CN102634015A - Synthesis method of poly(m-phenylenediamine) nanoparticles - Google Patents
Synthesis method of poly(m-phenylenediamine) nanoparticles Download PDFInfo
- Publication number
- CN102634015A CN102634015A CN2012101370914A CN201210137091A CN102634015A CN 102634015 A CN102634015 A CN 102634015A CN 2012101370914 A CN2012101370914 A CN 2012101370914A CN 201210137091 A CN201210137091 A CN 201210137091A CN 102634015 A CN102634015 A CN 102634015A
- Authority
- CN
- China
- Prior art keywords
- solution
- poly
- phenylene diamine
- water
- compound
- 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
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a synthesis method of poly(m-phenylenediamine) nanoparticles, which comprises the following steps: dissolving cupric compound in a water solution to obtain a solution 1; dissolving m-phenylenediamine monomer in a water solution to obtain a solution 2; dissolving persulfate in a water solution to obtain a solution 3; adding the solution 1 into the solution 2; dropwisely adding the solution 3; and after finishing adding the solution and completely reacting, separating out the product, thereby obtaining the poly(m-phenylenediamine) nanoparticles. The method disclosed by the invention can efficiently prepare the nano poly(m-phenylenediamine); and the method is economical and effective, is simple to operate, and greatly enhances the yield.
Description
Technical field
The present invention relates to a kind of compound method of poly m-phenylene diamine nanoparticle.
Background technology
With poly aromatic amine is that the conjugate polymer material of representative has become a focus of Recent study, and is widely used.Poly m-phenylene diamine is wherein a kind of very important conjugated polymer, owing to have a good environmental stability, characteristics such as excellent redox characteristic and molecular structure are controlled have received investigator's extensive concern, and have been applied in a plurality of fields.Reported the superior water treatmenting performance of poly m-phenylene diamine like Li etc.Li upstart etc. also systematic study the application of the synthetic and water treatment of poly m-phenylene diamine.Sun etc. have found that poly m-phenylene diamine has application potential at bio-sensing.
Current, nanometer is key content of poly aromatic amine synthetic.Compound method commonly used has soft template method, catalysis method, self-assembly method etc.These class methods are based on that chemical oxidising polymerisation puts forward, and can efficiently synthesize poly aromatic amine nano material.Simultaneously, these class methods generally adopt " fast mix " technology, are about to initiator solution (like, persulphate etc.) and mix with the aromatic amine monomer solution apace, suppress the diauxic growth of polymkeric substance with this, and the realization nanometer prepares poly aromatic amine.Be lower than the product productive rate that progressively drips the initiator gained but the shortcoming of this type of technology is the products therefrom productive rate, and, be not suitable for large-scale industrial production because the initiator that adds fast in enormous quantities may cause " implode " phenomenon.
Conventional chemical oxidative polymerization adopts and progressively drips initiator, can effectively overcome the fast deficiency that technology faces of mixing.But this technology also makes it be difficult to prepare nano level polymkeric substance, because this technology helps the diauxic growth of polymkeric substance, promotes the generation of coacervate.
In sum, the method for poly m-phenylene diamine that develop a kind of economical and effective, has high yield and have a preparation nanostructure of general applicability is very important.
Summary of the invention
The objective of the invention is according to deficiency of the prior art, a kind of economical and effective is provided, has high yield and has the method for poly m-phenylene diamine of the preparation nanostructure of general applicability.
For realizing above-mentioned purpose, the present invention realizes through following technical scheme:
The compound method of poly m-phenylene diamine nanoparticle may further comprise the steps, with getting solution 1 in the water-soluble solution of water-soluble cupric compound; With getting solution 2 in the water-soluble solution of mphenylenediamine monomer,, solution 1 is added in the solution 2 getting solution 3 in the water-soluble solution of persulphate;, dropwise add solution 3, add solution and fully after the reaction thereafter; Product is separated
Promptly get the poly m-phenylene diamine nanoparticle.
Described cupric compound comprises: copper sulfate, one or more in cupric chloride and the cupric nitrate.
The monomeric mol ratio of described cupric compound and mphenylenediamine is 1:80 ~ 1:10.
Described persulphate comprises one or more in ammonium persulphate, Potassium Persulphate and the Sodium Persulfate.
The monomeric mol ratio of described persulphate and mphenylenediamine is 0.5:1 ~ 3:1.
The concentration of aqueous solution of described cupric compound is 0.07 ~ 0.7mol/L; Described persulfate solution concentration is between 0.05 ~ 0.5mol/L, and the monomeric concentration of aqueous solution of mphenylenediamine is 0.02 ~ 0.5mol/L.
The described persulfate solution dropping time is 10-20min; After dripping, reacted 2 h ~ 5 hours.
Above-mentioned temperature of reaction is between 0 ~ 50 ℃.
Initiator described in the inventive method is a persulphate, and monomer is a mphenylenediamine.
Beneficial effect of the present invention: but method high-efficiency production of nano level poly m-phenylene diamine of the present invention, method economical and effective, simple to operate, and productive rate has lifting by a relatively large margin.The solvability of polymkeric substance in water and organic solvent extremely a little less than, help its application in fields such as water treatments.Synthetic poly m-phenylene diamine product can reach 353.8mg/g to orange G adsorptive capacity in the water body.
Description of drawings
Fig. 1 is the TEM figure of the poly m-phenylene diamine of embodiment 1 ~ 4 preparation.Can know that by figure synthetic poly m-phenylene diamine size is uniform nanoparticle about 100 ~ 150 nanometers.A, B, corresponding respectively copper compound of C and D and mphenylenediamine monomer mole ratio are 1:10,1:20,1:40 and 1:80 synthetic polymkeric substance.
Fig. 2 is the infrared spectrum of the poly m-phenylene diamine of embodiment 1 ~ 4 preparation.Polymkeric substance is at 3600-3000cm
-1Two absorption peaks be amino stretching vibration; 1620 and 1500cm
-1Near the absorption corresponding quinoid structure of difference and the stretching vibration of benzene formula structure; At 1250cm
-1Near absorption peak is the C-N stretching vibration of benzene formula structure.The existing research of contrast (Zhang, L.; Et al.Langmuir 2011,27,10327) can know that products therefrom is a poly m-phenylene diamine.A, B, corresponding respectively copper compound of C and D and mphenylenediamine monomer mole ratio are 1:10,1:20,1:40 and 1:80 synthetic polymkeric substance.
Fig. 3 is the XRD figure of the poly m-phenylene diamine of embodiment 1 ~ 4 preparation.There is a wide diffuse peaks in polymkeric substance in 2 °=15 ~ 35 scopes, do not have tangible peak crystallization.This shows that the synthetic poly m-phenylene diamine is an amorphous polymer.A, B, corresponding respectively copper compound of C and D and mphenylenediamine monomer mole ratio are 1:10,1:20,1:40 and 1:80 synthetic polymkeric substance.
Embodiment
Below in conjunction with embodiment the present invention is further specified, and can not limit the present invention.
Embodiment 1
Accurate weighing 3g mphenylenediamine also is added in the round-bottomed flask of 250ml.Add 100ml zero(ppm) water and be stirred to dissolving, with monomer solution with constant temperature water bath to 30 ° C; Accurate weighing 0.48g copper chloride dihydrate also is dissolved in the 5ml zero(ppm) water, and copper ion solution with constant temperature water bath to 30 ° C, is added in the mphenylenediamine solution more fast, carries out pre-reaction, and solution is by the limpid colourless deep yellow brown that becomes rapidly.Accurately weighing 6g Sodium Persulfate is dissolved in the 20ml zero(ppm) water, and it is fully dissolved, and the Sodium Persulfate solution with water is bathed constant temperature to 30 ° C.In about 10min, the Sodium Persulfate oxygenant is progressively dropped in the solution of round-bottomed flask initiated polymerization.Above-mentioned being reflected among 30 ° of C continues 3 hours.Reaction system solution becomes black rapidly by deep yellow brown, and generates with a large amount of solid particulates.After reaction finishes, remove reaction solution, then use the zero(ppm) water rinse, use the deprotonation of 1:1 ammoniacal liquor again, and, use the ethanol rinse again, product drying 12 hours under vacuum condition with the residual ammoniacal liquor of zero(ppm) water flush away with G-3 sand core funnel suction filtration.Products therefrom black solid powder is nano level poly m-phenylene diamine.
Repeat embodiment 1, change the add-on of cupric chloride, making cupric chloride and mphenylenediamine monomer mole ratio is 1:20,1:40 and 1:80.Products therefrom black solid powder is nano level poly m-phenylene diamine.
The comparative example 1
According to the method for embodiment 1, in reaction process, do not add copper compound, the preparation poly m-phenylene diamine.Products therefrom is micron-sized black solid powder, and its size is about 1 micron.
In conjunction with embodiment 1 ~ 4, visible cupric ion pre-reaction has remarkably influenced to the microscopic appearance of poly m-phenylene diamine product.Described compound method can directly obtain the poly m-phenylene diamine nanoparticle.
More than among each embodiment and the comparative example 1 corresponding reaction yield data as shown in table 1.
Table 1
| The comparative example 1 | Embodiment 1 | |
Embodiment 3 | Embodiment 4 | |
| N (cupric chloride: mphenylenediamine) | ?0:1 | 1:10 | 1:20 | 1:40 | 1:80 |
| Productive rate/% | ?61.4 | 63.4 | 65.4 | 67.4 | 71.8 |
Visible by data, adopt the cupric ion pre-reaction also can make the synthetic product productive rate of conventional chemical oxidation style that lifting is by a relatively large margin arranged.
Embodiment 5
Repeat embodiment 1, change cupric chloride into copper sulfate or cupric nitrate.Products therefrom is nano level black solid powder.
Following embodiment will be that illustration further specifies the application potential of poly m-phenylene diamine nanoparticle of the present invention in adsorbing domain to be adsorbed with the organic dye orange G.
Embodiment 6
Accurate weighing 3g embodiment 1 synthetic poly m-phenylene diamine nanoparticle, and add to the 1mol/L hydrochloric acid soln of 300ml, at room temperature stirred 6 hours.Thereafter suction filtration separates acidifying poly m-phenylene diamine nanoparticle, and uses the zero(ppm) water rinse, and drying is 12 hours in vacuum condition.Accurately the acidifying poly m-phenylene diamine nanoparticle of weighing 25mg adds to the 50ml orange G solution of 50ppm, and concussion is 2 hours among 30 ° of C of water-bath.Suction filtration is caught filtrating, measures orange G concentration in the filtrating.This routine orange G decreasing ratio reaches 99.8%.
Embodiment 7
Repeat embodiment 6, change the orange G strength of solution into 80,120,240,360 and 480ppm.The decreasing ratio of orange G is respectively 99.9%, 98.8%, 71.3%, 50.1% and 36.6%; Its adsorptive capacity is respectively 161.3mg/g, 237.4mg/g, 342.2mg/g, 345.6mg/g and 353.8mg/g.
The foregoing description only is used for that the present invention will be described, does not constitute the restriction to claim, and other essence means that it may occur to persons skilled in the art that are all in claim scope of the present invention.
Claims (8)
1. the compound method of poly m-phenylene diamine nanoparticle is characterized in that, may further comprise the steps; With getting solution 1 in the water-soluble solution of water-soluble cupric compound, with getting solution 2 in the water-soluble solution of mphenylenediamine monomer, with getting solution 3 in the water-soluble solution of persulphate; Solution 1 is added in the solution 2, thereafter, dropwise adds solution 3; After adding solution and abundant reaction, product is separated, promptly got the poly m-phenylene diamine nanoparticle.
2. the compound method of poly m-phenylene diamine nanoparticle according to claim 1 is characterized in that, described cupric compound comprises: copper sulfate, one or more in cupric chloride and the cupric nitrate.
3. the compound method of poly m-phenylene diamine nanoparticle according to claim 1 and 2 is characterized in that, the monomeric mol ratio of described cupric compound and mphenylenediamine is 1:80 ~ 1:10.
4. the compound method of poly m-phenylene diamine nanoparticle according to claim 1 is characterized in that, described persulphate comprises one or more in ammonium persulphate, Potassium Persulphate and the Sodium Persulfate.
5. according to the compound method of claim 1 or 4 described poly m-phenylene diamine nanoparticles, it is characterized in that the monomeric mol ratio of described persulphate and mphenylenediamine is 0.5:1 ~ 3:1.
6. the compound method of poly m-phenylene diamine nanoparticle according to claim 1 is characterized in that, the concentration of aqueous solution of described cupric compound is 0.07 ~ 0.7mol/L; Described persulfate solution concentration is between 0.05 ~ 0.5mol/L, and the monomeric concentration of aqueous solution of mphenylenediamine is 0.02 ~ 0.5mol/L.
7. the compound method of poly m-phenylene diamine nanoparticle according to claim 1 is characterized in that, the described persulfate solution dropping time is 10-20min; After dripping, reacted 2 h ~ 5 hours.
8. according to the compound method of claim 1 or 7 described poly m-phenylene diamine nanoparticles, it is characterized in that temperature of reaction is between 0 ~ 50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210137091 CN102634015B (en) | 2012-05-04 | 2012-05-04 | Synthesis method of poly(m-phenylenediamine) nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210137091 CN102634015B (en) | 2012-05-04 | 2012-05-04 | Synthesis method of poly(m-phenylenediamine) nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102634015A true CN102634015A (en) | 2012-08-15 |
| CN102634015B CN102634015B (en) | 2013-06-19 |
Family
ID=46618599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210137091 Active CN102634015B (en) | 2012-05-04 | 2012-05-04 | Synthesis method of poly(m-phenylenediamine) nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102634015B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875804A (en) * | 2012-09-25 | 2013-01-16 | 中南大学 | Synthetic method of polymetaphenylene diamine nanoparticle |
| CN103694471A (en) * | 2013-12-25 | 2014-04-02 | 哈尔滨工业大学 | Method for preparing poly(o-phenylenediamine) nanomicelle by utilizing aqueous phase method |
| CN103788369A (en) * | 2013-12-25 | 2014-05-14 | 哈尔滨工业大学 | Method for preparing poly(o-phenylenediamine) fluorescent nano-belt by virtue of water-phase method |
| CN103785364A (en) * | 2014-02-27 | 2014-05-14 | 中南大学 | Graphene-metal-poly(m-phenylenediamine) plural gel as well as quick preparation and application methods thereof |
| CN104530425A (en) * | 2014-12-10 | 2015-04-22 | 中南大学 | Copper doped poly(m-phenylenediamine) nanoparticle and synthesis and application method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3014685B1 (en) * | 2013-12-13 | 2016-11-25 | Oreal | PROCESS FOR COLORING KERATINIC MATERIALS FROM OLIGOMERS AND / OR COLOR POLYMERS FROM METAPHENYLENEDIAMINES, COMPOSITION, AND COLORING AGENT |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2274488C1 (en) * | 2004-10-18 | 2006-04-20 | Открытое акционерное общество "Пигмент" | Method of preparing catalyst for synthesis of n-methylaniline |
| EP1862198A2 (en) * | 2006-06-01 | 2007-12-05 | Henkel Kommanditgesellschaft auf Aktien | Brightening and/or dyeing agent with urea derivatives |
| CN101475686A (en) * | 2009-01-14 | 2009-07-08 | 华东理工大学 | Method for preparing polyaniline derivative-metal complex |
| WO2010130977A1 (en) * | 2009-05-12 | 2010-11-18 | Wista Laboratories Ltd. | Methods of chemical synthesis of diaminophenothiazinium compounds involving the use of persulfate oxidants |
| CN102247818A (en) * | 2011-05-27 | 2011-11-23 | 中南大学 | Adsorbent for removing sulfate ions contained in water body as well as preparation and application thereof |
-
2012
- 2012-05-04 CN CN 201210137091 patent/CN102634015B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2274488C1 (en) * | 2004-10-18 | 2006-04-20 | Открытое акционерное общество "Пигмент" | Method of preparing catalyst for synthesis of n-methylaniline |
| EP1862198A2 (en) * | 2006-06-01 | 2007-12-05 | Henkel Kommanditgesellschaft auf Aktien | Brightening and/or dyeing agent with urea derivatives |
| CN101475686A (en) * | 2009-01-14 | 2009-07-08 | 华东理工大学 | Method for preparing polyaniline derivative-metal complex |
| WO2010130977A1 (en) * | 2009-05-12 | 2010-11-18 | Wista Laboratories Ltd. | Methods of chemical synthesis of diaminophenothiazinium compounds involving the use of persulfate oxidants |
| CN102247818A (en) * | 2011-05-27 | 2011-11-23 | 中南大学 | Adsorbent for removing sulfate ions contained in water body as well as preparation and application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875804A (en) * | 2012-09-25 | 2013-01-16 | 中南大学 | Synthetic method of polymetaphenylene diamine nanoparticle |
| CN103694471A (en) * | 2013-12-25 | 2014-04-02 | 哈尔滨工业大学 | Method for preparing poly(o-phenylenediamine) nanomicelle by utilizing aqueous phase method |
| CN103788369A (en) * | 2013-12-25 | 2014-05-14 | 哈尔滨工业大学 | Method for preparing poly(o-phenylenediamine) fluorescent nano-belt by virtue of water-phase method |
| CN103788369B (en) * | 2013-12-25 | 2016-02-17 | 哈尔滨工业大学 | Aqueous phase prepares the method for poly-o-phenylenediamine fluorescence nano band |
| CN103785364A (en) * | 2014-02-27 | 2014-05-14 | 中南大学 | Graphene-metal-poly(m-phenylenediamine) plural gel as well as quick preparation and application methods thereof |
| CN103785364B (en) * | 2014-02-27 | 2016-01-13 | 中南大学 | A kind of Graphene-metal-poly m-phenylene diamine plural gel and fast methods for making and using same |
| CN104530425A (en) * | 2014-12-10 | 2015-04-22 | 中南大学 | Copper doped poly(m-phenylenediamine) nanoparticle and synthesis and application method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102634015B (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102634015B (en) | Synthesis method of poly(m-phenylenediamine) nanoparticles | |
| Kumru et al. | Enhanced dispersibility of graphitic carbon nitride particles in aqueous and organic media via a one-pot grafting approach | |
| CN103447092B (en) | Graphene oxide supported Schiff base palladium catalyst as well as preparation method and application thereof | |
| Huang et al. | In-situ formation of silver nanoparticles stabilized by amphiphilic star-shaped copolymer and their catalytic application | |
| CN102391445B (en) | Polyacrylate polymer terminated cyclodextrin polyrotaxane and preparation method thereof | |
| US20120172566A1 (en) | Metal cyanide complex catalyst and its preparation and application | |
| CN108752542B (en) | Amphiphilic block polymer with hypoxia and pH dual responsiveness and using azo bond as connecting bond and preparation method thereof | |
| CN102432875B (en) | Aqueous polyaniline and preparation method thereof | |
| Zhao et al. | New core–shell hybrid material IR-MOF3@ COF-LZU1 for highly efficient visible-light photocatalyst degrading nitroaromatic explosives | |
| CN108409976A (en) | The topological organic polymer of solubility based on full conjugate rigid structure and quasi- phthalocyanine activated centre and preparation | |
| CN107828032B (en) | Hyperbranched starlike poly ion liquid of one kind and its preparation method and application | |
| CN100400568C (en) | Prepn of poly-alpha-amino anthraquinone | |
| CN105461935A (en) | Hyperbranched polymer containing imidazole, preparation method and method thereof for stabilizing nano-silver | |
| CN102875978A (en) | Preparation method of gold nanoparticle/poly (3, 4-dioxyethyl) thiophene composite material | |
| Dikmen et al. | Thiazolo [5, 4-d] thiazole based dye modified microspheres as metal nanoparticle reactor template and hybrid catalyst | |
| CN102093497B (en) | Method for preparing high-stereoregularity acrylonitrile resin | |
| CN102875804A (en) | Synthetic method of polymetaphenylene diamine nanoparticle | |
| CN103772702A (en) | Poly 1-naphthylamine nano hollow structure and its preparation method | |
| Xue et al. | Controlled fabrication of polypyrrole capsules and nanotubes in the presence of Rhodamine B | |
| CN113663710B (en) | Magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction | |
| Bayarkhuu et al. | Magnetic Conjugated Polymer Nanoparticles with Tunable Wettability for Versatile Photocatalysis under Visible Light | |
| CN103265700A (en) | Polyfluoroaniline nano-wire preparation method | |
| CN108654697B (en) | Preparation method of mesoporous polyion liquid- (metal) phthalocyanine nano material | |
| CN109400850B (en) | Preparation method of superfine silver nano-particle and microporous organic polymer composite material and product thereof | |
| CN102120786B (en) | Method for preparing highly syndiotactic polyacrylonitrile resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |