CN100395278C - Prepn process of poly-1,8-naphthalenediamine - Google Patents
Prepn process of poly-1,8-naphthalenediamine Download PDFInfo
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- CN100395278C CN100395278C CNB2005100236284A CN200510023628A CN100395278C CN 100395278 C CN100395278 C CN 100395278C CN B2005100236284 A CNB2005100236284 A CN B2005100236284A CN 200510023628 A CN200510023628 A CN 200510023628A CN 100395278 C CN100395278 C CN 100395278C
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- naphthylenediamine
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- homopolymers
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Abstract
The present invention belongs to the field of preparing 1, 8-naphthylenediamine homopolymers. The method for preparing poly-1, 8-naphthylenediamine homopolymers of the present invention has the chemical oxidating preparing procedures that 1, 8-naphthylenediamine is dissolved in an organic solvent for full dissolution, and then the water solution of oxidant is filled in the solution of monomers and processed after complete reaction. The present invention uses water or the organic solvent as a polymerization medium for preparing 1, 8-naphthylenediamine homopolymers via a simple and easy chemical oxidating solution polymerizing method, yield is high, and the highest yield can reach 98.0%. The scale of yield can be large, magnifying experiments can be conveniently carried out, and rich material basis is provided for the functional study of developing naphthylenediamine homopolymers. Poly-1, 8-naphthylenediamine polymerized by chemical oxidation can have structures and molecular quantities which are different from electrically polymerized products, and thus, the poly-1, 8-naphthylenediamine can have different functions and developing space. The present invention provides a new economic and effective way for preparing 1, 8-naphthylenediamine homopolymers.
Description
Technical field
The invention belongs to 1, the preparation method field of 8-naphthylene diamine homopolymer.
Background technology
Amido in the naphthylene diamine polymer architecture and imido grpup can be given the multifunctionality of naphthylene diamine polymkeric substance, the most a bit are to be the metal ion such as the Ag of ppm level to volumetric molar concentration wherein
+, Hg
2+, Cu
2+, Pb
2+, VO
2+Deng susceptibility.Because of containing a large amount of free aminos in its structure, it and imido grpup are in the consecutive position, can form stable complex compound or redox reaction takes place with heavy metal ion generation complex reaction metal ion is reduced into the electric neutrality metal, thereby realize functions such as the enrichment of metal ion and detections.And the preparation of naphthylene diamine polymkeric substance mostly is electrochemical method greatly, yet there are no the report of synthetic poly-1,8 naphthylene diamine of chemical oxidative polymerization at home and abroad.The synthetic method of poly-1,8 naphthylene diamine is confined to the electrochemically oxidative polymerization method always, and its reacting environment is near electrode surface, the polymkeric substance that generates is film forming on electrode surface generally, obviously, its output area is restricted by the electrode area size, can't obtain number of polymers.Therefore can develop out a kind of new economical and effective, have good yield and have a preparation of general applicability poly-1, the method for 8-naphthylene diamine is very important.
Summary of the invention
Purpose of the present invention just provides a kind of economical and effective, have the poly-1 of good yield, the chemical oxidation preparation method of 8-naphthylene diamine.
The present invention adopts the mixing solutions of organic solvent or organic solvent and water as polymerisation medium, by simple chemical oxidation solution polymerization process, and preparation naphthylene diamine homopolymer.
Of the present invention poly-1, the chemical oxidation preparation method step of 8-naphthylene diamine is as follows: with 1, the 8-naphthylene diamine is dissolved in it is fully dissolved, and the aqueous solution with oxygenant adds in the above-mentioned monomer solution then, reacts completely to handle to get final product.
Organic solvent of the present invention can be methyl alcohol, ethanol, acetonitrile or propionitrile etc.
Oxygenant of the present invention is the blend of following one or more: ammonium persulphate ((NH
4)
2S
2O
8), Potassium Persulphate (K
2S
2O
8), potassium bichromate (K
2Cr
2O
7), iron trichloride (FeCl
3).
The mol ratio of monomer of the present invention and oxygenant is preferably 0.5: 1～and 2: 1.
Temperature of reaction is best at 10～30 ℃ among the present invention, and it is best that the reaction times generally is controlled at 6～10h.
By prepared poly-1 of the present invention, 8-naphthylene diamine (P18DAN) infared spectrum (see figure 1) is at 3100～3600cm
-1The place broad absorption band, 3100-3600cm have relatively occurred with monomeric infared spectrum
-1Broad absorption band be N-H stretching vibration characteristic absorbance, the 1260cm that causes by the C-N stretching vibration in the polymkeric substance
-1The appearance of place's absorption peak illustrates-existence of C-NH-C-structure, and the generation of polymer P 18DAN has been described.
Beneficial effect of the present invention: the present invention adopts water or organic solvent as polymerisation medium, and the chemical oxidation solution polymerization process by simple has prepared 1,8-naphthylene diamine homopolymer, and the productive rate height reaches as high as 98.0%.Production scale also can be very big, can carry out amplification test easily, for the functional study of opening up the naphthylene diamine polymkeric substance provides abundant basic substance.And poly-1,8 naphthylene diamine of chemical oxidising polymerisation may have structure and the molecular weight different with the electropolymerization product, and then will give that it is different functional and expand space.This invention is 1, and the preparation of 8-naphthylene diamine homopolymer provides cost-effective new way.
Description of drawings
Fig. 1 is 1, the FT-IR collection of illustrative plates of the P18DAN that 8-naphthylene diamine monomer and chemical oxidising polymerisation obtain.
Embodiment
Embodiment 1:
Accurately take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Took by weighing 1.141g (5mmol) ammonium persulphate than 1: 1 by the oxygenant monomer and be dissolved in the 50mL distilled water, place it in 20 ℃ of waters bath with thermostatic control and be preheated to temperature of reaction.The speed of 20 ℃ of oxidizing agent solutions about with 1/3s is added drop-wise in the monomer solution.Dropwise the back and continue reaction 6h.Reaction finishes, and filters, and is colourless to filtrate with the distilled water wash head product, the polymkeric substance filter cake transferred to continue agitator treating in the beaker and spend the night again, and obtains the soft black powder shaped polymer of quality after the suction filtration drying, output 0.672g, productive rate 85.0%.
Embodiment 2:
Accurately take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Took by weighing 0.5705g (2.5mmol) ammonium persulphate than 0.5: 1 by the oxygenant monomer and be dissolved in the 50mL distilled water, place it in 20 ℃ of waters bath with thermostatic control and be preheated to temperature of reaction.20 ℃ of oxidizing agent solutions are added drop-wise in the monomer solution.Dropwise the back and continue reaction 6h.Reaction finishes, and filters, and is colourless to filtrate with the distilled water wash head product, the polymkeric substance filter cake transferred to continue agitator treating in the beaker and spend the night again, and obtains the soft black powder shaped polymer of quality after the suction filtration drying, output 0.245g, productive rate 31.0%.
Embodiment 3:
Accurately take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Took by weighing 2.282g (10mmol) ammonium persulphate than 2: 1 by the oxygenant monomer and be dissolved in the 50mL distilled water, place it in 20 ℃ of waters bath with thermostatic control and be preheated to temperature of reaction.20 ℃ of oxidizing agent solutions are added drop-wise in the monomer solution.Dropwise the back and continue reaction 6h.Reaction finishes, and filters, and is colourless to filtrate with the distilled water wash head product, the polymkeric substance filter cake transferred to continue agitator treating in the beaker and spend the night again, and obtains the soft black powder shaped polymer of quality after the suction filtration drying, output 0.775g, productive rate 98.0%.
Embodiment 4:
Accurately take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Took by weighing 1.141g (5mmol) ammonium persulphate than 1: 1 by the oxygenant monomer and be dissolved in the 50mL distilled water, place it in 30 ℃ of waters bath with thermostatic control and be preheated to temperature of reaction.Under 30 ℃ oxidizing agent solution is added drop-wise in the monomer solution.Dropwise the back and continue reaction 6h.Reaction finishes, and filters, and is colourless to filtrate with the distilled water wash head product, the polymkeric substance filter cake transferred to continue agitator treating in the beaker and spend the night again, and obtains the soft black powder shaped polymer of quality after the suction filtration drying, output 0.679g, productive rate 85.8%.
Embodiment 5:
Accurately take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Took by weighing 1.141g (5mmol) ammonium persulphate than 1: 1 by the oxygenant monomer and be dissolved in the 50mL distilled water, place it in (about 10 ℃) in the room-temperature water bath.Oxidizing agent solution is added drop-wise in the monomer solution.Dropwise the back and continue reaction 6h.Reaction finishes, and filters, and is colourless to filtrate with the distilled water wash head product, the polymkeric substance filter cake transferred to continue agitator treating in the beaker and spend the night again, and obtains the soft black powder shaped polymer of quality after the suction filtration drying, output 0.620g, productive rate 78.4%.
Embodiment 6:
Accurately take by weighing 1.582g (10mmol) 1,8 naphthylene diamine and be dissolved in the 100mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Taking by weighing 2.282g (10mmol) ammonium persulphate than 1: 1 by the oxygenant monomer is dissolved in the 100mL distilled water.Place it in 20 ℃ of waters bath with thermostatic control and be preheated to temperature of reaction.Under 20 ℃ oxidizing agent solution is added drop-wise in the monomer solution.Dropwise the back and continue reaction 10h.Reaction finishes, and filters, and is colourless to filtrate with the distilled water wash head product, the polymkeric substance filter cake transferred to continue agitator treating in the beaker and spend the night again, and obtains the soft black powder shaped polymer of quality after the suction filtration drying, output 1.367g, productive rate 86.4%.
Embodiment 7:
Accurately take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Taking by weighing 1.141g (5mmol) ammonium persulphate than 1: 1 by the oxygenant monomer is dissolved in the 50mL distilled water.They all are placed in 20 ℃ of waters bath with thermostatic control are preheated to temperature of reaction, join in the monomer solution oxidizing agent solution is disposable, it is mixed, reaction 10h.Reaction finishes, and filters, and is colourless to filtrate with the distilled water wash head product, the polymkeric substance filter cake transferred to continue agitator treating in the beaker and spend the night again, and obtains the soft black powder shaped polymer of quality after the suction filtration drying, output 0.544g, productive rate 68.8%.
Embodiment 8:
Take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Take by weighing 0.8125g (5mmol) iron trichloride at 1: 1 by oxygen digital ratio and be dissolved in the 50mL distilled water, place it in 20 ℃ of waters bath with thermostatic control and be preheated to temperature of reaction.Under 20 ℃ oxidizing agent solution is added drop-wise in the monomer solution.Dropwise the back and continue reaction 6h, reaction finishes, and filters, colourless with the distilled water wash head product to filtrate, again the polymkeric substance filter cake is transferred in the beaker and to be continued agitator treating and spend the night, obtain scleroid black powder shaped polymer after the suction filtration drying, output 0.7689g, productive rate 97.2%.
Embodiment 9:
Take by weighing 0.791g (5mmol) 1,8 naphthylene diamine and be dissolved in the 50mL acetonitrile, ultrasonic 3～5 minutes, impel it fully to dissolve.Take by weighing 0.8125g (5mmol) iron trichloride at 1: 1 by oxygen digital ratio and be dissolved in the 50mL distilled water, place it in (about 10 ℃) in the room-temperature water bath.Oxidizing agent solution is added drop-wise in the monomer solution.Dropwise the back and continue reaction 8h, reaction finishes, and filters, colourless with the distilled water wash head product to filtrate, again the polymkeric substance filter cake is transferred in the beaker and to be continued agitator treating and spend the night, obtain scleroid black powder shaped polymer after the suction filtration drying, output 0.7248g, productive rate 91.6%.
The polymer architecture correspondence of determining definite C/H/N ratio, so can come the structure of analyzing polymers by the research to the C/H/N ratio.Table one is by prepared poly-1 of the present invention, the results of elemental analyses of 8-naphthylene diamine.
The ultimate analysis of table one P18DAN
Table one shows: P18DAN
FThe test C/H/N ratio that results of elemental analyses calculates is very approaching with the ratio that is calculated acquisition by the b structural formula, i.e. polymer P 18DAN
FModular construction is similar to structural formula b, this result shows, denitrification reaction has taken place in the P18DAN chain link in the oxypolymerization process, two nitrogen-atoms are sloughed in per five naphthylene diamine unit, the content of H is higher than the H content among the structural formula b in the molecular formula that results of elemental analyses calculates, and possible cause is polymer P 18DAN
FIn contain Fe
3+Ion and absorb water and make that detected H content is higher.P18DAN
SModular construction and structural formula d are comparatively identical.This result shows that the P18DAN chain link in the oxypolymerization process denitrification reaction has taken place, and two nitrogen-atoms are sloughed in per five naphthylene diamine unit, and have the quinoid structural formula in the P18DAN chain link, but a bit discrepancy of hydrogen atom number mainly is the influence of end amido.
Claims (4)
1. gather 1, the chemical oxidation preparation method of 8-naphthylene diamine, its step is as follows: with 1, the 8-naphthylene diamine is dissolved in it is fully dissolved, the aqueous solution with oxygenant adds in the above-mentioned monomer solution then, temperature of reaction is 10 ℃～30 ℃, and in 6～10 hours reaction times, the aftertreatment that reacts completely gets final product.
2. as claimed in claim 1 poly-1, the chemical oxidation preparation method of 8-naphthylene diamine is characterized in that described organic solvent is methyl alcohol, ethanol, acetonitrile or propionitrile.
3. as claimed in claim 1 poly-1, the chemical oxidation preparation method of 8-naphthylene diamine is characterized in that described oxygenant is the blend of following one or more: ammonium persulphate, Potassium Persulphate, potassium bichromate, iron trichloride.
4. as claimed in claim 1 poly-1, the chemical oxidation preparation method of 8-naphthylene diamine, the mol ratio that it is characterized in that described monomer and oxygenant is 0.5: 1～2: 1.
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|---|---|---|---|
| CNB2005100236284A CN100395278C (en) | 2005-01-26 | 2005-01-26 | Prepn process of poly-1,8-naphthalenediamine |
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|---|---|---|---|
| CNB2005100236284A CN100395278C (en) | 2005-01-26 | 2005-01-26 | Prepn process of poly-1,8-naphthalenediamine |
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| CN100395278C true CN100395278C (en) | 2008-06-18 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445319C (en) * | 2007-01-18 | 2008-12-24 | 同济大学 | Process for preparing water-soluble polysulfonated naphthylamine |
| CN104448307B (en) * | 2014-12-12 | 2016-07-27 | 湖南科技大学 | A kind of method preparing silicon dioxide/poly-1,8 naphthylenediamine nano composite materials and product |
| CN110078916A (en) * | 2019-04-23 | 2019-08-02 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of poly- 1,8- diaminonaphthalene nanotube |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162509A (en) * | 1989-03-06 | 1992-11-10 | Board Of Regents, The University Of Texas System | Process for preparing expanded porphyrins: large porphyrin-like tripyrroledimethine-derived macrocycles |
| JPH06322115A (en) * | 1993-05-14 | 1994-11-22 | Osaka Gas Co Ltd | Polyaminoazonaphthalene and its production |
-
2005
- 2005-01-26 CN CNB2005100236284A patent/CN100395278C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162509A (en) * | 1989-03-06 | 1992-11-10 | Board Of Regents, The University Of Texas System | Process for preparing expanded porphyrins: large porphyrin-like tripyrroledimethine-derived macrocycles |
| JPH06322115A (en) * | 1993-05-14 | 1994-11-22 | Osaka Gas Co Ltd | Polyaminoazonaphthalene and its production |
Non-Patent Citations (5)
| Title |
|---|
| Electrochemical Characterization ofpoly(1,8-diaminonaphthalene):A Fuctionalized Polymer. Joo-Won Lee.Electrochem Soc,Vol.139 No.12. 1992 * |
| Facile synthesis of poly(1,8-diaminonaphthalene)microparticleswith a very high silver-ion adsorbability by achemical oxidativepolymerization. Xin-Gui Li.Acta Materialia,Vol.52 No.18. 2004 * |
| Novel Multifunctional Polymers from Aromatic Diamines byOxidative Polymerizations. Xin-Gui Li.Chem. Rev.,Vol.102 . 2002 * |
| 新型合成聚合物重金属离子吸附剂及其吸附性能. 黄美荣.工业水处理，第25卷第1期. 2005 * |
| 芳香族二胺聚合物的合成及其性能. 秦伟.高分子学报，第4期. 1993 * |
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| CN1810853A (en) | 2006-08-02 |
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