CN102634015B - Synthesis method of poly(m-phenylenediamine) nanoparticles - Google Patents
Synthesis method of poly(m-phenylenediamine) nanoparticles Download PDFInfo
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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 synthetic method of poly m-phenylene diamine nanoparticle.
Background technology
Conjugate polymer material take poly aromatic amine as representative has become a focus of Recent study, and is widely used.Poly m-phenylene diamine is a kind of very important conjugated polymer wherein, and owing to having good environmental stability, the characteristics such as excellent redox characteristic and molecular structure are controlled have been subject to investigator's extensive concern, and have been applied in a plurality of fields.Reported the superior water treatmenting performance of poly m-phenylene diamine as 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 a synthetic key content of poly aromatic amine.Synthetic method commonly used has soft template method, catalysis method, self-assembly method etc.These class methods are based on chemical oxidising polymerisation and put forward, and can efficiently synthesize poly aromatic amine nano material.Simultaneously, these class methods generally adopt " fast mixed " technique, are about to initiator solution (as, persulphate etc.) and mix with the aromatic amine monomer solution rapidly, with this diauxic growth that suppresses polymkeric substance, realize nanometer beign preparation poly aromatic amine.But the shortcoming of this type of technique be the products therefrom productive rate lower than the products collection efficiency that progressively drips the initiator gained, and because add fast initiator may cause " implode " phenomenon in enormous quantities, be not suitable for large-scale industrial production.
Conventional chemical oxidative polymerization adopts and progressively drips initiator, can effectively overcome the deficiency that fast mixed technique faces.But this technique also makes it be difficult to prepare nano level polymkeric substance, because this technique is conducive to the diauxic growth of polymkeric substance, promotes the generation of coacervate.
In sum, a kind of method of poly m-phenylene diamine that develop 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 achieving the above object, the present invention is achieved through the following technical solutions:
The synthetic method of poly m-phenylene diamine nanoparticle, comprise the following steps, to get solution 1 in the water-soluble solution of water-soluble cupric compound, will get solution 2 in the water-soluble solution of mphenylenediamine monomer, will get solution 3 in the water-soluble solution of persulphate, solution 1 is added in solution 2,, dropwise add solution 3, after adding solution and abundant reaction thereafter, with product separation out
Namely get the poly m-phenylene diamine nanoparticle.
Described cupric compound comprises: copper sulfate, one or more in cupric chloride and cupric nitrate.
The mol ratio of described cupric compound and mphenylenediamine monomer is 1:80 ~ 1:10.
Described persulphate comprises one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
The mol ratio of described persulphate and mphenylenediamine monomer 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 concentration of aqueous solution of mphenylenediamine monomer is 0.02 ~ 0.5mol/L.
Described persulfate solution time for adding is 10-20min; After dripping, reacted 2 hours ~ 5 hours.
Above-mentioned temperature of reaction is between 0 ~ 50 ℃.
Initiator described in the inventive method is persulphate, and monomer is 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, be conducive to it in the application in the fields such as water treatment.Synthetic poly m-phenylene diamine product can reach 353.8mg/g to orange G adsorptive capacity in water body.
Description of drawings
Fig. 1 is the TEM figure of the poly m-phenylene diamine of embodiment 1 ~ 4 preparation.As seen from the figure, synthetic poly m-phenylene diamine size is uniform nanoparticle about 100 ~ 150 nanometers.A, B, C and D corresponding copper compound and mphenylenediamine monomer mole ratio respectively are 1:10,1:20, the polymkeric substance that 1:40 and 1:80 are synthetic.
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) as can be known, products therefrom is poly m-phenylene diamine.A, B, C and D corresponding copper compound and mphenylenediamine monomer mole ratio respectively are 1:10,1:20, the polymkeric substance that 1:40 and 1:80 are synthetic.
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, without obvious peak crystallization.This shows that synthetic poly m-phenylene diamine is amorphous polymer.A, B, C and D corresponding copper compound and mphenylenediamine monomer mole ratio respectively are 1:10,1:20, the polymkeric substance that 1:40 and 1:80 are synthetic.
Embodiment
The present invention is further described below in conjunction with embodiment, 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 distilled water to be stirred to dissolving, with monomer solution with constant temperature water bath to 30 ° C; Accurately weighing 0.48g copper chloride dihydrate also is dissolved in 5ml distilled water, and copper ion solution with constant temperature water bath to 30 ° C, then is added in mphenylenediamine solution 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 20ml distilled 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 reaction continues 3 hours in 30 ° of C.Reaction system solution becomes rapidly black by deep yellow brown, and generates with a large amount of solid particulates.After reaction finishes, remove reaction solution with G-3 sand core funnel suction filtration, then use the distilled water rinse, then use the deprotonation of 1:1 ammoniacal liquor, and wash away residual ammoniacal liquor with distilled water, then use the ethanol rinse, product drying 12 hours under vacuum condition.Products therefrom black solid powder is nano level poly m-phenylene diamine.
Embodiment 2 ~ 4
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, do not add copper compound in reaction process, the preparation poly m-phenylene diamine.Products therefrom is micron-sized black solid powder, and its size is 1 micron left and right.
In conjunction with the embodiments 1 ~ 4, visible cupric ion pre-reaction has remarkably influenced to the microscopic appearance of poly m-phenylene diamine product.Described synthetic method can directly obtain the poly m-phenylene diamine nanoparticle.
Reaction yield data corresponding in above each embodiment and comparative example 1 are as shown in table 1.
Table 1
| The comparative example 1 | Embodiment 1 | Embodiment 2 | 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 |
By data as seen, adopt the cupric ion pre-reaction also can make the synthetic product productive rate of conventional chemical oxidation style that by a relatively large margin lifting is 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 take absorption organic dye orange G as illustration further illustrates poly m-phenylene diamine nanoparticle of the present invention at the application potential of adsorbing domain.
Embodiment 6
The synthetic poly m-phenylene diamine nanoparticle of accurate weighing 3g embodiment 1, and add to the 1mol/L hydrochloric acid soln of 300ml, at room temperature stirred 6 hours.Thereafter suction filtration separates the poly m-phenylene diamine nanoparticle of acidifying, and uses the distilled water rinse, and drying is 12 hours in vacuum condition.Accurately the acidifying poly m-phenylene diamine nanoparticle of weighing 25mg, add to the 50ml orange G solution of 50ppm, and in 30 ° of C of water-bath, concussion is 2 hours.Suction filtration is caught filtrate, measures orange G concentration in filtrate.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.
Above-described embodiment only for the present invention will be described, does not consist of limitations on claims, 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 synthetic method of poly m-phenylene diamine nanoparticle, it is characterized in that, comprise the following steps, will get solution 1 in the water-soluble solution of water-soluble cupric compound, solution 2 will be got in the water-soluble solution of mphenylenediamine monomer, with getting solution 3 in the water-soluble solution of persulphate, solution 1 is added in solution 2, thereafter, dropwise add solution 3, after adding solution and abundant reaction, with product separation out, namely get the poly m-phenylene diamine nanoparticle.
2. the synthetic 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 cupric nitrate.
3. the synthetic method of poly m-phenylene diamine nanoparticle according to claim 1 and 2, is characterized in that, the mol ratio of described cupric compound and mphenylenediamine monomer is 1:80～1:10.
4. the synthetic 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 Sodium Persulfate.
5. the synthetic method of according to claim 1 or 4 described poly m-phenylene diamine nanoparticles, is characterized in that, the mol ratio of described persulphate and mphenylenediamine monomer is 0.5:1～3:1.
6. the synthetic 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 concentration of aqueous solution of mphenylenediamine monomer is 0.02～0.5mol/L.
7. the synthetic method of poly m-phenylene diamine nanoparticle according to claim 1, is characterized in that, described persulfate solution time for adding is 10-20min; After dripping, reacted 2 hours～5 hours.
8. the synthetic method of according to claim 1 or 7 described poly m-phenylene diamine nanoparticles, is characterized in that, temperature of reaction is at 30 ℃.
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| WO2015086676A1 (en) * | 2013-12-13 | 2015-06-18 | L'oreal | Method for dyeing keratinous substances starting from coloured oligomers and/or polymers resulting from meta-phenylenediamines, composition and dyeing agent |
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| CN102875804A (en) * | 2012-09-25 | 2013-01-16 | 中南大学 | Synthetic method of polymetaphenylene diamine nanoparticle |
| 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 |
| CN103694471B (en) * | 2013-12-25 | 2015-07-15 | 哈尔滨工业大学 | Method for preparing poly(o-phenylenediamine) nanomicelle by utilizing aqueous phase method |
| CN103785364B (en) * | 2014-02-27 | 2016-01-13 | 中南大学 | A kind of graphene-metal-poly-m-phenylenediamine composite gel and its rapid preparation and application method |
| CN104530425B (en) * | 2014-12-10 | 2017-05-03 | 中南大学 | Copper doped poly(m-phenylenediamine) nanoparticle and synthesis and application method thereof |
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