CN100340591C - Method of preparing aniline nano-fiber using lysotropic liquid crystal as form - Google Patents
Method of preparing aniline nano-fiber using lysotropic liquid crystal as form Download PDFInfo
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- CN100340591C CN100340591C CNB2005101235626A CN200510123562A CN100340591C CN 100340591 C CN100340591 C CN 100340591C CN B2005101235626 A CNB2005101235626 A CN B2005101235626A CN 200510123562 A CN200510123562 A CN 200510123562A CN 100340591 C CN100340591 C CN 100340591C
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Abstract
The present invention provides a method for preparing nanometer polymer fibers by using a lyotropic liquid crystal as a template, which belongs to the technical field of the preparation of nanometer aniline fibers. The present invention applies the orderly and special structure of a surfactant lyotropic liquid crystal to template polymerization reactions, namely that a polymerizable single crystal is firstly assembled to an interlayer of an LLC, and then, the LLC is used as a template in which the single crystal carries out polymerization reactions. The present invention has the advantages that the appearance of polymers can be effectively controlled by the template which is easy to degrade and is environment-friendly; the polymerization conditions are easy to control with a few polymerization influencing factors, nanometer polymers with various structures can be obtained, and the template is easy to remove when the reaction is finished.
Description
Affiliated field
The invention belongs to the aniline nano-fiber preparing technical field, particularly providing a kind of is the method that template prepares polymer nanofiber with lytropic liquid crystals (LLC).
Background technology
Document Supp S.I., Lebonheur V., et al., Science, 1997,276, point out among the 384-389, the nanostructure polymer materials has broad application prospects at aspects such as magnetics, electricity, optics, catalysis and chemical sensitisations, has therefore caused people's huge concern and has started the upsurge of studying.The preparation of nanometer polymer material at present comprises molecule self-assembly, mechanical disintegration, organic synthesis, micro-emulsion polymerization, template polymerization or the like, and wherein comparatively effectively the pattern of controlling polymers and the method for particle diameter are microemulsion polymerization method and template.Document Kageyama K., Tamazawa J., Aida T., Science, 1999, point out among the 285:2113 that template is meant selects a kind of material to be " mould ", impels component to grow or grow around mould in mould, the geometric parameter of material will be subjected to the restriction of template.Therefore, the shape and size that change template can realize that the expection of product structure is controlled.Employing has the film of nanometer micropore such as polycarbonate, Al
2O
3Films etc. or inorganic laminated clay be as template, makes monomer polymerization in these have the micropore of nanoscale or lamellar spacing, forms the material of nanometer polymer tubulose, wire or laminate structure.Template is more extensive and effective in the research work of preparation nanometer polymer.Document E1-Safty S.A., et al., Chem.Mater, 2004,16, point out among the 384-400 that form lytropic liquid crystals with surfactivity and have structural diversity mutually, the long-range periodic that presents the feature repetition interval of 2-15nm is arranged; They are the mesoporous silicon of template for preparing three-dimensional order with the tensio-active agent lytropic liquid crystals, and the mesoporous silicon of acquisition has the nanometer network structure and the very high surface-area of three-dimensional order.
LLC is binary or the multicomponent system that is formed by certain density tensio-active agent (SAA) and solvent.Parents SAA molecule exists with monomeric form when solution solubility is very low, or is adsorbed on the interface; Increase with strength of solution, the SAA molecule may pass through the dimer stage, forms pre-micella; When strength of solution reaches micelle-forming concentration when above, the SAA molecule associates mutually by the self-organization effect and forms stratiform, sphere or cylindrical micelle; Along with solubility continue to increase, the micella formation lytropic liquid crystals that will further associate.Under suitable temperature, along with the increase of concentration, the LLC that associate to form can present stratiform, six sides, cube etc. structure.
Summary of the invention
The objective of the invention is to: providing a kind of is the method that template prepares polymer nanofiber with lytropic liquid crystals (LLC); Owing to will be subjected to the restriction of template at the molecular chain structure of the confinement space of template interpolymer etc., therefore can prepare the polymkeric substance of different nano-scale structure.
The present invention be with the tensio-active agent lytropic liquid crystals structural in order and singularity be applied in the template polymerization reaction, promptly first polymerisable set of monomers is installed to the interlayer of LLC, be template with LLC again, make monomer polymerization reaction take place in template.Concrete preparation process is as follows:
1. in Glass Containers, take by weighing the 0.5-2.2g surfactant A; Get the 0.5-2.0ml deionized water to Glass Containers,, rock to B and dissolve fully to wherein adding 0.2-0.6g oxygenant B; B solution is joined among the A.Heat said mixture under 50～100 ℃ of temperature, make A and B evenly mixed.
2. get 0.5-2.5ml purified petroleum benzin amine in Glass Containers, to the sour C that wherein adds 1.0-2.5mmol, make the abundant acidifying of aniline, the mol ratio of aniline and sour C is 1.0～3.0.
3.50 under～100 ℃, acidifying aniline is dropwise joined in the Glass Containers that fills the mixing template, ultrasonic oscillation 15～60 minutes allows acidifying aniline and template form homogeneous phase.The mass ratio of tensio-active agent and water should be between 3: 1 to 1: 3, and the mol ratio of aniline and oxygenant should be between 5: 1 to 1: 3.Behind the mixing, 0～40 ℃ was reacted 8～72 hours down.
4. after reaction finishes,, use 30-60 ℃ deionized water rinsing then, till filtering filtrate is clear look liquid with 30-60 ℃ organic solvent D flushing several times.
5. the solid product that at last filtration is obtained carries out drying, and the exsiccant temperature is 50～60 ℃, and the time is 24～48 hours.
The polymkeric substance of separating is characterized with infrared spectra, transmission and scanning electron microscope etc., record about prepared polymer sizes 70 nanometers, pattern is rendered as nanofiber or the little spherical structure of nanometer.
Surfactant A of the present invention is any among Brij (hexadecanol Soxylat A 25-7) 56, Brij58, Brij76, the Brij78, and described oxygenant B is (NH
3)
2S
2O
8, Na
2S
2O
8, K
2S
2O
8In any;
Sour C of the present invention is HCl, H
3PO
4, H
2SO
4In any one.
Organic solvent of the present invention is any in acetone, ethanol, the tetrahydrofuran (THF).
Because the nano-scale of the polymkeric substance of preparation; special appearance; and characteristics such as polymkeric substance itself, make this polymkeric substance will have broad application prospects at aspects such as machinery, light, electricity, magnetic, microprogramming device, environment protection, stealth material, high-performance coating material and biological chemistries.
Advantage of the present invention is: first Brij series nonionic surface active agent lytropic liquid crystals is applied in the research of preparation nanostructure polymkeric substance as template, widened the polymerization means and the monomeric range of choice of preparation nano-scale polymkeric substance.This method is by the effective controlling polymers pattern of template, and selected template is degraded easily, and is environmentally friendly; In addition, polymerizing condition is easy to control, and the polymerization influence factor is few, can obtain the nano-scale polymerisate of various structures, and reaction is finished rear pattern plate and is easy to remove.
Embodiment
Embodiment 1:
A. measure the 0.83ml deionized water to the little cillin bottle of 25ml with transfer pipet, 0.300g ammonium persulphate (APS) and 1.00g surfactant B rij56 are added respectively wherein, heating makes the two evenly mixed.
B. the hydrochloric acid (37%) with 0.24ml (2.75mmol) slowly joins in the aniline of 0.5ml (5.5mmol).
C. acidifying aniline is dropwise joined in the cillin bottle that fills tensio-active agent, reacted 12 hours.
D. after reaction finishes, use hot alcohol flushing three times, use the deionized water rinsing of heat then.
E. the solid polymerization product vacuum-drying that filtration is obtained.
Embodiment 2:
A. measure the 0.83ml deionized water to the little cillin bottle of 25ml with transfer pipet, 0.300g ammonium persulphate (APS) and 1.00g surfactant B rij58 are added respectively wherein, heating makes the two evenly mixed.
B. the hydrochloric acid (37%) with 0.24ml (2.75mmol) slowly joins in the aniline of 0.5ml (5.5mmol).
C. acidifying aniline is dropwise joined in the cillin bottle that fills tensio-active agent, reacted 10 hours.
D. after reaction finishes, use hot acetone rinsing three times, use the deionized water rinsing of heat then.
E. the solid polymerization product vacuum-drying that filtration is obtained.
Embodiment 3:
A. measure the 0.83ml deionized water to the little cillin bottle of 25ml with transfer pipet, 0.35g Potassium Persulphate (KPS) and 1.00g surfactant B rij76 are added respectively wherein, heating makes the two with even.
B. with the H of 2.75mmol
3PO
4Slowly join in the aniline of 0.5ml (5.5mmol).
C. acidifying aniline is dropwise joined in the cillin bottle that fills tensio-active agent, reacted 20 hours.
D. after reaction finishes, use hot alcohol flushing three times, use the deionized water rinsing of heat then.
E. the solid polymerization product vacuum-drying that filtration is obtained.
Embodiment 4:
A. measure the 0.83ml deionized water to the little cillin bottle of 25ml with transfer pipet, 0.32g Potassium Persulphate (KPS) and 1.00g surfactant B rij78 are added respectively wherein, heating makes the two evenly mixed.
B. with the H of 2.75mmol
3PO
4Slowly join in the aniline of 0.5ml (5.5mmol).
C. acidifying aniline is dropwise joined in the cillin bottle that fills tensio-active agent, reacted 12 hours.
D. after reaction finishes,, use the deionized water rinsing of heat then with hot tetrahydrofuran (THF) flushing three times.
E. the solid polymerization product vacuum-drying that filtration is obtained.
Embodiment 5:
A. measure the 0.83ml deionized water to the little cillin bottle of 25ml with transfer pipet, 0.32g Sodium Persulfate and 1.00g surfactant B rij56 are added wherein, heating makes the two evenly mixed.
B. the sulfuric acid with 2.75mmol slowly joins in the aniline of 0.5ml (5.5mmol).
C. acidifying aniline is dropwise joined in the cillin bottle that fills tensio-active agent, reacted 12 hours.
D. after reaction finishes,, use the deionized water rinsing of heat then with hot tetrahydrofuran (THF) flushing three times.
E. the solid polymerization product vacuum-drying that filtration is obtained.
Embodiment 6:
A. measure the 0.83ml deionized water to the little cillin bottle of 25ml with transfer pipet, 0.32g Sodium Persulfate and 1.00g surfactant B rij76 are not added wherein, heating makes the two evenly mixed.
B. the sulfuric acid with 2.75mmol slowly joins in the aniline of 0.5ml (5.5mmol).
C. acidifying aniline is dropwise joined in the cillin bottle that fills tensio-active agent, reacted 12 hours.
D. after reaction finishes,, use the deionized water rinsing of heat then with hot tetrahydrofuran (THF) flushing three times.
E. the solid polymerization product vacuum-drying that filtration is obtained.
Claims (1)
1, a kind of is the method that template prepares polymer nanofiber with the lytropic liquid crystals, it is characterized in that: concrete preparation process is:
A. in Glass Containers, take by weighing the 0.5-2.2g surfactant A; Get the 0.5-2.0ml deionized water to Glass Containers,, rock to B and dissolve fully to wherein adding 0.2-0.6g oxygenant B; B solution is joined among the A, heat said mixture under 50～100 ℃ of temperature, make A and B evenly mixed;
B. get 0.5-2.5ml purified petroleum benzin amine in Glass Containers, to the sour C that wherein adds 1.O-2.5mmol, make the abundant acidifying of aniline, the mol ratio of aniline and sour C is 1.0～3.0;
℃ c.50～100 under, acidifying aniline is dropwise joined in the Glass Containers that fills the mixing template, ultrasonic oscillation 15～60 minutes, allow acidifying aniline and template form homogeneous phase, the mass ratio of tensio-active agent and water should be between 3: 1 to 1: 3, and the mol ratio of aniline and oxygenant should be between 5: 1 to 1: 3; Behind the mixing, O～40 ℃ following reaction 8～72 hours;
D. after reaction finishes,, use 30-60 ℃ deionized water rinsing then, till filtering filtrate is clear look liquid with 30-60 ℃ organic solvent D flushing several times;
E. the solid product that at last filtration is obtained carries out drying, and the exsiccant temperature is 50～60 ℃, and the time is 24～48 hours;
F, the polymkeric substance of separating is characterized with infrared spectra, transmission and scanning electron microscope, record about prepared polymer sizes 70 nanometers, pattern is rendered as nanofiber or the little spherical structure of nanometer;
Described surfactant A is any in hexadecanol Soxylat A 25-7 56, hexadecanol Soxylat A 25-7 58, hexadecanol Soxylat A 25-7 76, the hexadecanol Soxylat A 25-7 78; Described oxygenant B is (NH3)
2S
2O
8, Na
2S
2O
8, K
2S
2O
8In any; Described sour C is HCl, H
3PO
4, H
2SO
4In any one; Described organic solvent is any in acetone, ethanol, tetrahydrofuran (THF), the methylene dichloride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101235626A CN100340591C (en) | 2005-11-21 | 2005-11-21 | Method of preparing aniline nano-fiber using lysotropic liquid crystal as form |
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|---|---|---|---|
| CNB2005101235626A CN100340591C (en) | 2005-11-21 | 2005-11-21 | Method of preparing aniline nano-fiber using lysotropic liquid crystal as form |
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|---|---|
| CN1786051A CN1786051A (en) | 2006-06-14 |
| CN100340591C true CN100340591C (en) | 2007-10-03 |
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| CN101845148B (en) * | 2010-03-31 | 2011-11-16 | 北京科技大学 | Preparation method of polyaniline nanofiber array |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6027666A (en) * | 1998-06-05 | 2000-02-22 | The Governing Council Of The University Of Toronto | Fast luminescent silicon |
| CN1445311A (en) * | 2002-03-20 | 2003-10-01 | 新加坡纳米材料科技有限公司 | calcium carbonate/silicon dioxide-water(1/n) nano-compound particle and hollow silicon dioxide-water(1/n) nano-material and its preparation method |
| CN1621432A (en) * | 2004-10-26 | 2005-06-01 | 中国科学院长春应用化学研究所 | Process for preparing poly-o-phenylamine nano-belt |
-
2005
- 2005-11-21 CN CNB2005101235626A patent/CN100340591C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6027666A (en) * | 1998-06-05 | 2000-02-22 | The Governing Council Of The University Of Toronto | Fast luminescent silicon |
| CN1445311A (en) * | 2002-03-20 | 2003-10-01 | 新加坡纳米材料科技有限公司 | calcium carbonate/silicon dioxide-water(1/n) nano-compound particle and hollow silicon dioxide-water(1/n) nano-material and its preparation method |
| CN1621432A (en) * | 2004-10-26 | 2005-06-01 | 中国科学院长春应用化学研究所 | Process for preparing poly-o-phenylamine nano-belt |
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