CN106632026A - Method for preparing flake zinc pyrithione in micro flow field reactor - Google Patents
Method for preparing flake zinc pyrithione in micro flow field reactor Download PDFInfo
- Publication number
- CN106632026A CN106632026A CN201610920598.5A CN201610920598A CN106632026A CN 106632026 A CN106632026 A CN 106632026A CN 201610920598 A CN201610920598 A CN 201610920598A CN 106632026 A CN106632026 A CN 106632026A
- Authority
- CN
- China
- Prior art keywords
- pyrithione
- zinc
- sodium
- oxides
- flow field
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a method for preparing flake zinc pyrithione in a micro flow field reactor. The method comprises the following steps: controlling the temperature to be 0-100 DEG C by utilizing the micro flow field reactor, inputting aqueous solution of pyrithione-N-oxide aqueous solution and zinc salt aqueous solution by using a charging pump, rapidly mixing and precipitating, performing solid-liquid separation, washing, drying, thereby obtaining the flake zinc pyrithione. The method has the advantages of simplicity in operation, stable process and the like.
Description
Technical field
The present invention relates to a kind of utilization micro flow field reactor continuously can control the method for preparing sheet ZPT.Belong to essence
Thin chemical field.
Background technology
ZPT, also known as ZPT, the prosperous zinc of pyrrole thiophene, 2-pyridinethiol-1-oxide zinc complex, abbreviation ZPT.
It is efficient, safe anti-dandruff and itching-relieving agent and bactericide generally acknowledged both at home and abroad, can effectively prevents the generation of pityrosporum furfur, it is sterilized
Antipruritic effect substantially, with low irritant, it is possible to decrease the metabolism of epidermis.The significant anti-dandruff effect of ZPT and good
Good security so as to be widely used in the anti-dandruff agent of shampoo, the Long-Time Service product not only can be anti-dandruff well,
And hair aging can be delayed, postpone white hair and alopecia is produced.Convention amount is harmless, and Long-Time Service has no side effect.
The synthesis of Zinc Pyrithione Zinc 2-pyridinethiol-1-oxide has many document reports, and Zheng Zhanmiao is reported with pyridine as raw material, and synthesis ZPT (is changed
The world, 1993,34 (9):437-440)；Wang Yuanxiang is reported with PA as Material synthesis ZPT (Jiangsu
Work, 1991, the 2nd phase)；American scholar Berstein et al. is disclosed with 2- halogen pyridines as raw material, multistep reaction, synthesizes pyrrole
(US2809971,2786847,3589999,3590035,3773770), the research of the above is concentrated mainly on used by ZPT sulphur zinc
On raw material sodium pyrithione-N- oxides, the granule-morphology and particle size research to Zinc Pyrithione Zinc 2-pyridinethiol-1-oxide product is very few.
Hu Yongqi et al. is studied the granule-morphology and particle size of pyridinium zinc with reaction-crystallization method, is investigated
Impact of the factors such as concentration, reaction temperature, time, pH value, ultrasound to reacting, synthesizes claw type, prismatic in four-hole boiling flask
Zinc Pyrithione Zinc 2-pyridinethiol-1-oxide (Hebei University of Science and Technology's journal, 2010,31 (1):44-47)；The reaction of pyrithione-N- oxides and zinc ion
It is a rapid precipitation reaction, in traditional batch reactor, settling rate is far longer than mixing rate, the pyrrole sulphur of generation
Zinc local concentration is supersaturated, and so as to nucleation rate in precipitation process and generating rate skewness, causes particle diameter distribution wider,
It is susceptible to agglomeration.
Zhang Lixiong et al. passes through micro passage reaction, by adjusting reaction temperature, mol ratio, sodium pyrithione and zinc sulfate
Quickly mix in microchannel, precipitate, but had to the irregular particle of small particle (CN103242228A)；Luo Peicheng et al.
By T-shaped mixing reactor coprecipitation prepared copper pyrithione (Chinese Journal of Inorganic Chemistry, 2013,29 (8):1738-
1744) Archie chemical industry discloses the synthetic method of aspherical or non-sheet shape pyrithione zinc：Sodium pyrithione is with zinc ion on surface
In the presence of surfactant composition, under 20-60 DEG C, the reaction condition of pH4-9, the pyrithione zinc of aspherical or non-sheet shape is generated
(CN1298874A).Simultaneously Archie chemical industry also discloses that one kind disposably prepares particle diameter in high pressure turbulent flow reactor<1 μm
The method of ZPT, under organic dispersing agent effect, by high pressure and turbulence effect short grained size is subtracted
(US6017936)。
Document disclosed above and patent, although all the granule-morphology and particle size of ZPT are studied,
But all do not prepare sheet ZPT.Micro flow field reactor, due to being limited by microscopic dimensions, more traditional interval is anti-
Device is answered, reactant can be contacted uniformly, the mixing of rapid microcosmic, greatly enhance mass-and heat-transfer process.Effectively limit
The size of particle, the distributing homogeneity that improve particle.Appropriate surfactant is added in raw material, can effectively be kept away
Exempt from the generation of product agglomeration.
The content of the invention
The purpose of the present invention is for the deficiencies in the prior art, there is provided a kind of new synthetic method of sheet ZPT.Tool
Body is to provide a kind of utilization micro flow field reactor and continuously can control the method for preparing sheet ZPT.
The scheme that its technical problem of solution of the invention is adopted is as follows：
A kind of continuous controllable method for preparing sheet ZPT, it is concretely comprised the following steps：Using micro flow field reactor, control
Temperature processed is input into pyrithione-N- oxides (XPT) aqueous solution, zinc salt solution with feed pump, quickly at 0-100 DEG C
Mixed precipitation, separation of solid and liquid, washing, drying obtain sheet ZPT.
The duct internal diameter of the micro flow field reactor is 0.01-10mm, preferred 0.2-1mm；Length is 0.01-2m, preferably
0.01-0.5m。
Described temperature is preferably controlled in 0-40 DEG C.
Described pyrithione-N- oxides are pyrithione lithium-N- oxides, sodium pyrithione-N- oxides, pyrrole
One or several mixtures in pyridine thioketones potassium-N- oxides, pyrithione ammonium-N- oxides；Pyrithione-the N-
The concentration of oxide water solution is 0.05～3mol/L, preferably 0.1～1.5mol/L.
Described zinc salt be zinc sulfate, zinc nitrate, zinc chloride, zinc perchlorate, zinc fluoroborate, zinc acetate in one kind or
It is several；The zinc salt solution concentration is 0.05～3mol/L, preferably 0.1～1.5mol/L.
Described zinc salt is 0.75-0.5, preferred 0.55-0.5 with the mol ratio of pyrithione-N- oxides charging.
Described pyrithione-N- oxide water solutions, both zinc salt solutions or one of them, add dispersion
Agent, dispersant concentration in the solution is 0.001～0.01mol/L.
Described dispersant is methyl alcohol, ethanol, isopropanol, n-butanol, polyether sulfonate (SOPA), dodecyl sodium sulfate
(SDS), neopelex (SDBS), dodecyl sodium sulfonate ammonium (ACS), ethoxylated dodecyl alcohol sodium sulfonate (AES),
Lauryl alcohol ichthyodin (ALES), poly- naphthalene formaldehyde sulfonate, polyacrylamide (Drewfloc2278/2270), succinate sulphur
Hydrochlorate, DBSA amine, Brij 35 sodium sulphate, triethanolamine lauryl sulfate, secondary alkyl sulphur
Sour sodium, fatty alcohol sodium isethionate, N- sodium lauroyl glutamates, amide groups APEO magnesium sulfate, laruyl alcohol polyoxy
Vinethene carboxylic acid sodium, 1-isobutyl-3,5-dimethylhexylphosphoric acid, 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 1-isobutyl-3,5-dimethylhexylphosphoric acid triethanolamine, α-thiazolinyl
One or several mixtures in sodium sulfonate, lauryl alcohol polyoxyethylene sulfosuccinate disodium.
Beneficial effects of the present invention are as follows：
1st, there is provided a kind of method for being continuously synthesizing to pyridinium zinc, the pyridinium zinc being synthesized is laminated structure.
2nd, by specific micro flow field reactor, the mass-and heat-transfer of course of reaction is enhanced.
3rd, surfactant has been used, the agglomeration of ZPT particle has effectively been avoided.
Description of the drawings：
Fig. 1 prepares ZPT schematic diagram for micro flow field reactor
The stereoscan photograph (SEM) of the ZPT that Fig. 2 embodiments 1 are prepared
The stereoscan photograph (SEM) of the ZPT that Fig. 3 embodiments 2 are prepared
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further described, but protection scope of the present invention not limited to this：
Embodiment 1
Under the conditions of 0 DEG C, with flow pump respectively by the sodium pyrithione-N- oxide water solutions (abbreviation of 0.2mol/L
SPT, includes 0.001mol/L dodecyl sodium sulfates), the zinc sulfate solution of 0.11mol/L by the flow velocity of 15ml/min,
Internal diameter is injected into for 500 μm, mixes duct in the micro flow field reactor of 10cm, reacted suspension is filtered, deionized water
Washing, until electrical conductivity is less than 600 μ s/cm, is dried, and obtains sheet ZPT.
Embodiment 2
Under the conditions of 25 DEG C, with flow pump the pyrithione potassium-N- oxide water solutions of 0.2mol/L (are included respectively
0.001mol/L neopelexes), the zinc sulfate solution of 0.11mol/L press the flow velocity of 15ml/min, be injected into
Internal diameter is 500 μm, mixes duct in the micro flow field reactor of 10cm, reacted suspension is filtered, deionized water washing,
Until electrical conductivity is less than 600 μ s/cm, it is dried, obtains sheet ZPT.
Embodiment 3
Under the conditions of 25 DEG C, with flow pump respectively by the sodium pyrithione-N- oxide water solutions (abbreviation of 0.2mol/L
SPT, includes 0.002mol/L polyether sulfonates (Darvan-1)), the zinc nitrate aqueous solution of 0.11mol/L is by 15ml/min's
Flow velocity, is injected into internal diameter for 500 μm, mixes duct in the micro flow field reactor of 10cm, reacted suspension is filtered, and is gone
Ion water washing, until electrical conductivity is less than 600 μ s/cm, is dried, and obtains sheet ZPT.
Embodiment 4
Under the conditions of 0 DEG C, with flow pump respectively by the sodium pyrithione-N- oxide water solutions (abbreviation of 0.2mol/L
SPT, includes 0.001mol/L dodecyl sodium sulfates), the zinc sulfate solution of 0.11mol/L by the flow velocity of 15ml/min,
Internal diameter is injected into for 400 μm, mixes duct in the micro flow field reactor of 15cm, reacted suspension is filtered, deionized water
Washing, until electrical conductivity is less than 600 μ s/cm, is dried, and obtains sheet ZPT.
Embodiment 5
Under the conditions of 0 DEG C, with flow pump the pyrithione lithium-N- oxide water solutions of 0.2mol/L (are included respectively
0.001mol/L dodecyl sodium sulfates), the solder(ing)acid of 0.105mol/L press the flow velocity of 15ml/min, be injected into
Footpath is 500 μm, mixes duct in the micro flow field reactor of 10cm, reacted suspension is filtered, deionized water washing, directly
600 μ s/cm are less than to electrical conductivity, are dried, obtain sheet ZPT.
Embodiment 6
Under the conditions of 40 DEG C, with flow pump respectively by the sodium pyrithione-N- oxide water solutions (abbreviation of 0.2mol/L
SPT, includes 0.001mol/L ethoxylated dodecyl alcohol carboxylic acid sodiums), the zinc sulfate solution of 0.105mol/L is by 15ml/
The flow velocity of min, is injected into internal diameter for 500 μm, in mixing the micro flow field reactor that duct is 10cm, reacted suspension, and mistake
Filter, deionized water washing, until electrical conductivity is less than 600 μ s/cm, is dried, and obtains sheet ZPT.
Embodiment 7
Under the conditions of 40 DEG C, with flow pump respectively by the sodium pyrithione-N- oxide water solutions (abbreviation of 0.2mol/L
SPT, includes 0.001mol/L 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite), the zinc acetate aqueous solution of 0.1mol/L is by the stream of 15ml/min
Speed, is injected into internal diameter for 500 μm, mixes duct in the micro flow field reactor of 10cm, reacted suspension is filtered, go from
Sub- water washing, until electrical conductivity is less than 600 μ s/cm, is dried, and obtains sheet ZPT.
Claims (8)
- It is 1. a kind of continuously to can control the method for preparing sheet ZPT, it is characterised in that：Using micro flow field reactor, control temperature Degree is input into pyrithione-N- oxide water solutions, zinc salt solution with feed pump, quick mixed precipitation at 0-100 DEG C, Separation of solid and liquid, washing, drying, obtain sheet ZPT.
- 2. method according to claim 1, it is characterised in that：The duct internal diameter of the micro flow field reactor is 0.01- 10mm, preferred 0.2-1mm；Length is 0.01-2m, preferred 0.01-0.5m.
- 3. method according to claim 1, it is characterised in that：Described temperature control is at 0-40 DEG C.
- 4. method according to claim 1, it is characterised in that：Described pyrithione-N- oxides are pyrithione In lithium-N- oxides, sodium pyrithione-N- oxides, pyrithione potassium-N- oxides, pyrithione ammonium-N- oxides one Plant or several mixtures；The concentration of the pyrithione-N- oxide water solutions be 0.05～3mol/L, preferably 0.1 ～1.5mol/L.
- 5. method according to claim 1, it is characterised in that：Described zinc salt is zinc sulfate, zinc nitrate, zinc chloride, height One or several in zinc chlorate, zinc fluoroborate, zinc acetate；The zinc salt solution concentration is 0.05～3mol/L, preferably 0.1～1.5mol/L.
- 6. method according to claim 1, it is characterised in that：Described zinc salt feeds with pyrithione-N- oxides Mol ratio be 0.75-0.5, preferred 0.55-0.5.
- 7. method according to claim 1, it is characterised in that：Described pyrithione-N- oxide water solutions, zinc salt Both the aqueous solution or one of them, add dispersant, dispersant concentration in the solution be 0.001～0.01mol/L.
- 8. method according to claim 7, it is characterised in that：Described dispersant is methyl alcohol, ethanol, isopropanol, positive fourth Alcohol, polyether sulfonate, dodecyl sodium sulfate, neopelex, dodecyl sodium sulfonate ammonium, ethoxylated dodecyl alcohol Sodium sulfonate, lauryl alcohol ichthyodin, poly- naphthalene formaldehyde sulfonate, polyacrylamide, sulphosuccinates, DBSA Amine, Brij 35 sodium sulphate, triethanolamine lauryl sulfate, SAS, fatty alcohol ethoxy sulphur Sour sodium, N- sodium lauroyl glutamates, amide groups APEO magnesium sulfate, ethoxylated dodecyl alcohol carboxylic acid sodium, dodecane Base phosphate, 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 1-isobutyl-3,5-dimethylhexylphosphoric acid triethanolamine, α-sodium olefin sulfonate, lauryl alcohol polyoxy second One or several mixtures in alkene sulfosuccinate disodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610920598.5A CN106632026B (en) | 2016-10-21 | 2016-10-21 | The method of micro flow field reactor preparation sheet zinc pyrithione |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610920598.5A CN106632026B (en) | 2016-10-21 | 2016-10-21 | The method of micro flow field reactor preparation sheet zinc pyrithione |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632026A true CN106632026A (en) | 2017-05-10 |
| CN106632026B CN106632026B (en) | 2019-07-12 |
Family
ID=58856154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610920598.5A Active CN106632026B (en) | 2016-10-21 | 2016-10-21 | The method of micro flow field reactor preparation sheet zinc pyrithione |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632026B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298874A (en) * | 1999-10-01 | 2001-06-13 | 阿奇化工公司 | Non-ball shaped and non-flake type mercapto pyridine oxide salts and preph. method therefor |
| CN103242228A (en) * | 2013-04-27 | 2013-08-14 | 南京工业大学 | Method for continuously and controllably preparing small-particle-size pyrithione salt particles |
| CN104557485A (en) * | 2015-01-13 | 2015-04-29 | 南京工业大学 | Application of micro-flow field reactor in Friedel-Crafts reaction |
| CN105859533A (en) * | 2016-04-26 | 2016-08-17 | 浙江中山化工集团股份有限公司 | Preparation method for 1-acetyl-1-chloro-cyclopropane |
-
2016
- 2016-10-21 CN CN201610920598.5A patent/CN106632026B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298874A (en) * | 1999-10-01 | 2001-06-13 | 阿奇化工公司 | Non-ball shaped and non-flake type mercapto pyridine oxide salts and preph. method therefor |
| CN103242228A (en) * | 2013-04-27 | 2013-08-14 | 南京工业大学 | Method for continuously and controllably preparing small-particle-size pyrithione salt particles |
| CN104557485A (en) * | 2015-01-13 | 2015-04-29 | 南京工业大学 | Application of micro-flow field reactor in Friedel-Crafts reaction |
| CN105859533A (en) * | 2016-04-26 | 2016-08-17 | 浙江中山化工集团股份有限公司 | Preparation method for 1-acetyl-1-chloro-cyclopropane |
Non-Patent Citations (1)
| Title |
|---|
| 汪敦佳 等: "N-氧化-2-巯基吡啶锌盐的合成", 《日用化学工业》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632026B (en) | 2019-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108941599B (en) | Continuous preparation method of nano-copper | |
| CN106563811B (en) | A kind of method that sea urchin shape Ag-ZnO nano-particles are continuously prepared using micro passage reaction | |
| CN103934468A (en) | Supercritical hydrothermal synthesis method of nano metal or nano metal oxide particles | |
| CN103737018A (en) | Method for continuous and rapid preparation of nano nickel by microfluidics technology | |
| CN104070177A (en) | Simple and novel preparation method for silver and gold nano-particles | |
| CN106082351A (en) | The preparation method of a kind of FeOOH nanometer sheet and product thereof | |
| CN101890506A (en) | Method for preparing nano-copper | |
| CN101367548A (en) | Method of preparing hydrophobic nano-titanium dioxide powder | |
| CN105234426A (en) | Preparation method of ultrafine nano silver | |
| CN103754953A (en) | Preparation method of multi-morphologynano-sized zinc ferrite | |
| CN103170644B (en) | Multistep liquid phase reduction prepares the technique of superfine cupper powder | |
| CN103273074B (en) | Process method of continuously producing ultra-fine nickel powder | |
| CN108247077A (en) | A kind of method that micro- reaction prepares copper powder | |
| CN103769601A (en) | Preparing method of triangular flaky nanometer silver particles | |
| CN108101121A (en) | A kind of resource recycling method of iron content waste sulfuric acid solution | |
| Ni et al. | Ultrasonic assisted synthesis, characterization and influence factors of monodispersed dumbbell-like YF3 nanostructures | |
| CN106632026B (en) | The method of micro flow field reactor preparation sheet zinc pyrithione | |
| CN101942679A (en) | Method for preparing, pretreating and dispersing superfine copper powder | |
| CN1559663A (en) | Preparation method of microwave auxiliary ion liquid body of nanometer micropowder | |
| CN104692455B (en) | Titanyl sulfate preparation method | |
| CN106186045A (en) | A kind of preparation method of flower shape zinc oxide nano-particle cluster | |
| CN103242228A (en) | Method for continuously and controllably preparing small-particle-size pyrithione salt particles | |
| CN105436513A (en) | Preparation method for spherical water-based nano-silver paste | |
| CN108946791A (en) | The preparation method of micron order scandium fluoride | |
| CN103613108B (en) | A kind of ammonia legal system is for the method for flame retardant of magnesium hydroxide |
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: 20180723 Address after: 404100 salt chemical industry park, Wanzhou economic and Technological Development Zone, Chongqing Applicant after: Chongqing Jobon Technology Co., Ltd. Address before: 211300 36 high road, Gaochun Development Zone, Nanjing, Jiangsu. Applicant before: Jiangsu Zhongbang Pharmaceutical Co.Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |