CN108047017A - A kind of preparation method of iso-violanthrone dichloride - Google Patents
A kind of preparation method of iso-violanthrone dichloride Download PDFInfo
- Publication number
- CN108047017A CN108047017A CN201711399557.7A CN201711399557A CN108047017A CN 108047017 A CN108047017 A CN 108047017A CN 201711399557 A CN201711399557 A CN 201711399557A CN 108047017 A CN108047017 A CN 108047017A
- Authority
- CN
- China
- Prior art keywords
- violanthrone
- iso
- preparation
- dichloride
- halogenated alkane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
- C09B3/70—Benzo-, naphtho-, and anthra-dianthrones
- C09B3/74—Preparation from starting materials already containing the benzo, naphtho-, or anthradianthrone nucleus
- C09B3/76—Preparation from starting materials already containing the benzo, naphtho-, or anthradianthrone nucleus by halogenation
Abstract
A kind of preparation method of iso-violanthrone dichloride belongs to the preparing technical field of dyestuff.The preparation method comprises the following steps：Iso-violanthrone, water and sulfuric acid are sequentially added in container and is ground, crushes, then halogenated alkane is added in into the mixture after grinding, then chlorinating agent is added under liquid level, then pH value is adjusted to neutrality, mixture after adjustment is warming up to reflux, halogenated alkane steam completely it is net after filtering, the filter cake after filtering is cleaned with hot water colourless to filtrate, then takes out filter cake and dry finally obtained product.Technical solution using the present invention avoids that recycling using a large amount of solvents caused by full solvent chlorination is difficult and the disadvantage of pollution, and the product of synthesis is the bright-coloured feux rouges purple reducing dye that market is welcome, more gorgeous, original powder intensity higher redder than commercially available product.
Description
Technical field
The invention belongs to the preparing technical fields of dyestuff, and in particular to a kind of preparation method of iso-violanthrone dichloride.
Background technology
Iso-violanthrone dichloride, molecular formula C24H14Cl2O2, CAS：1324-55-6, trade name are vat brilliant violet
2R.The product is mainly used for the stamp of cotton, fiber crops, the dyeing of viscose fiber and its fabric, it can also be used to process organic pigment and work
Plastic colorant.Vat Brilliant Violet 2R is particularly important product in reducing dye, and dye cotton has bright-coloured bluish violet, and affinity is high,
Level-dyeing property is general, fair to dead cotton covering power, and fastness is excellent, and resistance to Sai fastness is up to 6 grades.Other every fastness are at 4-5 grades.Often
It is and all fine to the affinity and level-dyeing property of silk for cotton dyeing and direct printing, it is deep to be favored by market.
Existing Vat Brilliant Violet 2R production method is：Using benzanthrone as raw material, obtained through bromination, vulcanization, cyclic condensation different
Violanthrone, then through chlorination up to product.It is filtered, crush, dry finished product.
Many patents describe iso-violanthrone and chlorination reaction are carried out in organic solvent.In nitrobenzene（GB:336775）,
Chlorobenzene or o-dichlorohenzene（US1,525,117）, glacial acetic acid（US5,554,774）Middle carry out chlorination reaction.But it is anti-to carry out chlorination
At once it can cause recycling difficult using a large amount of organic solvents, and noxious material can be brought, such as use chlorobenzene or o-dichlorohenzene
The carcinogens such as Polychlorinated biphenyls may be brought by making solvent.
The content of the invention
The technical issues of solution：Largely cause recycling difficult, use using organic solvent for existing in the prior art
Organic solvent can bring the technical problems such as noxious material, and the present invention provides a kind of preparation method of iso-violanthrone dichloride, system
The advantages that product intensity obtained is high, in bright-coloured feux rouges, while avoid largely using organic solvent, energy conservation and environmental protection.
Technical solution：A kind of preparation method of iso-violanthrone dichloride, the preparation method comprise the following steps：
Step 1, which sequentially adds iso-violanthrone, water and sulfuric acid in container, to be ground, is crushed to fineness as 10 ~ 30 μm, wherein
The mass ratio of iso-violanthrone, water and sulfuric acid is 1：（1.98~4.07）：（0~2.19）；
Step 2 adds in halogenated alkane into the mixture after grinding, and temperature is 30 ~ 65 DEG C, then from liquid level in 8 ~ 20 h
The mass ratio of lower addition chlorinating agent, 2 ~ 3 h of heat preservation after adding, halogenated alkane and iso-violanthrone is 1 ~ 2.6:1；
Reactant after step 3 keeps the temperature step 2 adjusts pH to neutrality；
Mixed solution after step 4 adjusts step 3 is warming up to reflux, and halogenated alkane steams net rear filtering completely；
Step 5 cleans the filter cake after filtering with hot water colourless to filtrate, then takes out filter cake and is dried.
Preferably, the mass fraction of sulfuric acid is 98% in the step 1.
Preferably, the mass ratio of iso-violanthrone, water and sulfuric acid is 1 in the step 1:2.13:2.19.
Preferably, halogenated alkane is dichloroethanes, trichloroethanes or tetrachloroethanes in the step 2.
Preferably, the mass ratio of halogenated alkane and iso-violanthrone is 2 in the step 2:1.
Preferably, chlorinating agent is chlorine or liquor natrii hypochloritis in the step 2, and when chlorinating agent is chlorine, chlorine
The mass ratio of gas and iso-violanthrone is 1.3 ~ 1.6:1, when chlorinating agent is liquor natrii hypochloritis, liquor natrii hypochloritis and isoviolanthrene
The mass ratio of ketone is 5 ~ 7:1.
Preferably, when chlorinating agent is liquor natrii hypochloritis in the step 2, effective chlorine contains in liquor natrii hypochloritis
It measures as 13wt.%.
Preferably, pH is adjusted to neutrality with soda ash or sodium hydroxide in the step 3.
Advantageous effect：1. the present invention is that iso-violanthrone is suspended in dilute sulphur by use using aqueous medium-solvent suspension chloridising
In aqueous acid.A small amount of halogenated alkane, example dichloroethanes, trichloroethanes, tetrachloroethanes are added in, sodium hypochlorite or chlorine make chlorination
Agent.Chlorination reaction is carried out, avoids and causes recycling difficult using a large amount of high boiling organic solvents, on a small quantity compared with low boiling point halogenated alkane
Solvent recovery is easy, and energy consumption is relatively low.
2. drying process is saved using filter cake.
3. the present invention makes iso-violanthrone particle be crushed to 10~30 μm, chlorination effect is bright using being crushed before chlorination
Aobvious, chlorination finished product coloured light is in bright-coloured feux rouges.
4. preparation method of the present invention avoids the problems such as bringing noxious material simultaneously, example uses chlorobenzene or o-dichlorohenzene
The carcinogens such as Polychlorinated biphenyls can be brought by making solvent.
5. more gorgeous, redder, original powder intensity higher is obtained using the present invention（240-255%）Product.
Description of the drawings
Fig. 1 dyes K/S graphs for Vat Brilliant Violet 2R.
Specific embodiment
New preparation process of the invention in relation to iso-violanthrone dichloride, product iso-violanthrone dichloride（VAT
violet 1）Structure is as follows：
Embodiment 1
By 41.45g iso-violanthrone wet cakes（Moisture content 45wt.%）, it rolls over 100% iso-violanthrone dry product, 22.8 g and is put into container,
Add 30 g of water, 98 wt.% sulfuric acid, 50 g, then ground, smashing fineness adds in 1,1,2- trichloroethanes, 45 g up to 20 μm.Object
Material temperature degree is at 30 ~ 35 DEG C, then in being uniformly added into 100 mL liquor natrii hypochloritises in 6 h under liquid level（The content of effective chlorine is
13 wt.%）, separately at 35 ~ 45 DEG C in being uniformly added into 80 mL liquor natrii hypochloritises in 6 h again（The content of effective chlorine is 13
wt.%）, then 2 h are kept the temperature, determination sample chlorinty reaches reaction end when being 13 ~ 14 wt.%, after terminal reaches, add in 3
Wt.% sodium hydroxide solutions adjust pH=7 ~ 7.5, are warming up to reflux, steam trichloroethanes, the mistake after trichloroethanes steams only completely
Filter, the filter cake after filtering is cleaned with hot water colourless to filtrate, is then taken out filter cake and is dried, obtains bright-coloured feux rouges product.
Embodiment 2
By 38 g iso-violanthrone wet cakes（40 wt.% of moisture content）, roll over 100% iso-violanthrone dry product, 22.8 g and be put into container, add water
Then 30 g, 98 wt.% sulfuric acid, 45.0 g, ground, smashing fineness add in 1,2- dichloroethanes, 40 g, material liter up to 30 μm
Temperature is uniformly added into 180 mL liquor natrii hypochloritises to 55 DEG C under liquid level in 16 h（The content of effective chlorine is 13 wt.%）, then
Continue to keep the temperature 2 h, add in 20 wt.% dilute sodas solution adjustment pH=7, be warming up to reflux, steam dichloroethanes, dichloroethanes steams
Filtering after net cleans with hot water the filter cake after filtering colourless to filtrate.It then takes out filter cake to be dried, obtains bright-coloured feux rouges
Product.
Embodiment 3
By 45.6g iso-violanthrone wet cakes（50 wt.% of moisture content）, roll over 100% iso-violanthrone dry product, 22.8 g and be put into container, add
Then 70 g of water, ground, smashing fineness add in 50 g of tetrachloroethanes up to 10 μm, material is warming up to 45~50 DEG C.Then in
35 g of chlorine is slowly introducing in 20 h in liquid level bottom, keeps the temperature 2 h, 20wt.% dilute sodas solution adjustment pH=7 is added in, is warming up to
Reflux, steams tetrachloroethanes, after tetrachloroethanes steam completely it is net after filter, by the filter cake after filtering with hot water clean to filtrate without
Color then takes out filter cake and is dried, and obtains bright-coloured feux rouges product.
Embodiment 4
The former dyestuff iso-violanthrone dichloride in 0.05 g embodiments 1,2 mL 5wt.% are added in 300 mL ceramics dye vats
Pull open powder solution, 1 mL ethyl alcohol add in 200mL reducing solutions, and the reducing solution is sodium hydrosulfite and the aqueous solution of NaOH, wherein insuring
Powder 0.85g, NaOH1.1g are warming up to 60 DEG C, reduce 15 minutes, add in 5g cotton fabrics, are dyed 45 minutes at 60 DEG C.By fabric washing
It washs, air oxidation, with 0.5wt.% soap lyes soap boiling 15 minutes, cleans, dry, obtain purple dye product.
For the purple dye product compared with Vat Brilliant Violet 2R standard items, intensity is the 102.6% of standard items, coloured light △ H=
0.215, DC（Bright-colored degree）=0.318, dyeing K/S curves are consistent with standard items.Illustrate to be made according to an embodiment of the invention
Dyestuff be Vat Brilliant Violet 2R, quality index complies with standard product, and more gorgeous than standard items, redder.
Claims (8)
1. a kind of preparation method of iso-violanthrone dichloride, which is characterized in that the preparation method comprises the following steps：
Step 1, which sequentially adds iso-violanthrone, water and sulfuric acid in container, to be ground, is crushed to fineness as 10 ~ 30 μm, wherein
The mass ratio of iso-violanthrone, water and sulfuric acid is 1：（1.98~4.07）：（0~2.19）；
Step 2 adds in halogenated alkane into the mixture after grinding, and temperature is 30 ~ 65 DEG C, then from liquid level in 8 ~ 20 h
The mass ratio of lower addition chlorinating agent, 2 ~ 3 h of heat preservation after adding, halogenated alkane and iso-violanthrone is 1 ~ 2.6:1；
Reactant after step 3 keeps the temperature step 2 adjusts pH to neutrality；
Mixed solution after step 4 adjusts step 3 is warming up to reflux, and halogenated alkane steams net rear filtering completely；
Step 5 cleans the filter cake after filtering with hot water colourless to filtrate, then takes out filter cake and is dried.
A kind of 2. preparation method of iso-violanthrone dichloride according to claim 1, which is characterized in that the step 1
The mass fraction of middle sulfuric acid is 98%.
A kind of 3. preparation method of iso-violanthrone dichloride according to claim 1, which is characterized in that the step 1
The mass ratio of middle iso-violanthrone, water and sulfuric acid is 1:2.13:2.19.
A kind of 4. preparation method of iso-violanthrone dichloride according to claim 1, which is characterized in that the step 2
Middle halogenated alkane is dichloroethanes, trichloroethanes or tetrachloroethanes.
A kind of 5. preparation method of iso-violanthrone dichloride according to claim 1, which is characterized in that the step 2
The mass ratio of middle halogenated alkane and iso-violanthrone is 2:1.
A kind of 6. preparation method of iso-violanthrone dichloride according to claim 1, which is characterized in that the step 2
Middle chlorinating agent is chlorine or liquor natrii hypochloritis, when chlorinating agent is chlorine, the mass ratio of chlorine and iso-violanthrone for 1.3 ~
1.6:1, when chlorinating agent is liquor natrii hypochloritis, the mass ratio of liquor natrii hypochloritis and iso-violanthrone is 5 ~ 7:1.
A kind of 7. preparation method of iso-violanthrone dichloride according to claim 6, which is characterized in that the step 2
When middle chlorinating agent is liquor natrii hypochloritis, the content of effective chlorine is 13wt.% in liquor natrii hypochloritis.
A kind of 8. preparation method of iso-violanthrone dichloride according to claim 1, which is characterized in that the step 3
It is middle to adjust pH to neutrality with soda ash or sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399557.7A CN108047017B (en) | 2017-12-22 | 2017-12-22 | Preparation method of isoviolanthrone dichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399557.7A CN108047017B (en) | 2017-12-22 | 2017-12-22 | Preparation method of isoviolanthrone dichloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108047017A true CN108047017A (en) | 2018-05-18 |
| CN108047017B CN108047017B (en) | 2021-04-20 |
Family
ID=62130747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711399557.7A Active CN108047017B (en) | 2017-12-22 | 2017-12-22 | Preparation method of isoviolanthrone dichloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108047017B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778789A (en) * | 2021-01-06 | 2021-05-11 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| CN114213226A (en) * | 2021-12-29 | 2022-03-22 | 赤峰市恒祥化工有限公司 | Preparation method of isoviolanthrone |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2013790A (en) * | 1931-10-03 | 1935-09-10 | Du Pont | Bromination of pyranthrone |
| US2831871A (en) * | 1956-10-18 | 1958-04-22 | Southern Dyestuff Corp | Process for producing direct dyeing vat black dyestuff |
| BE665732A (en) * | 1964-08-17 | 1965-10-18 | ||
| RO82776A2 (en) * | 1981-08-11 | 1983-11-01 | Combinatul Chimic,Ro | PROCESS FOR OBTAINING BZ-3-BZ-3'-DICHLORIZODIBENZANTRONE |
| DE4014172A1 (en) * | 1990-05-02 | 1991-11-07 | Basf Ag | METHOD FOR HALOGENING POLYCYCLIC COMPOUNDS |
| CN1111663A (en) * | 1994-02-12 | 1995-11-15 | Basf公司 | The preparation of chlorinated violanthrones or isoviolanthrones |
| CN105541580A (en) * | 2016-02-19 | 2016-05-04 | 国药集团化学试剂有限公司 | Method for preparing vat golden yellow RK through oxidative bromination |
-
2017
- 2017-12-22 CN CN201711399557.7A patent/CN108047017B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2013790A (en) * | 1931-10-03 | 1935-09-10 | Du Pont | Bromination of pyranthrone |
| US2831871A (en) * | 1956-10-18 | 1958-04-22 | Southern Dyestuff Corp | Process for producing direct dyeing vat black dyestuff |
| BE665732A (en) * | 1964-08-17 | 1965-10-18 | ||
| RO82776A2 (en) * | 1981-08-11 | 1983-11-01 | Combinatul Chimic,Ro | PROCESS FOR OBTAINING BZ-3-BZ-3'-DICHLORIZODIBENZANTRONE |
| DE4014172A1 (en) * | 1990-05-02 | 1991-11-07 | Basf Ag | METHOD FOR HALOGENING POLYCYCLIC COMPOUNDS |
| CN1111663A (en) * | 1994-02-12 | 1995-11-15 | Basf公司 | The preparation of chlorinated violanthrones or isoviolanthrones |
| CN105541580A (en) * | 2016-02-19 | 2016-05-04 | 国药集团化学试剂有限公司 | Method for preparing vat golden yellow RK through oxidative bromination |
Non-Patent Citations (1)
| Title |
|---|
| 穆振义: "稠环酮(还原染料类)颜料-～ 蒽醌类、靛族系及芘酮(还原染料类)颜料", 《上海染料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778789A (en) * | 2021-01-06 | 2021-05-11 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| CN112778789B (en) * | 2021-01-06 | 2021-11-12 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| WO2022147994A1 (en) * | 2021-01-06 | 2022-07-14 | 贺潇寒 | Method for chlorinating indanthrone blue, violanthrone or isoviolanthrone |
| EP4053220A4 (en) * | 2021-01-06 | 2022-12-14 | He, Xiaohan | Method for chlorinating indanthrone blue, violanthrone or isoviolanthrone |
| US11939475B2 (en) | 2021-01-06 | 2024-03-26 | Xiaohan HE | Method for chlorinating blue anthrone, violanthrone or isoviolantrone |
| CN114213226A (en) * | 2021-12-29 | 2022-03-22 | 赤峰市恒祥化工有限公司 | Preparation method of isoviolanthrone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108047017B (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047017A (en) | A kind of preparation method of iso-violanthrone dichloride | |
| KR20160135789A (en) | Biocompatible and biodegradable natural disperse dyes for dyeing polyester fabrics | |
| CN102618084B (en) | Heterocyclic ring blue disperse dye and synthesizing method and application thereof | |
| CN104371347B (en) | A kind of Vat Blue RSN preparation method | |
| CN101724289B (en) | Method for preparing Vatdirectblack DB | |
| CN100590150C (en) | Synthetic process of vat blue RSN | |
| CN105086498A (en) | Heterocycle alkaline-washable carboxylic acid ethyl ester type disperse dye and preparation method thereof | |
| CN102660130B (en) | Method for producing reductive direct black BCN raw dye | |
| Ali et al. | Green strategy for dyeing wool fibers by madder natural dye | |
| Li et al. | Grafting printing of cellulose fabric with the reactive disperse dyes containing N-substituted 3-chloro-2-hydroxypropyl group | |
| CN111749029B (en) | Ink suitable for polyester cotton printing and dyeing and preparation method thereof | |
| CN107337662B (en) | Water-soluble bi-fluorenyl quinoid thiophene derivative, preparation method and dyeing application thereof | |
| US20180258287A1 (en) | Biocompatible and biodegradable natural disperse dyes for dyeing polyester fabrics | |
| CN106398273B (en) | The preparation method of phthalocyanine blue | |
| CN104893340A (en) | Novel technology for dispersing turquoise blue GL | |
| CN107904985A (en) | A kind of preparation method of the stamp liquid containing purple potato pigment | |
| CN107916016A (en) | A kind of preparation method of vat yellow 3RT | |
| KR20180021022A (en) | Brilliant blue azo dye and method of preparation thereof, and its use | |
| CN109486239B (en) | Disperse dye composition and preparation method and application thereof | |
| CN101676334A (en) | Orange monoazo pigment | |
| KR101710419B1 (en) | Natural dyeing method of woven pile fabric using natural indigo | |
| US619883A (en) | Administrator of | |
| JPS5828300B2 (en) | Shinkinazis azoganryonoseihou | |
| CN109487576A (en) | One kind exempting from reduction cleaning liquid nanometer dispersion mill base | |
| JPS6047308B2 (en) | Monoazo compounds, their preparation and use as colorants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210325 Address after: 221011 west head of Jiali Road, Xuzhou Industrial Park, Jiangsu Province Applicant after: Jiangsu Jiali Fine Chemical Co.,Ltd. Address before: 221011 west head of Jiali Road, industrial park, Jiawang District, Xuzhou City, Jiangsu Province Applicant before: XUZHOU KAIDA FINE CHEMICAL Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |