 2,2'-dioxyazo
Benzene, 2,2'-dioxy-5,5'-dimethyl
Azobenzene, p-bromoazobenzene, p-ni
Troazobenzene, phenoazoxide; aromatic unsaturated compounds, e.g. 2,3,4,5
-tetraphenylcyclopentan-2-ene-1
-one, 1,2,3-triphenylazulene,
2,2'-dimethyldiphenylacetylene, 4,
4'-diethyldiphenylacetylene, 3,4,
3′,4′-tetramethyldiphenylacetylene,
2,2'-dichlorodiphenylacetylene, 2,
2'-dibromodiphenylacetylene, 2-nitro
Diphenylacetylene, 2,2'-dinitrodiphene
Nyl acetylene, 2,2'-diaminodiphenyla
Cetyl, 2,2'-dimethoxydiphenylacetylene
Ren, stilbene, α-methylstilbene, α-
Ethylstilbene, α,β-dimethylstilbe
α,β-diethylstilbene, α,β-dichloromethane
Lorstilbene, α,β-dibromustilbene,
2-Chlorstilbene, 4,4'-diiodostil
Ben, α-nitrostilbene, α,β-dinitro
Stilbene, 2,4,6-trinitrostilbene
2-aminostilbene, 2,2'-diaminos
tilbene, 4,4'-di(dimethylamino)stil
Ben, 2,2'-dicyanstilbene, 2-oxy
Stilbene, 2-methoxystilbene, 2,2'-
Dioxystilbene, 2-2'-dimethoxystil
Ben, 4,4'-dialkoxystilbene, 3,
5,2',4'-tetraoxystilbene; and
In addition, polyphenyl and its derivatives, such as biphenyl
enyl, terphenyl, quaterphenyl, kin
cuphenil, sexifenil, septiphenil,
Octyphenyl, Novifenil, Decifenyl, etc.
can be mentioned. Next, naphthalene derivatives include alkyl, alkenyl and phenylnaphthalene.
such as -methylnaphthalene, 2-methyl
naphthalene, 1-ethylnaphthalene, 2-ethyl
Naphthalene, 1,2-dimethylnaphthalene, 1,
4-dimethylnaphthalene, 1,5-dimethylnaphthalene
Talin, 1,6-dimethylnaphthalene, 1,7-
Dimethylnaphthalene, 2,3-dimethylnaphthalene
2,6-dimethylnaphthalene, 2,7-dimethylnaphthalene
Tilnaphthalene, 1-propylnaphthalene, 1-
Isopropylnaphthalene, 2-isopropylnaphthalene
Talin, trimethylnaphthalene, diisopyrnaf
Talin, 1-vinylnaphthalene, 2-vinylnaphthalene
Talin, 1-propenylnaphthalene, 1-allyl
Naphthalene, 1-isopropenylnaphthalene, 2
-isopropenylnaphthalene, 1-phenylnaph
Talin, 2-phenylnaphthalene, 1,4-diphthalene
enylnaphthalene, 1,2,4-triphenylna
Phthalin; dinaphthyls, such as 1,1'-dinaphthyl,
1,2'-dinaphthyl, 2,2'-dinaphthyl; naphthylarylmethanes, e.g. 1-ben
Zilnaphthalene, 2-benzylnaphthalene, 1-
(α-chlorobenzyl)naphthalene, 1-(α,α
-dichlorobenzyl)naphthalene, diphenyl-
α-naphthylmethane, diphenyl-β-naphthyl
Methane, 1,8-dibenzylnaphthalene, di-α
-naphthylmethane, α-naphthyl-β-naphthyl
Methane, di-β-naphthylmethane; naphthylarylethanes, e.g. 1-phene
Netylnaphthalene, 1,2-di-α-naphthyl ether
1,2-di-β-naphthylethane, 1,1
-α-dinaphthylethane; hydronaphthalenes, such as 1,2-dihydre
lonaphthalene, 1,4-dihydronaphthalene,
1,2,3,4-tetrahydronaphthalene; nitronaphthalene and its derivatives, e.g.
Ftopyridazine, 7,8-benzoquinone, 5,6
-benzoquinone, naphthazarine, diperimidine,
Nitromethylnaphthalene, nitroalkylnaphthalene
Phosphorus, nitrophenylnaphthalene, halonitrona
Phthaline, halodinitronaphthalene, nitrosona
Phthalin, dinitrotetralin, dibenzofena
gin, methylbenzoindole, 9-chloro-1
-Azaanthracene, quinolinoquinoline, 1,
2,3-triazaphenalene, perimidone, peri
Midine, dibenzaacridine, benzophenazine
-12-oxide, diaminonaphthalene, triamine
nonaphthalene, tetraaminonaphthalene, N-e
Chyl-α-naphthylamine, N-methylnaphthyl
Amine, N,N-dimethylnaphthylamine, N-
Methyl-N-ethylnaphthylamine, trimethyl
Naphthylammonium salt, N-phenylnaphthyl
Amine, N-benzylnaphthylamine, N-naph
thylethylenediamine, N-naphthylglycine,
N-β-cyanomethylnaphthylamine, N-acetic acid
Tilnaphthylamine, N-formylnaphthylamine
N-benzoylnaphthylamine, N-phthalo
ilnaphthylamine, aminomethylnaphthalene,
Nitronaphthylamine, dinitronaphthylamine
chlorine, halonitronaphthylamine, aminotetraly
diaminotetralin; halogenated naphthalenes, e.g. 1-fluoro
lunaphthalene, 1-chlornaphthalene, 1-chloro
Ru-3,4-dihydronaphthalene, 1-iodona
Phthalin, 1-bromnaphthalin, 1-chloro-
4-chloromethylnaphthalene, 1-bromo-2-
Bromomethylnaphthalene, 1,4-difluorona
Phthalin, 1,2-dichlornaphthalin, 1,6
-dichlornaphthalene, 1,7-dichlornaphthalene
Phosphorus, 1,5-dichloronaphthalene, 1,8-di
Chlornaphthalene, 2,3-dichlornaphthalene
1,4-dibromnaphthalene, 1,4-diyo
donaphthalene, perylene, 1,2,3-tric
Lornaphthalene, 1,2,4-tribromnaphtha
Phosphorus, 1,2,3,4-tetrachlornaphthalene
1,4,5-tribromo-3,8-dimethyl
naphthalene, 1,3,6,7-tetrachlornaf
Talin, 1,3,5,8-tetrabromnaphtali
1,2,3,4,5-pentachlornaphthalene
Naphthyl hydroxylamine, naphthyl biradi
and naphthylureas, e.g. α-naphthyl
Hydroxylamine, N'-phenyl-N-α-
naphthyl-N-oxyurea, β-naphthylthiohyl
Droxylamine, N-nitroso-α-naphthyl
Hydroxylamine, neocouferon, 2-oxy
C-1,1'-azonaphthalene, α-naphthylhydride
Radin, 1,2-dibenzocarbazole, 4,4
-diamino-1,1'-binaphthyl, 3,4-ben
Zucarbazole, 2,2'-cyamino-1,1'-bi
Naphthyl, N'-acetyl-N-β-naphthyl
Drazine, N'-lauroyl-N-β-naphthyl
Hydrazine, N'-phenyl-N-α-naphthyl
Hydrazine, N'-(2,4-dinitrophenyl)
-N-α-naphthylhydrazine, 2-α-naphthylhydrazine
-5-nitrobenztriazole, N,N'-
Di-α-naphthylhydrazine, 1,1′-diamino
-2,2'-binaphthyl, N,N'-di-5-tetra
Rylhydrazine, N'-(2,4-dinitrophenyl
)-N-β-naphthylhydrazine, 2-β-naphthylhydrazine
Phthyl-5-nitrobenztriazole, N'-
Triphenylmethyl-N-β-naphthylhydrazide
N,N'-di-β-naphthylhydrazine, N
-Methyl-N-(2,4-dinitro-1-naphthi
) hydrazine, 2-amino-(naphtho-1',
2′:4,5-thiazole), 1,2:5,6-di
Benzophenazine, 2-amino-(naphtho-2',
1′:4,5-thiazole), 2,3-dihydrazi
Nonaphthalene, 2-phenyl-1,3-bisbene
Zylidene amino (naphtho-2',3':4,5-imy
dazoline), N-acetyl-α-naphthylnitro
Soamine, N-ethyl-α-naphthylnitrosoa
Min, N-phenyl-α-naphthylnitrosamide
α,α′-dinaphthylnitrosamine, amber
acid bis(β-naphthylnitrosamide), N-e
Thyl-β-naphthylnitrosamine, N-phenylated
Ru-β-naphthylnitrosamine, N-acetyl
-2-methyl-1-naphthylnitrosamine,
4,5-benzindazole, naphthyl nitro
amine, 1-nitro-2-naphthylamine, α-naphthylamine
phthylurea, N,N'-di-α-naphthylurea,
4-Chlor-1-naphthylcarbamoyl chloride
Do, 2,4'-dichlor [naphtho-1',2':4,5
-thiazole], 2-mercapto[naphtho-1′,
2′:4,5-thiazole], 2-chlor[naphtho
-1',2':4,5-thiazole], 2-mercap
[naphtho-2',1':4,5-thiazole], 2
-chlor[naphtho-2',1':4,5-thiazole
]; Naphthalene-based aralkyl compounds, such as dibetanyl
nzanthracene, acenaphthene, α-chlorene
Chillnaphthalene, phenylnaphthyl chlormeth
Diphenylnaphthylchloromethane, Nitromethane
tilnaphthalene, aminomethylnaphthalene, (naphthalene)
phthylmethyl)amine, α-phenyl(naphthyl)
methyl)amine, N-benzyl(naphthylmethy)
)amine, trimethyl(naphthylmethyl)amine
Monium salt, tri(naphthylmethyl)amine, di
(naphthylmethyl)amine, (β-naphthylethyl)
) Alcohol, dimethylnaphthyl carbinol
phenylnaphthyl carbinol, diphenyl
naphthyl carbinol, 9-phenylbenzofur
Orene, naphthylpropylene oxide, ethyl
(naphthylmethyl)ether, phenyl (naphthylmethyl)ether
methyl) ether, naphthylacetaldehyde
de, naphthylacetone, ω-naphthylacetophene
non, acenaphthenone, dihydrophenalon,
Enalon, benzoindanone, naphthylacetoni
tolyl, 9,9'-dichlorodibenzofluorene,
α-nitro-β-naphthylethylene, γ-naphthylethylene
Ruaryl alcohol, β-naphthyl acrolei
Methyl (β-naphthyl vinyl) ketone, naphthyl vinyl
Tylphenanthrene dicarboxylic acid anhydride; naphthol, naphthalene sulfonic acids, e.g.
9-oxynaphthacenequinone, 2'-naphthalene
N-2-indole indigo, 1-methoxynaf
Talin, 1-ethoxynaphthalene, 1-phenox
Synaphthalin, α-naphthol salicylic acid ester
β-naphthol, α-naphthol, α-naphthol
Tall benzoate, α-naphthol acetate
Stell, phenyl-β-oxynaphthylbenzal
iminomethane, β-naphtholphenylmethyla
Min, methylene-di-β-naphthol, dinaphtho
Pyran, 1'-naphthol-2-indoleindi
Go, 2-methoxynaphthalene, 2-ethoxynaf
Talin, N-p-oxyphenyl-2-naphthyl
Amine base, β-naphthol salicylic acid ester
2-methyl-1-naphthol, 1,2-naphthol
Tamethylenequinone, 1,2-dioxynaphthalene
Naphthalene indole indigo, α, β-na
Futhophenoxazine, β, γ-naphthophenoxa
gin, 4-oxy-10-methyl-1',2'-benzo
Carbazole, Dioxynaphthofluorane, Zina
Phthoquinone, 2,6-naphthoquinone, oxyben
Zoacridine, 9-oxy-3-dimethylamino
naphthophenoxazine, 1,2,4-trioxy
naphthalene, 1,4,5,6-tetraoxynaf
Talin, thio-α-naphthol, 4-mercapto
-1-naphthol, 1,5-naphthalenedithio
methyl-α-naphthyl sulfide, 1,1′-
Naphthyl sulfide, 1,1'-thiodi-2-naph
Toll, 1,1'-naphthyl disulfide, 1,
1'-dithiodi-1-naphthol, thio-β-naphthol
Toll, naphthothioindigo, 1-amino-2-
naphthalene thiol, naphthothianthrene, 2-
Mercapto-1,2-naphthothiazole; naphthaldehydes and their derivatives, e.g.
For example, α-naphthaldehyde, 2-(2,4-dini
trophenyl)-1-(α-naphthyl)ethylene,
2-methyl-1-naphthaldehyde, 2,3-di
Methyl-1-naphthaldehyde, 4-bromo-1
-naphthaldehyde, 4-nitro-1-naphthore
Rudehyde, 2,4-dinitro-1-naphthalde
Hyde, 4-amino-1-naphthaldehyde, 2-
Oxy-1-naphthaldehyde, 1-naphthalene
-2′-indole indigo, 1,2-bis(2-
oxy-1-naphthyl)ethylene, 1,2:7,
8-dibenzoxanthylium chloride, 2-ox
C-1-naphthylethenylpyrylium salt, 5,6
-benzocoumarin, bis(2-methyl-3-yne)
Drill) (2-oxy-1-naphthyl)methane,
4,5-Benzindoxazene, 2-acetoxy
-1-naphthonitrile, 4-methoxy-1-naph
Toaldehyde, 1,4-bis(4-methoxy-1
-naphthyl)-1,3-butadiene, 2-naphtha
Phosphorus-2'-indole indigo, 3-acetyl-
6,7-benzocoumarin, 4-chloro-1-oxy
C-2-naphthaldehyde, naphthalene dialde
hydro, 5-oxy-2-naphthalene-indole
-Indigo, 5,6,7,8-tetrahydro-2
- naphthaldehyde, imidochloride, naphtho
mido, naphthanilide, naphthonitrile, β-na
Phthoimidic acid ethyl ester, β-naphthamide
α-naphthoamidoxime, α-naphthohydra
dido, naphthostyryl, oxynaphthonitrile,
1,2:7,8-dibenzoxanthone, 1,2-
Benzoxanthone, 1,1'-binaphthylene-2,
8';8,2'-dioxide,2,3; 6,7-dibe
nzoxanthone, 3-oxy-2-naphthoanil
1,3-bis(3-oxy-2-naphthoyl)
oxy)benzene, 2,4-dioxyphenyl-
3-oxy-2-naphthylketone, 4-aryl
Azo-3-oxy-2-naphthanilide, 3,4
Dihydronaphthalene-1,2-dicarboxylic anhydride
substance, 2-aminonaphthalimide, naphthalohydra
Dido, α-pyridnaphthalone, N-methylnaphtha
limides; as well as acetonaphthenes, benzoylnaphthalenes, e.g.
For example, 1,2;5,6-dibenzanthracene,
2'-Methyl-2,1'-dinaphthyl ketone, 2-methyl
Styryl-1,1'-dinaphthyl ketone, styryl-2
-naphthylketone, β-naphthoylacetone, β
-naphthoylacetophenone, 1-(β-naphthi
)-1-chloroethylene, 2-[tris(β-sil)
(ethyl)acetyl]naphthalene, 1,3,5
-tri(β-naphthyl)benzene, dimethyl 2-
Naphthyl carbinol, 4,5;4',5'-dibene
Zothioindigo, styryl 1-naphthyl ketone,
β-acetonaphthone, 1-propionylnaphthalene
1-butylnaphthalene, 1-isobutylnaphthalene
Talin, 1-stearoylnaphthalene, 1-ben
Zoylnaphthalene, 1-o-tolylnaphthalene
p-biphenyl 1-naphthyl ketone, 1,
2,5,6-dibenzanthracene, 1-acety
-3,4-dihydronaphthalene, 1-acetyl
-7-bromnaphthalene, 1-aminoacetylna
Phthalin, 2-aminobenzoylnaphthalin, 1
-Acetyl-2-oxynaphthalene, 1-acetylene
-2-methoxynaphthalene, 1-acetyl-4
-Ethoxynaphthalene, 2-cinnamoyl-1-
naphthol, 7,8-benzochromone, 3-acetyl
thyl-2-methyl-7,8-benzochromone,
3,4-dimethyl-7,8-benzocoumarin, 4
-Methyl-3-phenyl-7,8-benzocumari
1-benzoyl-2-oxynaphthalene, 4
-oxybenzanthrone, 4-benzoyl-1
-naphthol, 3-oxy-1,2-benzofur
Olenone, 2-acetyl-4-chloro-1-oxy
Synaphthalin, α-naphthylglyoxal, β
-Naphthylglyoxal, 1,4-dibenzoy
lunaphthalin, phenyl 4-methyl-1-naphthi
Examples include rujiketone. In addition, as polynuclear aromatic compounds, anthracenes and their derivatives, such as a
anthracene, 1,2-dihydroanthracene, 1
-Chloranthracene, 1,4-dichloranthus
helix, 1,2,7-trichloroanthracene,
1,2,3,4-tetrachloroanthracene, 1
-Nitroanthracene, 9,10-dinitroant
Spiral, 1-aminoanthracene, 2-dimethyl
Aminoanthracene, 2-anilinoanthrace
9-methylaminoanthracene, 1,4-di
Aminoanthracene, 1-oxyanthracene,
9,10-dihydroanthrol, 10-methylanthrole
thranol, 10-phenylanthranol, 10-
Nitroantranol, 2-amino-1-antho
Ranol, 1,2-dioxyanthracene, 9,
10-Dioxyanthracene diacetate, 1-methane
tylanthracene, 4-chloro-1-methylane
thracene, 1,5-dichloro-2-methylantho
helix, 9-ethylanthracene, 9-vinylacene
anthracene, 9-propylanthracene, 9-y
Sopropylanthracene, 9-butylanthrace
9-isobutylanthracene, 9-isoamide
Luanthracene, 1,3-dimethylanthrace
9,10-diethylanthracene, 1-phenylene
Luanthracene, 9-phenylanthracene,
1,5-dichloro-9-phenylanthracene,
10-nitro-9-phenylanthracene, 9-be
Benzylanthracene, 1-benzhydryl anthracene
helix, 9,10-diphenylanthracene, 9,
10-dibenzylanthracene, 9,10-dipheni
Le-9,10-dihydroanthracene, 1-(β-
naphthyl)anthracene, 9-(α-naphthyl)-
10-phenylanthracene, 9,10-di(α-na)
phthyl) anthracene, 1,1′-biantryl,
2,2'-biantryl, 9,9'-biantryl,
Anthracene-9-aldehyde, 1-acetyla
anthracene, 9-benzoylanthracene, 10-
Nitroanthrafuenone, 9,10-dibenzoyl
anthracene, anthrone, 9-mercaptoan
Thoracene, 9,10-disodium-9,10-dihyde
Droanthracene, 10-bromo-9-anthryl
Magnesium bromide, anthrylmarkylichlor
Lido; phenanthrenes and derivatives thereof, such as
phenanthrene, 9,10-dihydrophenanthre
1,2,3,4-tetrahydrophenanthre
1-chlorophenanthrene, phenanthrene
-9,10-dichloride, 1-bromophenanthre
1-iodophenanthrene, 9-(chlormet)
methyl)phenanthrene, 1-(bromomethyl)phenanthrene,
Enanthrene, 4,5-bis(bromomethyl)fluoride
enanthrene, 1-nitrophenanthrene, 10-
Bromo-9-nitrophenanthrene, 1-amino
Phenanthrene, 9,10-diaminophenanthrene
9,9′-azoxyphenanthrene, 9,9′-
Azophenanthrene, 1-oxyphenanthrene
cholesterol, estrone, androste
Ron, 10-bromo-9-phenanthrol, 9-
Nitro-3-phenanthrol, 4-amino-1
-phenanthrol, 10-benzoazo-9-feu
Nanthrol, 1,2-dioxyphenanthrol
Retyl-3,8-diol, 2,3,5,6
-tetraoxyphenanthrene, 1-methylphenylene
Nanthrene, 1-ethylphenanthrene, 1-bi
Nilphenanthrene, 1,2-dimethylphenan
Trene, 9,10-diethylphenanthrene, 9,
10-dipropylphenanthrene, 2-ethyl-1
-Methylphenanthrene, 7-isopropyl-1
-Methylphenanthrene, 9,10-dihydrolethe
N, aminoethene, 3-acetaminolethene, 6
-acylaminolethene, 9-phenyl phenant
Ren, 9-benzylphenanthrene, 1-(α-
naphthyl)phenanthrene, 1,1'-bihuenane
Tolyl, 9,9'-biphenanthryl, 1-fuena
antraldehyde, 2-phenanthraldehyde, 9
-phenanthraldehyde, 1-acetylphenan
Tren, 2-propionylphenanthrene, 3-
Acetyl lethene, 1-benzoylphenanthrene
phenanthrenequinones, such as phenanthrene;
Ren-1,2-quinone, phenanthrene-1,4
-quinone, phenanthrene-3,4-quinone, phenanthrene
Enanthrene-9,10-kylene, 2-phenyl-
3-acetoxy-4,5-biphenylenefuran,
7-isopropyl-1-methylphenanthrene
Non, 1-chlorophenanthrenequinone, 2-butylene
romphenanthrenequinone, 2-iodophenan
Trenquinone, 2,7-dibromophenanthrene
Quinone, 2-nitrophenanthrenequinone, 2,
5-dinitrophenanthrenequinone, 2-amino
phenanthrenequinone, 2,7-diaminophena
ntrenequinone, 3,6-diaminophenanthre
quinone, 2,5-diaminophenanthrene quinone
2-oxyphenanthrene-1,4-quino
3-oxyphenanthrenequinone, 2-oxy
Cyrethenequinone, 3-oxylethenequinone, 6-
Oxyrethenequinone, 2-oxy-3,4-dini
Trophenanthrenequinone, 2-amino-3-o
xyphenanthrenequinone; and polynuclear aromatic compounds and derivatives thereof, such as
Pentacene, hexacene, benzophenanthre
benzo[a]anthracene, naphtho[2,
1,a]pyrene, dibenzo[a,j]anthrace
pyrene, coronene, 1,12-benzoperile
n, obalene, dibenzoanthracene, naphtase
N, terramycin, aureomycin, rubre
o-toluoyl-1-naphthalene, benzoa
Intraquinone, 5,6-dioxy-5,6-dihydrogen
Drobenzoanthracene, chrysene, tripheni
Ren, dibenzonaphthacene, hexahydropyrene
perylene, 3,9-dichloroperylene, tet
lachlorperylene, 3,9-dibromperylene,
3,10-dinitroperylene, 4,6-dibenzoy
-1,3-dimethylbenzene, 6,13-dihyde
lopentacene, naphtho[2,3-a]anthrace
N, dispirane, dibenzo[a,h]anthrace
Picene, Picene, Pisylene Ketone, Picene-5,6-
Quinone, dibenzo[c,g]phenanthrene, benzene
Benzo[a]pyrene, benzo[a]pyrene-1,6
-Quinone, mesobenzaanthrone pericarboxylic acid
Anhydride, anthraceno[2,1-a]anthrace
dibenzo[a,1]naphthacene, fuenant
Ren [2,3-a] anthracene, naphtho [2,
3-a]pyrene, dibenzo[a,h]pyrene, dibenzo
Benzo[a,1]pyrene, zetrene, antoan
Tren, benzo[1,12]perylene, heptase
Tetrabenzo [a, c, h, j] anthrace
Tribenzo[a,i,l]pyrene, Tetrahydryl
Drodimethyl dinaphthyl, mesonaphthodianthrae
mesoanthrodianthine, 2,3;8,9
-Dibenzocoronene, pyrantrene, etc.
Ru. In addition, examples of quinones and derivatives thereof include benzoquinones and derivatives thereof, such as di-
Benzoquinoyl disulfide, 2,5-bis(fluoride)
enylthio)-p-benzoquinone, bibenzoquino
N, Vitruquinone, Fenicin, Ausporai
Indophenol, Indoaniline, Hydro
Blue, Indamine, Meldora Blue, Urus
Tarblue, Ulster Red, 4,4'-Dihue
Noquinone, 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'-te
tert-butyl-4,4'-stilbenquino
Naphthoquinones and derivatives thereof, such as
1,2-naphthoquinone, 3-oxy-2,2'-bi
Naphthyl-1,4; 3',4'-diquinone, 5,6-
Benzoquinoxaline, 1,2-benzophenazi
2-Benzeneazo-1-naphthol, 4-
(2,4-dioxyphenyl)-1,2-dioxy
naphthalene, 4-(3,4,5-trioxyphene)
1,2-dioxynaphthalene, 1,2-
naphthoquinone-1-phenylimide, 1,2-beta
Nzophenoxazine, 1,2-naphthoquinone-2
-Chlorimide, 1,2-naphthoquinone-bis-
Chlorimide, 2-anilino-1,4-naphthoki
Non-4-anyl, 2-oxy-1,4-naphtho
Quinone-4-anyl, 1,2-naphthoquinone-1
-oxime benzoate, 1,2-naphthoquinone
-1-oxime methyl ether, 1-nitroso-
2-naphthol, 2-nitroso-1-naphthol
Le, Naft [1', 2': 3, 4] Furazan, 1, 2
-naphthoquinone-2-oxime benzoate,
1,2-naphthoquinone-2-oxime methyl ether
ter, 3-anilino-1,2;8,9-dibenzo
Phenazine, Naphthyl Blue, Naphthyl Biots
1,2;5,6-dibenzophenazine, naph
g[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-benziindiazene, 2
-diphenylmethyl-1,4-naphthoquinone, metal
tilnaphtho[2′,3′:4,5]triazole-1′,
4'-quinone, 1,2,4-triacetoxynaphtha
Phosphorus, 1,4-naphthoquinone phenyl imide,
1,4-naphthoquinone-mono-(p-dimethyla
(minoanyl), 1,4-naphthoquinone achilimine
do, 4-nitroso-1-naphthol, phenylka
Rubamate, 4-nitroso-1-naphthylamide
4-benzhydryl-1,2-naphthoquino
2-benzhydryl-1,4-naphthoquino
3-benzhydryl-2-methyl-1,4-
naphthoquinone, 3-geranyl-2-methyl-1,
4-naphthoquinone, 3-falnesyl-2-methy
Ru-1,4-naphthoquinone, 2-methyl-3-ph
Ityl-1,4-naphthoquinone, vitamin K ₁ ,
vitamin K ₂ , 3-allyl-2,6-dimethyl-
1,4-naphthoquinone, 2,6-dimethyl-3-
phytyl-1,4-naphthoquinone, 2,3-dia
Lyle-6;7-dimethyl-1,4-naphthoquino
2-phenyl-1,4-naphthoquinone, 2-
Methyl-1,4-naphthoquinone, 2,6-dimethy
-3-phenyl-1,4-naphthoquinone, 3-
benzyl-2-methyl-1,4-naphthoquinone,
2-Methyl-3-(β-phenylethyl)-1,4
-naphthoquinone, 3-cinnamyl-2-methyl-
1,4-naphthoquinone, 2-benzhydryl-
1,4-naphthoquinone, 4,7-diketo-8-di
Phenylmethyl-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-diben
Zothianthrene, 5,8-dioxy-2,3;
6,7-dibenzothianthrene-1,4-quino
2,3-diphenoxy-1,4-naphthoquino
N, Zinaft [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-naphthoquinon-2-yl)
-benzidine, 2-anilino-1,4-naphthoki
Non-4-anyl, 4-anilino-1,2-naph
toquinone-2-anyl, phenylrosindaline,
2-anilino-1,4-naphthoquinone-4-(p
-dimethylaminoanyl), 2-anilino-1,
4-naphthoquinone dianyl, 2-anilino-3-
Phenyl-1,4-naphthoquinone, 2-anilino
-3-bromo-1,4-naphthoquinone, 2-ani
Lino-4-chloro-1,4-naphthoquinone, 2,
3-dianilino-1,4-naphthoquinone, 2,3
-dianilino-1,4-naphthoquinonedianyl,
Nitrosoaminonaphthoquinone, 3-chloro-2-
Phenylnitrosamino-1,4-naphthoquino
phenyl-bis-(3-anilino-1,4-
Nastoquinon-2-yl)-amine, 3-chlor
-2-(p-tolylnitrosamino)-1,4-na
Futhoquinone, 2,7-dioxy-1-nitrosona
Phthalin, 4-benzenazo-1,3-dioxy
naphthalene, di-(3-oxy-1,4-naphtho)
Quinonyl-2-)methane, anhydroalkanni
Diquinoxalino [2′, 3′: 1, 2; 2″, 3″:
3,4] Naphthalene, 3,4-phthaloylfraza
and anthraquinones and derivatives thereof, such as
1,2-anthraquinone, 2,3-anthraquino
1,4-anthraquinone, 9,10-anthraquinone
Quinone, 1,5-anthraquinone, 2,6-anthraquinone
Traquinone, 1,10-anthraquinone, 9,9-
bis(p-oxyphenyl)anthrone, anthron
Laquinone bisdiphenyl methide, bisphenyl bis
Drazon, benzantrone, anthrahydrox
Non, β-ethylanthraquinone, 1,3,5,
7-tetramethylanthraquinone, 2,2'-dia
anthraquinonylethane, 2,2'-dianthraquino
nylethylene, 1,2,3-trioxyanthra
quinone, anthrachrison, entrooxyane
Traquinone, Alizarin, Quinizarin, Anthra
Rufuin, chrysazine, histazaline, anthra
Flavins, isoanthraflavins, anthragallo
pearl, purpurin, oxyantral fin,
Ntrapurpurin, Oxychrisazine, Oxif
Labo Purpurin, Rufuiopine, Quinalizarin,
Alizarin pentacyanine, lufigarol, alizarin
ntracene blue WR, alizarin hexacyani
2-chlorquinizarin, 1-nitroanthra
Quinone, purpurin, 2,4,6,8-tetrabu
Romuanthrachrysone, 3-aminoanthrapur
Purine, 1,8-dinitroanthraquinone, α-
Aminoanthraquinone, 1,1'-dianthraquinone
Nil, dianthraquinone imide, 1,4-dimethy
Ruaminoanthraquinone, 5-amino-1-nito
rho-6,8-dibromoanthraquinone, 1,5-
Tetramethyldiamino-4,8-dinitroant
Laquinone, anthraquinone acridone, bis-N
-(2-oxyanthraquinolyl)-p-phenylene
diamine, leucoquinizarin, quinizaringuli
1-amino-2,4-dibromoanthrachylene
Non, 1,4-diacylaminoanthraquinone,
Anthraquinone-β-aldehyde, o-diazide
6,7-phthaloyl-1,9-benzant
Ron, oxynitrosoanthraquinone, 1,1'-
dianthraquinonyl, azoxyanthraquinone,
8-Chlorpyrazoleanthrone, 2,6-dihy
Drazinoanthraquinone, anthraquinone diazo
salt, β-anthraquinone hydrazine, azo
xyanthraquinone, pyrazoleanthrone, 1
-(anthraquinonyl-2-)-3-methylpyrazo
Ron, 1-hydroxylaminoanthraquinone,
1,5-dihydroxylaminoanthraquinone,
1-nitrosoanthraquinone, 1-hydrazinore
anthraquinone, 1,5-dihydrazinoanthraquine
Non, 1-azidoanthraquinone, 2-azidore
anthraquinone, anthraquinone methyl sulfoxy
Do, 1,4-dirodane anthraquinone, β, β'-
dianthraquinonyl sulfide, anthraquinone
Sulfenyl chloride, 2,2'-dianthraquino
Nyl, 1,1'-dianthraquinonyl, Helianth
Ron, mesobenzodianthrone, 2,2'-diami
No-1,1'-dianthraquinonyl, flavanthro
2,2′-dianthryl, mesonaphthodiant
Ron, 1,1'-dianthraquinonylamine,
Zarin quinone, histazarin quinone, alizarin
Quinone, 6-oxyquinizaline quinone, etc.
It will be done. Furthermore, as non-benzene aromatic compounds,
For example, azulene, cyclodecapentane, cyclo
Tetradecaheptane, cyclooctadecanonae
cyclotetracosadodecaene, bepthalene,
Fullbaren, Sesquifulbaren, Heptafulbaren
perinaphthene, indeno[2,1-a]peri
naphthene, dibenzo [bf] oxepine, dibenzo
[bf] Thiepin, indolizine, cyclo[3,2,
2] Azine, 4,5-benzotropolone, 3,4
-benzotropolone, 5H-benzocyclohepte
7H-benzocycloheptene, colchicine,
colchiceine, colchinol methyl ether, di
Tropyl ether, ditropyl sulfide, cyclopene
Tadienyltropylidene, benzazulene, cal
Vinol, psoipone, 4,5-benzotropo
2-phenyltropone, naphthocyclohepta
Dienone, Naphthotropone, Tribenzotropo
1-amino-1,3-dicyanazulene,
hydrazone, 3-phenyl-1-oxa
Azlanone-2,2-benzyltropone, 3-methane
Chil-2-phenyltropone, 2,7-diphenylated
lutropon, 2-(α-naphthyl)-tropone,
2,7-tetramethylene-4,5-benzotropo
2,7-diphenyl-4,5-benzotropo
N, Naphth [2', 3'-4, 5] Trophon, Naft
[2′,1′−2,3] Tropon, dibenzosuberan,
Naphtho [1', 2'-2, 3] tropone, dibenzos
Verol, 4-oxy-2-phenyltropone,
4,5,7-tribromo-2-phenyltropo
3,5'-ditropolone, 3-(p-methoxy)
phenyl) tropolone, 4-oxy-2-phenylated
lutropon, 3-(α-naphthyl)tropolone,
3,4-diphenyltropolone, 3,7-diben
Diltropolone, 4-(γ-phenylpropyl)
Tropolone, 3,5'-vitropolonyl, 4-(p
-nitrostyryl) tropolone methyl ether,
2-amino-1,3-dicyanazulene, benzo
[b] Tropothiazine, 5-bromo-2-phenylated
Lutropon, 4-bromo-2,7-diphenylto
Ropon, diphenyl biphenyl carbinol, chi
Examples include Azinotropone and the like. Next, heterocyclization with 5 or more conjugated π bonds
Specific examples of compounds include the following compounds.
Ru. First, as oxygen-containing heterocyclic compounds, furan and its derivatives, such as 2,5-di
Phenylfuran, 2-phenylfuran, 3-methyfuran
R-diphenylfuran, lepiden, pyridoxy
benzofuran, isobenzofuran, dibenzofuran, 2,4-diphenylfuran;
Ran and its derivatives, e.g. dibenzofura
N, furano [2′,3′-7,8] flavone, egono
ol, eupalin, 1,3-diphenylisoben
Zofran, tetraphenyl glycol, tetraf
Enylphthalane, 9-phenylanthracene, o
-oxymethyltriphenylcarbinol, 3,
3'-diphenylphthalide, 1-phenylfurata
1,1-phenylfuratane, 3,3-diphene
Nilphthalide, Rubrene, α-Solinine, Diben
Zofuran, 2,2'-dioxybiphenyl, 2,
2'-diaminobiphenyl, phenazone, dibenzo
Quinone, 2-hydroxybenzofuran, 2-methy
Rubenzofuran, benzo[a]benzofuran, benzofuran
dibenzo[b]benzofuran, dibenzo[a,f]di
Benzofuran, dibenzo[c,d]dibenzofuran
dibenzo[c,e]dibenzofuran, bi(2
-dibenzofuryl), bi(3-dibenzofuryl); pyran and pyrone derivatives, such as 2-p-
Oxyphenyl-4,6-diphenylpyrylium
Ferrichloride, anhydrobase, benzopyra
4-p-oxyphenyl-2,6-diphenyl
Rupyrillium ferrichloride, 6-phenylicuma
Phosphorus; chromenol and chromene derivatives, e.g.
6-methyl-2,3-diphenylchromone, 6-
Methyl-2,3-diphenyl-4-(p-tolyl)
-1,4-benzopyran-4-ol, chromano
alcohol, γ-chromene, oxycoumarone, chromene
cyanidin chloride, chloride, fissetyl
6-oxy-3-methoxy-5,7-dimethylene
Luflavirium chloride, 4,4'-diflavirene
-3,3'-oxide, chlicinidine, apigenidine
N, lotoflavinidin, lutelinidin, galangi
Nigin, phycenidine, morinidine, flavonoid
min, pelargonidin, cyanidin, delphini
Gin, petunidin, syringidin, hirsutiji
N, apigeninidin, caradyulin, dracolo
Gin, dracolbin; flavones, flavonols and isoflavone inducers
Conductors, e.g. flavonols, flavones, fukuge
Chin; coumarin and isocoumarin derivatives, e.g.
7-oxy-3,4-benzocoumarin, dicoumaro
Angelicin, Psoralen, Bergapte
velcaptol, xanthotoxin, xane
totoxal, isopinpinerine, pimpinelli
N, olocerol, olocerone, peucedanine,
Oxypeucedanin, Ostrutol, Medakeni
N, nodakenetin, seserine, xanthyretin,
xanthoxyletine; and xanthones and related compounds, such as dixa
tyrene, 9-phenylxanthene, isoxane
ton, 1,2,7,8-dibenzoxanthene,
3,9-diphenylxanthene, 9,9-diphene
Examples include nilxanthene. Next, as the nitrogen-containing heterocyclic compound, pyrroles, such as 1-phenylpyrrole,
5-phenylpyrrole-2-aldehyde, phenyl
-2-pyrylketone oxium, 2-phenyl
pyrrole, 2-methyl-1-phenylpyrrole,
2-methyl-4-phenylpyrrole, 2-methyl
-5-phenylpyrrole, 3-methyl-5-phene
Nylpyrrole, 2,4-diphenylpyrrole,
2,5-diphenylpyrrole, 2,3-diphenyl
Lupirole, 2,3,5-triphenylpyrrole
1,2,3,5-tetraphenylpyrrole,
2,3,4,5-tetraphenylpyrrole, diphenylpyrrole
enyl-2-pyrylcarbinol, pyrrolesic
Lotrimethine dye, pyrrole polymethylene dye,
biliverdin, bilirubin, prodigiosin,
Tercobilin; indoles, e.g. 5,7-dichloro-2
-phenylindole, 7-chloro-2-phenylated
Reindole, 5,7-dibromo-2-phenyl
Indole, 7-bromo-5-chloro-2-phene
Nilindole, 2-(3′-indolyl)-3-y
sonitrosoindolenine, roseindole, to
Lyptophan blue, indolo[3,2-c]ki
Norin, indolo[1,2-c]quinazoline, 2
-phenylindole, 3-nitro-2-phenylated
Ruindole, 3-phenylindole, N-methane
Chil-3-phenylindole, 3-(o-nito
Lofenyl) indole, 2,3-diphenyl
indole, 3-triphenylmethylindole,
2-Methyl-3-triphenylmethylindole
2-phenyl-3-triphenylmethylin
Dole, 2-(1-naphthyl)-3-triphenyl
Methylindole, 2-(2-naphthyl)-3-to
rifenylmethylindole, 3,3'-diindo
Lyle, 3,2'-diindolyl, 3,3'-dehydro
Diindole, rose indole, 3-nitroso
-2-phenylindole, 3-nitro-2-phenyl
Enylindole, 2-methyl-3-phenyla
Zoindole, 2-phenyl-3-phenylazo
Indole, 6-oxy-3-phenylindole
Le, tryptophan, 4,5-benzotryptophane
Anne, 6,7-benzotryptophan, zeolase
in; oxo derivatives of indole, e.g. 3-(4
-ethoxy-1-naphthyl)oxindole,
indophenine, indigoazine, indigoero
-3G; Isoindoles, e.g. 1-chloro-4-
Methylphthalazine, 1-benzylidenephthalimide
gin, 2-methyl-3-phenylphthalimidi
2-methyl-1,3-diphenylisoindo
2,5-diphenylisoindole, β-
Isoindigo, dimethylimino-β-isoindigo
G; Carbazoles, such as 1-phenyl-1,
2,3-benzotriazole, 2,2'-diamino
Diphenyl, 1,1'-dicarbazole; polyphyllins, such as polyphyllazine, macerate
Gnesium octamethyltetraazaporphyri
azadipyromethine, phthalocyanine, diaza
Coproporphyrin, porphyrin, mesotetrough
enylporphyrin, chlorophyll-b, chloro
File-a; Oxazoles, such as 2-phenyloxa
sol, 4-phenyloxazole, 5-phenyl
Luoxazole, 2-methyl-4-phenylox
Sasol, 2-methyl-5-phenyloxazole
4-methyl-2-phenyloxazole, 5
-Methyl-2-phenyloxazole, 4,5-
Dimethyl-2-phenyloxazole, 2,4-
Diphenyloxazole, 2,5-diphenyloxazole
xazole, 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-aminophe
oxazole, 2-(o-aminophenyl)
Oxazole, 4,5-dimethyl-2-phenyl
Oxidooxazole, 4-methyl-2,5-di
Phenyl oxide oxazole, 2,4,5-t
rifenyl oxide oxazole, 4-(o-methane)
Toxicarbonylbenzal)-2-phenyl-5
-Oxazolone, oxacarbocyanine dye, fluorescent
enanthrooxazole; isoxazoles, e.g. 4-nitro-3
-Phenyl isoxazole, 5-amino-3-
Methyl-4-phenyl isoxazole, 5-benzene
Nzoyl-3,4-diphenyl isoxazo
thiazoles, such as 4-phenylthiazole
fluor, 5-phenylthiazole, 5-(p-fluor)
phenyl)thiazole, 2-methyl-4-phenylated
Luciazole, 4-methyl-5-phenylthiazo
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)bife
Nyl, 2-amino-4-phenylthiazole, 2
-amino-5-phenylthiazole, 2-amino
-4,5-diphenylthiazole, 2-phenyl
Azothiazole, 2-amino-4-methyl-5-
Phenylazothiazole, 4-methyl-2-phene
Nylazothiazole, α-naphthothiazole, β
-naphthothiazole, naphtho[2,3]thiazole
Naphtho[1,2]thiazole, 2-methyl
[1,2]thiazole, 2-phenylnaphtho[1,
2] Thiazole, 2-methylnaphtho[2,1]thi
Azole, 4-bromo-2-phenylnaphtho
[2,3]thiazole, 2-oxynaphtho[2,
1] Thiazole, 2-aminonaphtho[1,2]thi
Azole, 2-aminonaphtho[2,1]thiazole
2-mercaptonaphtho[1,2]thiazole
2-mercapto[2,1]thiazole; imidazoles, such as 2-phenylimida
sol, 4-phenylimidazole, 4-methyl
-2-phenylimidazole, 2,4-dipheny
limidazole, 4,5-diphenylimidazole
2,4,5-triphenylimidazole, 2
-bromo-4-phenylimidazole, 5-bromo
-1-ethyl-2-phenylimidazole, 5
-chloro-1,2-diphenylimidazole, 2
-phenylazoimidazole, 2-methyl-4-
Phenylazoimidazole, 2-(o-aminof)
(enyl)benzimidazole; pyrazoles, such as 3-phenylpyrazo
ru, 5-phenylpyrazole, 4-phenylpyrazole
sol, 1-methyl-3-phenylpyrazole,
1-Methyl-5-phenylpyrazole, 3-methy
-5-phenylpyrazole, 1,3-diphenyl
Lupyrazole, 1,5-diphenylpyrazole,
1,3,4-triphenylpyrazole, 1,3,
5-triphenylpyrazole, 1,4,5-tri
Phenylpyrazole, 5-amino-3-phenyl
Pyrazole, 3-amino-5-phenylpyrazo
5-methyl-1,3-diphenylpyrazole
-4-aldehyde, 3,5-diacetyl-4-ph
enylpyrazole, 4-benzoyl-1,5-di
phenylpyrazole; oxadiazoles, e.g. 3-phenylpyrazole;
Razan, 3,4-diphenylfurazan, Naruto
[1,2]furazane, phenylfuroxane, 3-
Methyl-5-phenyl-1,2,4-oxadia
sol, 2,5'-diphenyl-1,3,4-oxy
Thiadiazole; Thiadiazoles, e.g. 5-phenyl-
1,2,3-thiadiazole, 2-phenyl-
1,3,4-thiadiazole, 5,5'-dipheny
Rub-2,2'-bis(1,3,4-thiadiazole)
), 2-oxy-5-phenyl-1,3,4-
Thiadiazole, 2-methylsulfonyl-5-phenyl
enyl-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-phenyltetra;
sol, 1,5-diphenyltetrazole, 1-
Oxy-5-phenyltetrazole, 1-amino
-5-phenyltetrazole; Pyridine related compounds, e.g. 2-phenyltetrazole
Lysine, 2,2'-dipyridyl, 2-chloro-6-
Phenylpyridine, 2,6-dichloro-3-phene
Nylpyridine, 2,2'-azopyridine, 3,3'-
Azopyridine, benzene-4-azopyridine, 5
-chloro-2,2'-azopyridine, 5,5'-dichloro-2,2'-azopyridine,
Lor-2,2'-azopyridine, 4-pyridylazo
Resorcin, 4-pyridyl-m-phenylenedia
amine, 3-pyridyl-m-phenylenediamine; quinoline and related compounds, e.g.
quinaldine, quinaldine-N-oxide,
Chiruquinaline, 2-phenylquinaline, 3-methy
Lucinaline, 3-phenylquinaline, 4-methyl
Quinaline, 4-phenylquinoline, 6-methylquinoline
Norine, 6-ethylquinoline, 6-phenylquino
Phosphorus, 2,4-dimethylquinoline, 2,4-diph
enylquinoline, quinoline-4-methanol,
Norine [6,5-f]quinoline, quinophthalone,
flavaaniline, quinoline blue, ethylrez
de, vinacyanol, naphthocyanol, clip
tocyanin, xenocyanin, azacyanin,
6,6′-octahydroquinoline, Bestrun Red,
2,3'-biquinoline, 2,5'-biquinoline, 2,
6′-biquinoline, 2,7′-biquinoline, 3,3′-
Biquinoline, 4,5'-biquinoline, 4,6'-biquinoline
Quinoline, 5,5'-biquinoline, 6,6'-biquino
phosphorus, 6,7′-biquinolin, 6,8′-biquinolin
7,7′-biquinoline, 8,8′-biquinoline,
2-fluoroquinoline, 3-fluoroquinoline,
4-fluoroquinoline, 5-fluoroquinoline,
6-fluoroquinoline, 7-fluoroquinoline,
8-fluoroquinoline, 3-bromoquinoline, 4
-Chlorquinoline, 2,4-dichloroquinoline,
3-nitroquinoline, 4-nitroquinoline, 2,
3-quinolinediol, quinoline-2-thio
2-oxyquinoline-3-thiol, 2-a
Minoquinoline, 8-aminoquinoline, 2-hydra
Diquinoline, pyrroloquinoline, thiazoloquinoline
pyrimido[4,5-b]quinoline, benzo
[f] Quinoline; Isoquinoline and related compounds, such as 1-
Methylisoquinoline, 3-bromomethylisoquino
Phosphorus, 1-phenylisoquinoline, 4-phenyl
Isoquinoline, 1,1'-biisoquinoline, 5,
5′-biisoquinoline, 1-chloroisoquinoline,
5-iodoisoquinoline, 5-bromoisoquinol
5-Nitroisoquinoline, Isoquinoline-
1,3-diol, 6,7-methylenedioxy
Soquinoline, 1-aminoisoquinoline, 1-sia
isoquinoline, 1-phenylbenzo[g]3,
4-dihydroisoquinoline, 3-(p-aminof
enyl)-5,8-dihydro-8,9-dimethoxy
Shiimidazo[5,1-a]isoquinoline; acridine and related compounds, such as acridine
gin, 1-methylacridine, 9-phenylac
Lysine, 9-(3-pyridinyl)acridine, 2
-Chloracridine, 2-bromoacridine, 2
-acridinol, acridine-3,6-diol
, 4-methoxyacridine, 9-phenoxia
Clidine, 1-nitroacridine, 4-aminoa
Clidine, 1-aminoacridine, 9-phenyl
Aminoacridine, 9-oxyacridine, cridine
Sanilin, acriflavine, 3,6-diamino-
4,5-dimethylacridine, acrinol; phenanthridines, such as 3,4-benzo
Quinoline, 6-methylphenanthridine, 6-a
Minomethylphenanthridine, 6-phenylphene
Nanthridine, 6-chlorphenanthridine, 6
-bromophenanthridine, 6-nitrophenane
Tolidine, 1-aminophenanthridine, 3-o
xyphenanthridine; 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, e.g.
1,7-phenanthroline, 1,10-phenanth
loline, 4,7-phenanthroline, 8-methyl
-1,7-phenanthroline, 4,10-dioxy
-1,7-phenanthroline, 3,5-dichlor
-1,10-phenanthroline, 2-amino-1,
10-phenanthroline, 5-oxy-4,7-ph
Enanthroline, 5-amino-4,7-phenan
Troline; pyridindoles, e.g. 1,9-pyrido
indole, 2,9-pyridindole, 4,9
-pyridindoles; naphthyridines 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-naphthyridin-4-ol, 3-amino-
1,5-naphthyridine, 2-amino-1,5-na
Phthyridine, 2-oxy-1,7-naphthyridine
Oxazines and related compounds, e.g.
xazinone, resazurin, carocyanine, nile
Blue A, Meldora Blue, Brilliant Credit
Le Blue; Thiazines and related compounds, such as o-ben
Zaminophenyl-β-phenoxycarbonyl ether
Tylsulfide, phenothiazine, nitropheno
Thiazine, 3-chloro-10-ethylphenothiazide
4-amino-4'-anilinodiphenyldisul
Fido, 2-chloro-10-(3-dimethylamino
propyl) phenothiazine, chlorpromazine,
10-(2-dimethylamino-1-propyl)phene
Notiazine hydrochloride, 10-[2-(1-pyrrolidyl)
ethyl]phenothiazine hydrochloride, 10-(1-methyzate)
(3-piperidylmethyl)phenothiazine, 2
-acetyl-10-(3-dimethylaminopropyl)
Phenothiazine, methylene blue; pyridazine and related compounds, e.g.
Phosphorus, 3-methylcinnoline, 4-chlorcinnoline
Phosphorus, 3-bromocinnoline, 4-cinnolino
ru, 4-aminocinnoline, phthalazine, 4-ethyl
Chill-2-phenylphthalazinone, phthalazinthi
All, 1(2H)-phthalazinone, 3-phenyl
Pseudophthalazine, 4-methyl-3-phenyl
Pseudophthalazone, 2,3-dihydro-1,4
-phthalazinediones; pyrimidines and related compounds, e.g.
pyrimidine, 4,6-dimethyl-2-
Phenylpyrimidine, 2,4,6-triphenyl
Pyrimidine, alloxanthin, 2,6-dioxy
-4-phenylpyrimidine, 4,6-dioxy-
2-phenylpyrimidine, 5-chloro-4,6-
Dioxy-2-phenylpyrimidine, sulfazide
Azine, sulfisomidine, tonzylamide hydrochloride
vitamin B1, thiochrome, cocarboxyla
aromycin, 6-(2-furfuryl)a
Minopurine, pteridine, 2,4-pterindio
2-amino-6-methyl-4-pteridino
ole, xanthopterin, leucopterin, iso
Xanthopterin, quinazoline, 4-chlorquina
Zoline, 2,4-dichloroquinazoline, 4-quina
Zolinone, 2,3-diphenyl-4-quinazoli
pyrazine-related compounds, such as 3,6-diphenylene;
Nilpyrazinol, quinoxaline, 2-methylquinoxaline
Noxaline, 2,3-dimethylquinoxaline, 2
-Chlorquinoxaline, 2,3-dichloroquinoxaline
sarin, 2-(o-aminoaniline)quinoxane
N,N'-diphenyl-2,3-piperadio
2-quinoxalinol, 2,3-quinoxalinol
diol, 2-aminoquinoxaline, 2,3-
Diaminoquinoxaline, methylquinoxaline-2
-carboxylic acid ester, 2-(d-arabotetra
(oxybutyl) quinoxaline, flavazole,
Lucazidone, phenazine, phenazine-5-oxy
Sid, phenazine-5,10-dioxide, 5-methane
Tilphenadinium methyl sulfate, 10-methyl
Chil-5,10-dihydro-2-phenazinecarbo
Nitrile, 2-phenazinecarbonitrile, 1-
Phenazinol, 1-methoxyphenazine, 2-
Phenazinol, 1,6-dioxyphenazine-
5,10-dioxide, 1-aminophenazine, 2
-Aminophenazine, 2,3-diaminophenazine
N, neutraraled, 5,10-dihydrofena
gin, 5-methyl-5,10-dihydrophenadi
1,2,3,4-tetrahydrophenazine; tri- and tetra-hetero-six-membered cyclic compounds;
For example, 2,4,6-triphenyl-s-tria
gin, 2,4-dichloro-6-o-chloroanili
-s-triazine, 5,6-diphenyl-as-
triazine, 2,6-diphenyl-2,3,4,
5-tetrahydro-as-triazine, 5,6-di
phenyl-as-triazin-3-ol, 1,
2,4-benzotriazine, 1,2,4-benzo
triazin-3-ol, 3-phenyl-1,
2,3-benzotriazin-4-(3H)-one,
1,2,3-benzotriazin-4-ol,
1,2,3-benzotriazine-4-thiol,
3-amino-1,2,3-benzotriazine,
2,3-diphenylosotetrazine, 5,6-di
Methyl-2,3-diphenylosotetrazine, 5
-cyan-2,3-diphenylosotetrazine,
5,6-dibenzoyl-2,3-diphenyl-oso
Tetrazine, 2,3-dibenzoyl-5-methyl
Osotetrazine, 2,3-dibenzoyl-5,6
-dimethylosotetrazine, 2,3-dibenzoy
-5,6-diphenylosotetrazine, 2,3
-bis(2,4-dichlorophenyl)-5,6-
Diphenyl-1,2,3,4-tetrahydro-ν
-tetrazine, 1,2,3,4-tetraethoxy
xycarbonyl-5,5-diphenyl-1,2,
3,4,5,6-hexahydro-v-tetradi
7-methyl-2-(4-methylphenyl)-
1,2-dihydrobenzoterolazine, 3,6-di
phenyl-1,2-dihydro-s-tetrazine,
1,3-diphenyl-1,4,5,6-tetrahydrogen
Dro-s-tetrazine, 3,3,6,6-tetra
Phenyl-1,2,3,6-tetrahydro-s-
Examples include tetrazine, etc. Furthermore, as the sulfur-containing heterocyclic compound, sulfur-containing heterocyclic compounds such as 2-phenylene
ruthiophene, 2,4-diphenylthiophene,
2,3,4,5-tetraphenylthiophene, salt
metaphenylene acid, metapyrylene hydrochloride, citric acid
Chlorotene, thenyldiamine hydrochloride, α-kinkuti
enyl, α-sexithienyl; fused thiophene compounds, such as 3,3′-di
iminothioindigo, indigorone, dihydrona
Phtho[2,1-b]thianaphthene, 1,3-diph
enylisothianaphthene, dibenzothiophene,
2-nitrodibenzothiophene, aminodibenzo
Thiophene, 2,8-diaminodibenzothiophene
dibenzothiophene-5-dioxide, 4-
Oxydibenzothiophene, 2,8-dioxydi
Benzothiophene, 2-chlorodibenzothiophene
1-bromodibenzothiophene, 2,8-di
Bromodibenzothiophene, 2-iododibenzo
Thiophene, 2-acetyldibenzothiophene,
2,8-Diacetyldibenzothiophene, naphtho
Thiophene, 3-oxythiophhanthrene, 2,
3-thiophanthraquinone, 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-na
Phtho[2,1-b]thiophenaldehyde, naph
tho[1,2-c]thiophene, 2H-naphtho[1,
8] Thiophene, benzo[b]thiophantre
6,11-benzo[b]thiophanthraquino
benzo[g]thiophantrene, 4,5-benzo
Benzothiophanthrene, 8,9-benzothiofur
Nthrene; a five-membered monocyclic compound containing two heteroatoms, e.g.
For example, 5-phenyl-1,2-dithiol-3-thiol
3,4-dihydronaphtho-2,1-trithi
on, thiaflavones, thiacoumarins, thiaxanes
ten, thiaxanthhydrol, thiaxanth
N, Mirasil D, bisthiaxanetyrene; six-membered cyclic compound having two or more heteroatoms
2,5-diphenyl-1,4-dithi
adiene, thiophenaldehyde, thianthre
2,7-dimethylthianthrene, 1-thianthrene
Trenyllithium, 1-chlorothianthrene, fluoride
Enoxathiin, 2-vinylphenoxathiin,
2-aminophenoxathiin, 2-nitropheno
Xatiin, 3,7-dinitrophenoxatii
10,10-diphenylphenoxathiin, 2,
5-diphenylthiophene; and the like. Furthermore, other compounds include bicyclic compounds that share a nitrogen atom, such as
Nconine, 2-phenylpyrocholine, 3-ethyl
-2-phenylpyrocholine, 3-benzyl-2-
Phenylpyrocholine, 3-nitroso-2-phenylated
Lupyrocholine, 2:3-benzopyrocholine, 1,
5,8-trimethyl-2:3,-benzopyrocholi
1-ethyl-5,8-dimethyl-2:3-benzene
Zopyrrocholine, 1,8-dimethyl-2:3-beta
Zopyrrocholine, 3-phenyl-7:8-benzo
Pyrocholine, cyclo[3.3.3] azine, cyclo
[3.2.2] Azine, 2-phenylcyclo [3.2.2] azine
Zine, 2,3-diphenylcyclo[3.2.2]azi
tricyclazine, 7-methylbenzo[a]k
Noridinium bromide, 7-phenylbenzo[a]
Quinolidinium bromide, benzo[b]quinolidinium
um salt, tetrahydro-Ψ-berberine, tetra
Hydroberberine, laudanosoline, tetrahydride
rho-2,3,9,10-tetraoxy-7-methyl
Dibenzopyrocorinium chloride, homolaudanozo
Phosphorus, octadehydromatrine, canadine metoyo
alkaloids, such as nicotyline, 3'2-
dipyridyl, cusparin, galiporin, 1-methy
Ru-2-quinolone, cashimiroin, 2-pentyl
Quinoline, 4-oxy-2-pentylquinoline,
4-methoxy-2-pentylquinoline, 1-methy
-2-pentyl-4-quinolone, 4-methoxy
-2-phenylquinoline, 7-methoxy-1-meth
Chil-2-phenyl-4-quinolone, Kusparei
N, dictumunin, skinmianin, evolitori
Macrin, Coxagin, Coxaginine, Mac
Rosidin, Frindelcyamine, Evoxoidi
Evoxin, Eboratin, Aclonisidine,
Medicosmin, aclonidine, γ-fuagarin,
cinchonine, quininone, quinotoxin, N-bro
mucinotoxin, dihydrocinchonisin, hetero
quinine, evoxanthidine, xanthoxoline,
1,3-dimethoxy-10-methylacridone, ester
Voxanthine, xanthoevoquine, mericopine,
mericopidine, mericopicin, acronisin,
lindersine, hapaverine, papaveraldine, la
Udanosine, Laudanine, Codamine, Protopapa
Verine, almepavine, 4,4'-5-trimethoxy
C-2-vinylstilbene, coclaurine, d-
Isococlaurine, Neprotin, Colpaverine,
Ferrodendrin, Magnocurarine, Cochrane
narcotine, narcotrine, aponarcine
cinchonine, cinchonine, cinchotoxin, didehydrohydrogen
Dolastin, Bicuculline, Adormidine, Corlu
Midine, cordrastine, magnolamine, velva
amine, o-methylberbamine, etc. The present invention provides (a) the above-mentioned compound as a scale adhesion preventive agent.
At least one type of π-bonded compound and (b) an inorganic compound
There is also a method of using in combination with at least one of
Regarding this, please apply these to the inner wall of the polymerization vessel.
chloride ions in the reaction mixture during the polymerization process.
Control the concentration to below 100ppm, preferably below 50ppm.
Similarly, by controlling the schedule effectively and reliably.
It is possible to prevent the adhesion of rolls. inorganic compounds
It does not have the ability to prevent scale adhesion by itself.
However, when this is combined with a conjugated π bond compound as in this invention,
Scale adhesion of conjugated π-bonded compounds when combined
The preventive effect is surprisingly improved. However,
This effect also reduces the chloride ion concentration in the reaction mixture.
It is effectively demonstrated by keeping it below 100ppm.
I found out that it can be done. Chlorine ion concentration is 100ppm
If it exceeds the scale, the scale adhesion prevention effect is insufficient and the scale
It is not possible to effectively prevent oil adhesion. As mentioned above, the conjugated π bond compound of component (a) and (b)
When applying the mixture of component inorganic compounds, (a)
The ratio of component (b) to component (b) is per 100 parts by weight of component (b).
It is preferable that the component is 0.1 to 2000 parts by weight,
More preferably, the amount is 1 to 1000 parts by weight.
stomach. The inorganic compound of this (b) component is orthosilicone.
acid, metasilicic acid, mesodisilicic acid, mesotrisilicic acid,
Mesotetrasilicic acid, sodium metasilicate, orthoke
Sodium silicate, sodium disilicate, tetrasilicic acid
Sodium, potassium metasilicate, hydrogen disilicate
Potassium, lithium orthosilicate, orthosilicate
Hexalithium oxide, water glass, 12-tungsten silica
Acid, iso-12-silicotungstic acid, 10-keita
ungstic acid, potassium 12-silicotungstate
Potassium iso-12-silicotungstate, 10
- Potassium silicotungstate, 12-kaitung
Sodium stenate, iso-12-keitungste
Sodium phosphate, Keimolybdic acid, Keimolyb
Potassium denate, sodium silicomolybdate
Which silicic acids or silicates; alkaline substances such as magnesium, calcium, barium, etc.
Potassic earth metals, zinc group metals such as zinc, aluminum
Aluminum metals such as aluminum, titanium, tin such as tin
Group metals, iron, iron group metals such as nickel, chromium, metals
Manga of chromium group metals such as liveden, manganese, etc.
Copper group metals such as copper and silver, platinum group metals such as platinum
Oxygenates and acetates of metals selected from metals, etc.
Metals such as nitrates, hydroxides or halides
Salt; colloidal gold, colloidal silver, colloidal sulfur, water
Colloid of ferric oxide, colloid of stannic acid, silica
Acid colloid, manganese dioxide colloid, oxidation
Molybdenum colloid, barium sulfate colloid
colloid of vanadine pentoxide, aluminum hydroxide
colloid of umum, colloid of lithium silicate
Mechanical crushing, ultrasonic irradiation, electrical dispersion, etc.
Inorganic colloids prepared by chemical methods
is exemplified. Among these, especially silicates
colloids, silicate colloids, ferric hydroxide colloids, etc.
preferable. By the method of the present invention, a conjugated π-bonded compound can be
Alternatively, a conjugated π bond compound and the inorganic compound are combined.
When applying the mixture to the inner wall of the polymerization vessel, etc.,
In addition, other scale adhesion prevention agents can be used together.
Wear. Typical scale adhesion inhibitors
Among them, dyes and pigments can be mentioned.
Ru. Examples of dyes and pigments include monoazo and
Polyazo dyes/pigments, metal complex azo dyes/pigments,
Stilbene azo dyes, thiazole azo dyes, etc.
Zo-based dyes and pigments; anthraquinone derivatives, anthrone derivatives, etc.
Anthraquinone dyes/pigments; indigo derivatives, thioindigo derivatives, etc.
Digoid dyes/pigments; Phthalocyanine dyes/pigments; Diphenylmethane dyes, triphenylmethane dyes
dyes, pigments, xanthene dyes, macridine dyes, etc.
Carbonium dyes/pigments; azine dyes, oxazine dyes, thiazine dyes, etc.
quinoneimine dyes; methine dyes such as polymethine or cyanine dyes
quinoline dyes; nitro dyes; benzoquinone and naphthoquinone dyes; naphthalimide dyes and pigments; perinone dyes; sulfur dyes; fluorescent dyes; azoitsk dyes;
It can be used alone or in combination of two or more.
Among these exemplified dyes and pigments, especially azine-based
Dyes are preferred. These dyes and pigments are further added.
A concrete example is as follows. Examples of azo dyes and pigments include:
can be lost. As monoazo and polyazo dyes, for example, Basic Yellow 32, 34 and 36;
Quo oranges 2, 32, 33 and 34;
17, 18, 22, 23, 24, 32, 34, 38, 39 and
40;Basic Violet 26 and 28;Basic Violet
Tsuku Blue 58, 59, 64, 65, 66, 67 and 68;
Issitsuku Brown 1, 4, 11 and 12; Bassits
Kuburatsuku 8; Azoituku 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; Dispersed 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; Daspers 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 Olene
Di 1, 2, 5, 6, 14 and 45; Solventrets
Dos 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; Pigmen
Toledo 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;
Electrets 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; die
Recto 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;
Do 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; Assisted Biorect 7;
11, 97 and 106; acid blue 29, 60, 92,
113, 117 and 120; acid green 19, 20 and
and 48; acid brown 2, 4, 13, 14, 20,
53, 92, 100, 101, 236, 247, 266, 268, 276,
277, 282, 289, 301 and 302;
Ku1, 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; modern training
Tudo 7, 9, 17, 19, 21, 26, 30, 63 and 89;
Mordaunt Violet 5 and 44; Mordaunt
Blue 7, 13, 44, 75 and 76; Mordant Grip
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;
Dredred 7 and 9; As metal complex azo dyes, for example, Solvent Yellow 61 and 80;
Ranges 37, 40 and 44; Solvent Red 8,
21, 83, 84, 100, 109 and 121; Solventb
Round 37; Solvent Black 23; Acid Bra
Tsuku 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; Assured 180, 183;
184, 186, 194, 198, 199, 209, 211, 215, 216,
217, 219, 256, 317, 318, 320, 321 and 322;
Assisted Violet 75 and 78; Assisted Bull
-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; assist
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; Da
Direct Violet 47 and 48;
Roux 90, 98, 200, 201, 202 and 226; direct
Examples of stilbene azo dyes include Direct Black 62; Examples of thiazole azo dyes include Direct Red 9 and 11. Anthraquinone dyes and pigments include the following:
can be mentioned. Examples of anthraquinone derivatives include: Basic Violet 25; Basic Blue
21, 22, 44, 45, 47, 54 and 60;
Azo component 36; Butt yellow 2, 3,
10, 20, 22 and 33; butt orange 13 and
15; Battled 10, 13, 16, 31, 35 and 52;
Bat Violet 13 and 21; Bat Blue
4, 6, 8, 12, 14, 64, 66, 67 and 72;
Green 8, 13, 43, 44 and 45;
Round 1, 3, 22, 25, 39, 41, 44, 46, 57,
68, 72 and 73; butt black 8, 14, 20,
25, 27, 36, 56, 59 and 60; Disperse Ole
11; Dispersed 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
Low 51; Solvent Violet 13 and 14;
Solvent Blue 11, 12, 35 and 36; Solvent
Green 3; Pigment Red 83 and 89; Pigment
Mento Blue 22; Assisted Violet 31, 34,
35, 41, 43, 47, 48, 51, 54, 66 and 68;
Tsudo 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; Modern Red 3 and
11; Mordant Blue 8 and 48; Mordant Blue
Rack 13; Pigment Violet 5; As anthrone derivatives, for example, Butt Yellow 1 and 4; Butt Orange
1, 2, 3, 4 and 9; butt violet
1, 9 and 10; Bat Blue 18, 19 and 20;
Butt green 1, 2, 3 and 9; Butt bra
Tsuku 9, 13, 29 and 57; buttred 13;
Examples include Tsudred 80, 82 and 83. The following are indigoid dyes and pigments:
Can be mentioned. Indigo derivatives include, for example, Batt Blue 1, 3, 5, 35 and 41;
Soft Butt Blue 1; Pigment Violet
19 and 122; acid blue 74 and 102;
Reclaimed Butt Blue 5 and 41;
Rejuvenated Butt Black 1; Hood Black
Ru 1; As thioindigo derivatives, for example, Butt Orange 5; Butt Red 1, 2 and
61; Bat Violet 2 and 3; Pigment
Red 87 and 88; Butt Brown 3 included.
Ru. As phthalocyanine dyes and pigments, 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 are mentioned. Carbonium dyes and pigments include the following:
Can be mentioned. Diphenylmethane dyes include, for example, Basic Yellow 2; triphenylmethane dyes include, for example, Basic Cred 9; Basic Violet.
1, 3 and 14; Basic Blue 1, 5, 7,
19, 26, 28, 29, 40 and 41;
1 and 4; Solvent Violet 8; Sol
Bent Blue 2 and 73; Pigment Violet
3; Pigment Blue 1, 2 and 3; Pigment Blue 1, 2 and 3;
Direct Green 1, 2 and 7; Direct Blue
41; Assisted Violets 15 and 49; Assisted
Blue 1, 7, 9, 15, 22, 83, 90, 93, 100,
103 and 104; acid green 3, 9 and
16; Mordant Violet 1; Mordant Bull
-1, 29 and 47; Food Violet 2; Fu
Food Green 2; As a xanthene dye, for example, Basic Red 1; Solvent Red 49;
Pigment Red 81 and 90; Pigment Violet
1, 2 and 23; Assured 51, 52,
87, 92 and 94; Modern Treads 15 and 27;
Food Red 14; Examples of acridine dyes include Basic Orange 14 and 15. Examples of quinone imine dyes include:
It will be done. As the azine dye, for example, BASIC RED 2; BASIC BLACK 2;
Solvent Black 5 and 7; Acid Blue
59; Acid Black 2; As an oxazine dye, for example, Basic Blue 3; Direct Blue 106 and
and 108; As thiazine dyes, for example, Basic Yellow 1; Basic Blue 9;
24 and 25. Examples of methine dyes include the following: As polymethine (or cyanine) dyes, e.g.
For example, Basic Yellow 11, 13, 14, 19, 21, 25,
28, 33 and 35; Basic Orange 21 and
22; Basic Cred 12, 13, 14, 15, 27, 29,
35, 36 and 37; basic violet 7,
15, 21 and 27. Examples of quinoline dyes include Basic Green 6; Disperse Yellow.
54 and 56; Solvent Yellow 33; Ashitudoi
Erow 3 is an example. Examples of nitro dyes include Disperse Yellow 1, 33, 39, 42, 49 and
and 54; acid yellow 1. As benzoquinone and naphthoquinone dyes
For example, Disperse Blue 58 and 108;
Rounds 103, 104, 106, 160, 161, 165 and 188
can be mentioned. Examples of naphthalimide dyes and pigments include Pigment Red 123; Bat Violet 23.
and 29; acid yellow 7. Perinone dyes include, for example, Butt Orange 7 and 15. Sulfur dyes include, for example, Solubilized Sulfur Yellow 2;
Sulfur Yellow 4; Sulfur Orange 3;
Sulfuaretu 2, 3, 5 and 5; Solyu
Billized Sulfur Blue 15; Sulfur Blue
Roux 2, 3, 4, 6, 7, 9 and 13; Salhua
- Greens 2, 3, 6, 14 and 27;
Rised Sulfur Brown 1 and 51; Sal
Fur Brown 7, 12, 15 and 31; Sulfur
Black 1, 2, 5, 6, 10, 11 and 15;
Yellow 35, 42 and 43; Blue 43 and
and 56. Examples of fluorescent paints include Fluorescent Brightening Agene.
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 are mentioned. Examples of azoitsk dyes include azoitsk diazo component 17, 20, 22,
24, 26, 31, 35, 41, 47, 48, 109 and 121;
Zoitsuku cutlet spring 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; Azoitsk Brown 2, 7, 11 and
15; Azoitsuku Black 1 and 5; Azoitsuku
Yellow 1 and 2; Azoitsk Orange 2, 3
and 7; Azoic Cred 1, 2, 6, 9, 16
and 24; azoic violet 1, 2, 6,
7, 9 and 10; Azoitsk Green 1 is mentioned.
It will be done. Examples of reactive dyes include 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 Ole
1, 2, 4, 5, 7, 13, 14, 15, 16, 18,
20, 23 and 24; Reactive Bread 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;
Eve 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 grid
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. Furthermore, pigments include chrome yellow, zinc yellow,
ZTO type zinc chromate, red lead, iron oxide powder, zinc
Inorganic materials such as lead white, aluminum powder and zinc dust
Examples include pigments. a conjugated π-bonded compound, optionally further comprising:
Applying a composition containing inorganic compounds to the inner wall of the polymerization vessel, etc.
To apply, either neat or dissolved in a suitable solvent.
Alternatively, you can prepare a coating solution by dispersing it and apply it.
stomach. The concentration of the scale inhibitor in the coating solution is usually
It is preferably 0.01% by weight or more. When preparing the coating solution, water, various
Species organic solvents, e.g. gasoline, petroleum, benzene
mineral spirits, petroleum naphtha, VM&
P. naphtha, decalin, tetralin, P-cymene
Any aliphatic hydrocarbons; aromatic carbons such as benzene, toluene, xylene, etc.
Hydrogenides; trichlorethylene, perchlorethylene,
Loloform, carbon tetrachloride, ethylene trichloride, one odor
Benzene chloride, benzene monochloride, benzene dichloride, etc.
Which halogenated hydrocarbons; amyl alcohol, ethyl alcohol, isoplasts
Lopyl alcohol, 2-ethylbutyl alcohol
alcohol, 2-ethylhexyl alcohol, cyclohexyl
Sanol, methyl alcohol, methyl amyl alcohol
Coal, benzyl alcohol, butyl alcohol
Alcohols such as acetone, acetonylacetone, diisobutyl
Ketone, diethyl ketone, dipropyl ketone, methane
tylamyl ketone, methyl butyl ketone, methyl
Cyclohexanone, Methyldipropylketone, Methyl
Tyl ethyl ketone, methyl normal hexyl ketone, methyl
methyl isobutyl ketone, methyl propyl ketone,
Ketones such as medicyl oxide; acetate esters, butyrate esters, propion
Esters such as acid esters and formate esters
Class: Butyl lactate, isopropyl lactate, ethyl lactate,
Ethyl oxypropionate, diethyl maleate
Alcohol esters such as ethyl acetoacetate, ethyl pyruvate, etc.
esters; isopropyl ether, ethyl ether, diethyl ether
Chilcarbitol, diethyl cellosolve, butyl
Ethers such as ether; acetonylmethanol, diacetone alcohol
dihydroxylacetone, piruvyl alcohol
Ketone alcohols such as isopropyl cellosolve, carbitol, glycol, etc.
Sidol, cellosolve, glycol ether, beer
cellosolve, butyl carbitol, butyl
Cellosolve, Methyl Derbitol, Methyl Celloso
Rub, triethylene glycol monoethyl ether
Ether alcohols such as alcohol; acetal ethyl ether, acetonyl methano
ethyl ether, methyl ethoxyethyl ether
Ketone ethers such as ether; butyl carbitol acetate, butyl cellosol acetate
bu, carbitol acetate, cellosolve acetate, acetic acid 3
-Methoxybutyl, methyl carbitol acetate, vinegar
Ester ethers such as acid methyl cellosolve; etc. can be used. Methylalcohol is highly compatible with water as an organic solvent.
alcohol, ethyl alcohol, allyl alcohol, n
-Propyl alcohol, isopropyl alcohol
Alcohols such as acetone, acetonyl acetone, diacetone
Ketones such as alcohol; acetic acid ethylene glycol monomethyl ether,
Acetic acid diethylene glycol methyl ether, acetic acid
Esters such as monoethyl ether; dioxane, ethylene glycol monomethyl ether
ether, ethylene glycol monoethyl ether
Ethers such as; tetrahydrofuran, furifuryl alcohol, etc.
Which furans; acetonitrile, N,N-dimethylformamide
non-probiotics such as di-, N,N-dimethylacetamide
When using a tonic solvent, etc., dissolve the scale adhesion preventive agent.
Add water to the coating solution to the extent that it does not impede the properties and dispersibility.
In addition, the economical efficiency of the coating solution and the safety during transportation and storage are improved.
You can aim for the top. The above conjugated π bond compound or an inorganic compound thereto
Apply the mixture to the inner wall of the polymerization vessel, etc.
When installing, to improve the adhesion to walls etc.
Various fixatives can be used as required.
Ru. The fixative is used to prevent scale adhesion.
How to use it by adding it to a coating solution containing
Before applying the anti-adhesive agent, use a fixing agent or
Apply the solution to the wall, etc., and then apply scale on top of it.
There are methods such as applying multiple coats of anti-stick agent.
Appropriate depending on the type of anti-stick agent and the type of fixing agent.
Choose your preferred usage. As such a fixative
The following polymer compounds can be used.
Ru. Olefin polymers, e.g. polyethylene
polyethylene sulfonic acid, polypropylene,
Poly(1-butene), polyisobutene, polysic
lopentene, polycyclopentylethylene, poly
Cyclohexylethylene, poly(3-cyclohexyl)
sil-1-propene), poly(4-cyclohexy
(1-butene), poly(5-cyclohexyl-
1-pentene), poly(cyclotrifluorethyl)
), poly(tetrafluoroethylene); diene polymers, such as polyalene, poly(tetrafluoroethylene);
Butadiene, polyisoprene, polychloropyrene
Poly(1-methoxybutadiene), Poly(2-methoxybutadiene)
-tert-butyl-1,3-butadiene), poly
(cyclopentadiene), poly(1,3-cyclohexane)
xadiene), poly(dimethylfulvene), poly
(4-vinyl-1-cyclohexane), poly(1,
5-hexadiene), poly(1,5-cyclooct)
tadiene), poly(bicyclo-2,2,1-hep)
ter-2,5-diene), poly(5,7-dimethyl
-1,6-octadiene), poly(diallyl phthalate)
), poly(diallyldimethylsilane), poly
(Diallylphenylphosphine oxide); Acetylene polymers, such as polyacetylene
Poly(cyanoacetylene), Poly((hydroxy)
(dimethyl)acetylene), poly(butoxyacetylene)
), poly(phenylacetylene), poly(diphenyl)
enyl diacetylene), poly(pyridylacetylene)
aliphatic vinyl, vinylidene polymers, e.g.
For example, polyvinyl alcohol, polyallyl alcohol
poly(vinyl formal), poly(vinyl formal)
acetal), poly(vinyl butyral), poly
(vinyl isobutyral), poly(vinyl cyclohexyl)
xanone ketal), poly(vinyl acetate),
Poly(vinyl chloroacetate), poly(vinyl
isobutyrate), poly(vinyl pivalate), poly
poly(vinyl n-caproate), poly(vinyl caproate)
(prelate), poly(vinyl laurate), poly
(vinyl palmitate), poly(vinylbenzoei)
), poly(vinyl sulfate), poly(vinyl sulfate),
chloride), poly(vinylidene chloride), poly
poly(vinyl bromide), poly(vinyl methyl ester)
ether), poly(vinyl ethyl ether), poly
(vinyl n-propyl ether), poly(vinyl n-propyl ether)
sopropyl ether), poly(vinyl n-butyl)
ether), poly(vinyl isobutyl ether),
Poly(vinyl tert-butyl ether), poly(vinyl tert-butyl ether)
(nil neopentyl ether), poly(vinylcal)
bomethoxymethyl 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 keto)
), poly(methyl isopropenyl ketone), poly
(1-nitropropylene), poly(vinyl sulfophyl)
fluoride), poly(vinyl sulfonic acid), poly(vinyl sulfonic acid),
nyldiphenylphosphine oxide), poly(vinyl diphenylphosphine oxide),
nyldiphenylphosphine sulfide), poly
(dimethyl-2-cyano-2-propene-1-pho
sulfonate), poly(diethyl-2-cyano-2
-propene-1-phosphonate), poly(male
Aromatic vinyl polymers, such as polystyrene
poly(α-methylstyrene), poly(4-methylstyrene)
rorostyrene), poly(4-bromostyrene), poly
poly(dichlorostyrene), poly(4-methoxys)
styrene), poly(2,5-dimethoxystyrene),
Poly(vinyl-bis(1-ethoxyethyl)hydride)
roquinone), poly(4-vinyl-phthalic acid), poly
(4-vinyl-phenylboric acid), poly(diphenylboric acid)
(4-styrylphosphine oxide), poly
(diphenyl-4-styrylphosphine sulfur
), poly(9-vinylanthracene), poly
(4-vinyl-biphenyl), poly(acenaphthylene)
Heterocyclic vinyl polymers, such as poly(N), polyindene;
-vinylcarbazole), poly(9-△ ^Five -Pente
nylcarbazole), poly(9-△ ^Five -hexenyl
carbazole), poly(N-vinylpyrrolidone),
Poly(2-vinylpyridine), poly(4-vinyl
pyridine), poly(2-methyl-2-vinylpyridine)
gin), poly(2,4-dimethyl-6-vinyl-
S-triazine), poly(N-vinyl-1,2,
4-triazine), poly(N-vinylbenztriazine)
azole), poly(N-morpholinone-(3)), poly
Coumaron; acrylic and methacrylic polymers, e.g.
For example, polyacrylic acid, polymethacrylic acid, poly
(methyl acrylate), poly(ethyl acrylate)
), poly(butyl acrylate), poly(5-silane)
ano-3-thia-phenyl acrylate), poly
(methyl methacrylate), poly(ethyl methacrylate)
rate), poly(n-propyl methacrylate),
Poly(n-butyl methacrylate), poly(iso
butyl methacrylate), poly(n-hexyl methacrylate),
acrylate), poly(2-ethylbutyl methacrylate),
rylate), poly(n-octyl methacrylate)
), poly(n-lauryl methacrylate), poly
(4-(tert-butyl)phenyl methacrylate),
Poly(bornyl methacrylate), poly(β-(N
-carbasyl)ethyl methacrylate), poly
(tert-butyl crotonate), polyacrylonite
Ryl, polymethacrylonitrile, polyacrylic
amide, poly(N,N-dimethylacrylamide)
), poly(N-(1,1-dimethyl-3-oxo)
butyl) acrylamide), poly(acrylopipe)
lysine), poly(acrylomorpholide), poly(9
-acrylic carbazole), polymethacrylic
Amide, polyacrolein, poly(α-methylalpha)
chlorein), poly(diacrylylmethane), poly
Poly (acrylic anhydride), poly (meth)
(krylic anhydride); polyethers, such as polyformaldehyde
polyacetaldehyde, poly(monochloroacetic acid), polyacetaldehyde,
cetaldehyde), polychloral, polypropylene
onaldehyde, polyacrolein, poly(2-
Formyl-△ ^Five -dihydropyran), poly(tran)
-1,2-cyclohexanedicarboxalde
hyde), poly(glutardialdehyde), poly(β
-methylglutardialdehyde), poly(β-ph)
enylglutardialdehyde), poly(dimethyl
ketene), polyacetone, poly(monobromoacetate)
), poly(7-oxa-bicyclo[2,2,
1] Heptane, poly(3-phenoxylene), poly
Poly(2,6-xylenol), Poly(ethyleneol)
oxide), poly(propylene oxide), poly(silica)
clopentene oxide), poly(cyclohexene)
oxide), poly(phenyl glycidyl ether)
), poly(1,2-di(epoxyethyl)ben)
), poly(3,3-bis(chloromethyl)o)
xetane), poly(tetrahydrofuran); polysulfides, polysulfones, e.g.
poly(thiocarboxyl fluoride), poly(ethylene)
dichloride-sodium tetrasulfide),
Poly(dichlorodiethyl ether-sodium di
sulfide), poly(dichlorodiethyl ether)
- Sodium tetrasulfide), poly(phenylene)
(ethylene sulfide), poly(ethylene sulfone),
poly(propylene sulfone), poly(1-butene)
poly(5-norbornene sulfone), poly(5-norbornenesulfone),
poly(styrene sulfone), poly(1-pentinsulphone)
poly(1-hexyl sulfone), poly(1-hexyl sulfone), poly
(1-heptinesulfone), poly(butadienesulfone)
poly (isoprene sulfone), poly (dimethyl)
(methylbutadiene sulfone), poly(1,5-hexyl)
sadiensulfone), poly(cis, cis-cyclo
-octadiene sulfone), poly(norbornadiene)
enesulfone); various addition polymers, e.g.
isocyanate), poly(ethylene diisocyanate)
), poly(trimethylene diisocyanate),
Poly(tetramethylene diisocyanate), poly
(5-iminohydantoin), poly(perfluoro
glutarodinitrile), poly(1-(perfluoro)
butyryl)aziridine); Formaldehyde resins, such as phenol
formaldehyde resin, melamine form
Aldehyde resin, urea-formaldehyde resin
ion, aniline-formaldehyde resin, p-to
Ruenesulfonamide-formaldehyde resin
polyesters, such as poly(11-oxyu
poly(hexamethylene saccharide), poly(hexamethylene saccharide)
), poly(hexamethylene sebacate), poly(hexamethylene sebacate),
Poly(hexadecamethylene sebacate), Poly(hexadecamethylene sebacate)
xamethylene α, α′-dibutyl sebacate),
Poly(octamethylene cis-hexahydrotere)
phthalate), poly(octamethylene trans
-hexahydroterephthalate), poly(hexahydroterephthalate),
methylene maleate), poly(hexamethylene
malate), poly(hexamethylene acetylene diamide)
carboxylate), poly(ethylene terephthalate)
), poly(p-phenylene isophthalate),
poly(4,4'-biphenylene isophthalate),
Poly(hexamethylene carbonate), poly(p
-phenylene carbonate), poly(m-phenylene carbonate), poly(m-phenylene carbonate),
poly(4,4'-isopropylene carbonate), poly(4,4'-isopropylene carbonate),
redene diphenylene carbonate), poly(4,
4′-(2-pentylene)diphenylene carbonate
), poly(1,2-bis(hydroxymethyl))
carborane-adipic acid), poly(allyl sulfonate)
poly(hydroquinone-aryloxy), poly(hydroquinone-aryloxy)
-phosphoryl dichloride), poly(hydroquino
(chloromethyl)phosphoryl dichloride),
Poly(hydroquinone-(N-dimethyl)phorphor)
Phosphoramidic acid dichloride
Polyamides, such as poly(isocyanate);
), poly(vinyl isocyanate), poly(butylene)
polyisocyanate), poly(3-aminopropio
(6-aminopropionic acid), poly(6-aminopropionic acid), poly(6-aminopropionic acid),
(11-aminoundecanoic acid), poly(hexamethylene)
poly(decamethylene adipamide), poly(decamethylene adipamide)
), poly(3,3′-(methylimino)bistrime)
(tyreneadipamide), poly(benzidine-isof
tarric acid), poly(pyromeric dianhydride)
- aromatized diamine), poly(1,6-hexyl
Sameethylene-bis(carboxyethyl)sulfui
), poly(1,6-hexamethylenediamine-
Benzene-1,3-bis-sulfonic acid chloride
), poly(trans-2,5-dimethyl-pipe
Radin-4,4'-sulfonyl-dibenzoylchloro
poly(bis(3-aminopropyl)), poly(bis(3-aminopropyl))
(enyl phosphine-adipic acid), poly(bis
(3-aminopropyl)phenyl phosphine-
terephthalic acid), poly(bis(3-aminopropylene)
methyl phosphine oxide-adipic acid),
Poly(bis(3-aminopropyl)n-octyl)
phosphine-adipic acid), poly(bis(3-a
Minopropyl) phenylphosphine oxide
dipic acid), poly(hexamethylene diamine-bi
(2-carboxyethylene)phenylphosphine
poly(hexamethylene diamine), poly(hexamethylene diamine)
Bis(p-carboxyphenyl)phenylphosph
poly(piperazine-bis(2-
carboxyethyl)-phenylphosphineoxy
polyurea, polyurethanes, e.g.
rear, poly(1,10-decamethylenediamine-
1,6-hexamethylene-bis-ethyl urethane
), poly(diphenylmethane-4,4'-diiso
cyanate-4,4'-diphenylmethane), poly
(Toluene-2,4-diisocyanate-N,
N'-bis(trimethylsilyl)-P,P'-diami
Nodiphenyl ether, polyurethane, polyurethane
Tanpoly (propylene oxide) basis
(basis); various linear condensation polymers, e.g.
ethylcarbodiimide), poly(diallylcarbodiimide), poly(diallylcarbodiimide),
diimide), poly(di-n-butylcarbodiimide)
), poly(methylisopropylcarbodiimide)
), poly(di-n-hexylcarbodiimide),
Poly(diphenylcarbodiimide), poly(4,
4′diphenylenemethane-carbodiimide), poly
(hexamethylene carbodiimide), poly(1,3
-xyylenecarbodiimide), poly(3-methane)
methyl-1,4-phenylenecarbodiimide), po
Li(2,2'-dimethyl-biphenylenecarbodiyl)
poly(2,2'-dimethoxy-biphenylene), poly(2,2'-dimethoxy-biphenylene)
(carbodiimide), poly(1,5-naphthylene)
carbodiimide), poly(adipyl dihydrazide)
-succinoyl chloride), poly(adipyldi
hydrazide-isophthaloyl chloride), poly
(Isophthalic dihydrazide-terephthaloyl
chloride), poly(2,5-dimethylbenzylene)
), poly(p-xylylene), poly(2,5-di
methylxylylene), poly(2,5-dimethoxy
-p-xylylene), poly(p-xylylidene),
Poly(α-cyano-m-xylylidine), poly
(α-cyano-p-xylylidine), poly(nitro
phenylene), poly(tetramethyl-p-phenylene)
dimethylene), poly(2,5-dihydroxy
-p-phenylene dimethylene), poly(4,4'-
oxydiphenylene dimethylene), poly(2,5
-dimethoxy-p-phenylene dimethylene); heterocyclic condensation polymers, such as poly(benzene);
zoimidazole), poly(alkylene-5,5'-
dibenzimidazole), poly(arylene-5,
5′-dibenzimidazole), poly(pyromeliz)
toimide), poly(benzoxazole), poly
(oxadiazole), poly(oxadiazole)
), poly(dithiazoles), poly(benzothiazo
), poly((1,4-xylylenyl)-2-mer
tilpiperazine), poly(quinoxaline), poly
(S-triazinyleneimide); natural polymers, modified natural polymers, e.g.
Rubber, cyclized rubber, hydrochloric acid rubber, chlorinated rubber, guttape
Luca, cellulose, methylcellulose, ethylcetate
Lulose, propylcellulose, butylcellulose
Allyl cellulose, benzyl cellulose, hydrogen
Droxyethylcellulose, carboxymethylcellulose
Lulose, cyanoethylcellulose, cellulose
triformate, cellulose acetate, cellulose
- triacetate, cellulose tripropione
Cellulose Tributyrate, Cellulose Tributyrate, Cellulose Tributyrate
Licaproate, cellulose tricarvanilate
, cellulose nitrate, cellulose trinitrate
rate, starch, amylose, amylose
Tate, amylose carbanilate, amylopec
Chin, alginic acid, chitin, glycogen, ara
Gum beer, gum tragacanth, heparin, pecti
lin, rosin, copal, sierracus, casein,
collagen (calf-skin), collagen
(ichthyocol), gelatin, peanut protein
soy protein, nuclear protein (calf
thymus), nuclear protein (sperm of
seaurchin), poly(sarcosine), sericin,
Lux, wool, zein, polyadenylic acid, deoxy
Silibonucleic acid, ribonucleic acid; polysiloxanes, such as polysiloxane,
Polydimethylsiloxane; organometallic polymers, such as poly(bis(i)
midazolate) - metal ()), poly(aluminum)
Mutriisopropylate-ethylenediamine);
and inorganic polymers, such as polymetaphosphates,
etc. By the method of the present invention, conjugated π-bonded compounds and field
In some cases, inorganic compounds may also be present on the inner wall surface of the polymerization vessel.
There is a risk of scale adhesion on the equipment and equipment attached to the polymerization reactor.
a certain part, i.e., a part that comes into contact with monomers during the polymerization process
(including areas that may come into contact)
Ru. The monomers shall come into contact with each other in the equipment attached to the polymerization reactor.
For example, stirring blades, stirring shafts, condensers,
Header, buttful, search coil, bolt, nut
There are Tsuto etc. There are no particular restrictions on the materials of the polymerization vessel mentioned above.
For example, stainless steel or glass lined
You can use the one you have prepared. These applications
The surface roughness (JIS B0106 standard)
Rmax) is preferably 10 μm or less, and
Furthermore, it is more preferably 5 μm or less. Apply scale adhesion prevention agent to the inner wall surface of the polymerization vessel, etc.
There are no particular restrictions on the method of applying the cloth, such as brush painting.
After filling the polymerization vessel with coating solution,
In addition to methods for extracting
No. 57-61001, No. 55-36288, Special Publication No. 56-
No. 501116, No. 56-501117, JP-A-59-11303
The automatic coating method described in et al. can be used. The method of the present invention involves the production of vinyl chloride in an aqueous medium.
homopolymerization of vinyl monomers and vinyl chloride monomers and others
It can be applied to copolymerization with vinyl monomers.
Wear. The form of polymerization can be suspension polymerization or emulsion polymerization.
stomach. Examples of vinyl monomers that can be subjected to polymerization include
For example, vinyl acetate, vinyl propionate, etc.
Nylester, acrylic acid, methacrylic acid or
are their esters or salts, maleic acid or
Fumaric acid and their esters or anhydrides
substances, such as butadiene, chloroprene, and isoprene.
Una diene monomer, as well as styrene and acrylic
Nitriles, vinylidene halides, vinyl ethers
Examples include. In these suspension polymerization and emulsion polymerization, polymerization is generally
As a catalyst, for example, t-butyl peroxy neo
decanate, di-2-ethylhexyl peroxy
Dicarbonate, 3,5,5-trimethylhexane
Noel peroxide, α-cumyl peroxine
Odecanoate, cumene hydroperoxy
cyclohexanone peroxide, t-butylene
peroxypivalate, di-2-ethoxyethyl
luperoxydicarbonate, benzoylpero
xide, lauroyl peroxide, 2,4-
Dichlorobenzoyl peroxide, diisopro
Pil peroxydicarbonate and acetyl cylindrical
Organic peroxides such as chlorhexyl peroxide
substance, α, α′-azobisisobutyronitrile, α,
α′-azobis-2,4-dimethylvaleronitrile
Azo catalysts such as, potassium persulfate, ammonium persulfate
A water-soluble peroxide such as umum is used. Ma
In addition, as a dispersant, for example, polyvinyl acetate may be used.
Saponified products, polyacrylic acid, vinyl acetate and anhydrous macerates
Copolymer of leic acid, hydroxypropylmethyl
Cellulose derivatives such as cellulose, and
natural and synthetic polymer compounds such as latin.
Suspending agent; sorbitan monolaurate, sorbitan
Nonionic emulsifiers such as triolate, lauryl
Sodium sulfonate, alkylbenzene sulfonate
Emulsifiers such as anionic emulsifiers such as sodium chloride
Other additives include calcium carbonate,
Fillers such as titanium oxide, tribasic lead sulfate, and
Calcium thearate, dibutyltin dilauret
and stabilizers such as dioctyltin mercaptide,
Rice wax, stearic acid, cetyl alcohol
lubricants such as silica, plasticizers such as DOP and DBP,
Chain transfer of chloroethylene, mercaptans, etc.
agents, PH regulators, etc. are added to the polymerization system. The present invention
According to the method, such catalysts, dispersants, additives
Regardless of the type of material, in any polymerization system.
Can effectively prevent scale adhesion
Ru. [Example] Hereinafter, the present invention will be specifically explained using examples.
However, the scope of the present invention is not limited to these.
do not have. Example 1 As shown in Table 1, for each experiment, the conjugated π bond
Dissolve or disperse the compound in a solvent and optionally
By adding the inorganic compounds and polymer compounds shown in the same table.
A coating solution was prepared. Inorganic compounds and polymers for each experiment
Compound ratio and conjugated π bond compound of coating solution
The concentrations are also shown in Table 1. Apply the coating liquid to an inner volume of 1000
Polished inner wall surface and stirring of stainless steel polymerization vessel
Apply it to the parts that come into contact with the monomer, such as a machine, and heat it for 20 minutes at 70℃.
After drying for a minute, it was thoroughly washed with water. Next, chloride is added to the polymerization vessel coated in this way.
Vinyl monomer 200Kg, ion exchange water 400Kg, partial separation
44g of polyvinyl alcohol, Hydroxypro
Pyl methylcellulose 56g, t-butyl peroxide
Add 60g of cineodecanate and heat at 52℃ for 7 hours.
It matched. After polymerization is complete, take out the polymer and place it in the polymerization vessel.
0.1m inside ³ /m ² ・Water flow rate of hr is as shown in Table 1.
I washed it with water. From the above application and preparation,
Repeat the steps up to washing with water after each batch.
The test was repeated up to 200 times. in the reaction mixture during the polymerization process in each experiment.
The chloride ion concentration is based on the raw material vinyl chloride monomer.
The content of methyl chloride and hydrochloric acid contained in
Temperature of the ion-exchanged water (in the range of 10 to 80℃),
and degree of vacuum after charging ion exchange water and suspension agent.
Controlled by changing (-750 to 100mmHg)
did. In addition, the methyl chloride used in each experiment
Various raw vinyl chloride monomers with different hydrochloric acid contents
The body consists of two types of vinyl chloride monomers, namely (1) methyl
Contains 40 to 50 ppm of luchloride and 0 to 2 ppm of hydrochloric acid.
(2) Methyl chloride 1000-3000ppm, hydrochloric acid 1
~10ppm in the range of 80:100~20:0
They were prepared by mixing in various weight ratios. After the polymerization of each batch is completed, the chlorine ion in the slurry is
The method for specifying on-concentration according to JIS K0102 (1974)
the average value and the highest value of those measurements.
The values and minimum values are shown in Table 1 for each experiment. As a result, specifically, for example, Experiment No. 16, 30
and 36, preparation must be done under the following conditions.
The chlorine ion concentration (average value)
It was controlled at 220ppm, 20ppm and 10ppm. Γ Experiment No. 16: Adjust the temperature to 27℃ as the preparation water.
Partially saponified poval, hydro
Xypropyl methylcellulose and t-butyl
After charging peroxyneodecanate, polymerization
Evacuate the inside of the chamber to a vacuum level of -150 mmHg, then
Contains 40ppm of chloride and 0.02ppm of hydrogen chloride.
A vinyl chloride monomer was charged. Γ Experiment No. 30: Adjust the temperature of the preparation water to 30℃ and
Except that the degree of vacuum after filling was changed to -500mmHg,
It was prepared in the same manner as Experiment No. 16. Γ Experiment No. 36: Adjust the temperature of the preparation water to 30℃ and
The actual results were as follows, except that the degree of vacuum after filling was changed to -600mmHg.
It was prepared in the same manner as Experiment No. 16. Also 10th, 30th, 50th, 100th, 150th and 200th
Visually check the scale adhesion after each batch.
Evaluate based on the following criteria, and then after the final batch
For scale adhesion amount (g/m ² ) was also measured.
Ta. The results are also shown in Table 1. A: No scale adhesion B: A few percent of sand-like scale adhesion C: Partially thin scale adhesion (adhesion rate 10%)
Degree) D: Partially thick scale adhesion (adhesion rate about 10%)
degree) E: Partially thin scale adhesion (adhesion rate 50%)
Degree) F: Partially thick scale adhesion (adhesion rate about 50%)
degree) G: Thick scale adhered to the entire surface H; Thick scale adhered to the entire surface In addition, the experiment numbers marked with * in Table 1 are comparative examples.
Show that something is true. In particular, experiments No. 1 and 2 were carried out in the polymerization vessel.
This is an example where no compound was applied to the wall surface.
Ru. In addition, the coating solutions of Experiment Nos. 33 and 34 were mixed with 100 parts of water.
Dissolve 1 part of soda sulfide, add 0.5 part of dye, 80
Prepared by heating at ℃ for 30 minutes.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Example 2 As shown in Table 2, for each experiment, a conjugated π bond compound was dissolved or dispersed in a solvent, and the inorganic compounds and polymer compounds shown in the table were added and applied as necessary. A liquid was prepared. Table 2 also shows the blending ratio of the inorganic compound and polymer compound in each experiment and the concentration of the conjugated π bond compound in the coating solution. Apply the coating solution to the polished inner wall surface of a stainless steel polymerization vessel with an internal volume of 1000 mm and the parts that come into contact with monomers such as the stirrer, and heat it at 70℃ for 20 minutes.
After drying for a minute, it was thoroughly washed with water. Next, 200 kg of vinyl chloride monomer, 400 kg of ion-exchanged water, 0.25 kg of hydroxypropyl methyl cellulose, 0.25 kg of sorbitan monolaurate, and α,α′-azobis-
Prepare 50g of 2,4-dimethylvaleronitrile,
Polymerization was carried out at 57°C for 10 hours. After the polymerization was completed, the polymer was taken out and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr as shown in Table 2. The above operations from coating and preparation to washing with water after polymerization were repeated for each batch, up to a maximum of 200 batches. Control of the chlorine ion concentration, evaluation of the state of steel adhesion, etc. were carried out in the same manner as in Example 1. The conditions and results are shown in Table 2. Note that the experiment numbers marked with * in Table 2 indicate comparative examples. In particular, Experiment Nos. 113 and 114 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Example 3 As shown in Table 3, for each experiment, the conjugated π bond compound was dissolved or dispersed in a solvent, and the inorganic compounds and polymer compounds shown in the table were added and applied as necessary. A liquid was prepared. Table 3 also shows the blending ratio of the inorganic compound and polymer compound in each experiment and the concentration of the conjugated π-bond compound in the coating solution. Apply the coating solution to the polished inner wall surface of a stainless steel polymerization vessel with an internal volume of 1000 mm, and the parts that come into contact with monomers such as the stirrer, and heat at 60℃ for 20 minutes.
After drying for a minute, it was thoroughly washed with water. Next, 160 kg of vinyl chloride monomer, 40 kg of vinyl acetate monomer, 400 kg of ion-exchanged water, 600 g of gelatin, and 2 kg of trichloride were added to the polymerization vessel coated in this way.
Kg, prepare 350g of lauroyl peroxide,
Polymerization was carried out at 70°C for 6 hours. After the polymerization was completed, the polymer was taken out and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr as shown in Table 3. The above operations from coating and preparation to washing with water after polymerization were repeated for each batch, up to a maximum of 200 batches. Control of the chlorine ion concentration, evaluation of the steel adhesion state, etc. were performed in the same manner as in Example 1. The conditions and results are shown in Table 3. Note that the experiment numbers marked with * in Table 3 indicate comparative examples. In particular, Experiment Nos. 167 and 168 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Example 4 As shown in Table 4, for each experiment, a conjugated π-bond compound was dissolved or dispersed in a solvent, and the inorganic compounds and polymer compounds shown in the table were added and applied as necessary. A liquid was prepared. Table 4 also shows the blending ratio of the inorganic compound and polymer compound in each experiment and the concentration of the conjugated π-bond compound in the coating solution. Apply the coating solution to the polished inner wall surface of a stainless steel polymerization vessel with an internal volume of 1000 mm, and the parts that come into contact with monomers such as the stirrer, and heat it at 80℃ for 10 minutes.
After drying for a minute, it was thoroughly washed with water. Next, 200 kg of vinyl chloride monomer, 400 kg of ion-exchanged water, 40 g of partially saponified polyvinyl alcohol, 60 g of hydroxypropyl methyl cellulose, and 80 g of di-2-ethylhexyl peroxydicarbonate were charged into the polymerization vessel coated in this manner.
Polymerization was carried out at ℃ for 7 hours. After the polymerization was completed, the polymer was taken out and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr as shown in Table 4. Application of the above,
The operations from preparation to washing with water after polymerization were repeated for each batch, up to 200 batches. Control of the chlorine ion concentration, evaluation of the steel adhesion state, etc. were performed in the same manner as in Example 1. In addition, the number of fibers of products obtained from the 10th, 30th, 50th, 100th, 150th, and 200th batches of polymers produced in each experiment was measured as follows. 100 parts by weight of polymer obtained by dehydrating and drying the slurry after polymerization, DOP50
part by weight, 1 part by weight of dibutyltin dilaurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of titanium oxide and 0.05 part by weight of carbon black.
After kneading with two rolls at 150℃ for 7 minutes, it was made into a sheet with a thickness of 0.2mm.
The number of fisheyes contained in the sheet per 100 ^cm2 was investigated. The conditions and results are shown in Table 4. Note that the experiment numbers marked with * in Table 4 indicate comparative examples. In particular, Experiment Nos. 207 and 208 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

【table】

【table】

【table】

【table】

【table】

[Table] [Effects of the Invention] As is clear from the above Examples and Comparative Examples, by controlling the chlorine ion concentration in the reaction mixture during the polymerization process to 100 ppm or less according to the present invention, the production of conjugated π-bonded compounds can be improved. It is possible to bring out the scale prevention effect reliably and strongly, and the adhesion of scale can be effectively prevented. Also,
When an inorganic compound is used in combination with a conjugated π bond compound, the scale prevention effect is improved, but in this case as well, the effect can be made effective and reliable by keeping the chlorine ion concentration in the reaction mixture at 100 ppm or less. Therefore, the labor and time for removing scale can be saved, the polymerization vessel can be used continuously, and the operating rate can be improved. Also,
The cooling capacity of the polymerization vessel can be maintained constant and there is no risk of scale being mixed into the product, improving the quality of the product polymer.

Claims (1)

[Scope of Claims] 1. A method in which a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a vinyl monomer copolymerizable with the monomer is subjected to suspension polymerization or emulsion polymerization in an aqueous medium. , at least one selected from aromatic compounds and heterocyclic compounds (excluding dyes and pigments) having 5 or more conjugated π bonds on the inner wall surface of the polymerization vessel and on the parts of the polymerization vessel accessory equipment that are in contact with the monomers. 1. A method for producing a vinyl chloride polymer, which comprises applying a seed and controlling the chlorine ion concentration in the reaction mixture to 100 ppm or less during the polymerization process. 2. In a method of carrying out suspension polymerization or emulsion polymerization of a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a vinyl monomer copolymerizable with the monomer in an aqueous medium, the inner wall surface of a polymerization vessel, and at least one member selected from (a) aromatic compounds and heterocyclic compounds (excluding dyes and pigments) having five or more conjugated π bonds in the part of the polymerization vessel accessory equipment that comes into contact with the monomer.
A method for producing a vinyl chloride polymer, comprising applying seeds and (b) at least one inorganic compound, and controlling the chlorine ion concentration in the reaction mixture during the polymerization process to 100 ppm or less.