CN103910880A - Preparation method for helical structure polyaniline, helical structure polyaniline and application - Google Patents
Preparation method for helical structure polyaniline, helical structure polyaniline and application Download PDFInfo
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Abstract
The invention relates to a preparation method for helical structure polyaniline, the helical structure polyaniline obtained by the method and application. The method includes: based on traditional emulsion polymerization methods, introducing short-chain fatty alcohol into a reaction system to form a special vesicle structure, and taking the vesicle as a soft template to prepare the levo-structure and dextro-structure intertwined composite structure, levo-structure or dextro-structure helical polyaniline formed by winding of over one polyaniline nanofiber. According to the method provided by the invention, the helical structure polyaniline can be prepared without introducing a traditional chiral dopant, a chiral template or a chiral inducer and other chiral materials, and especially the composite structure polyaniline with intertwined levo-structure and dextro-structure can be obtained. The antistatic and wave-absorbing properties of the helical structure polyaniline are superior to those of non-helical structure polyaniline. Also, the helical structure polyaniline has excellent electromagnetic performance, and can be used for preparation of anti-static materials, wave-absorbing materials and electrode materials, etc.
Description
Technical field
The invention belongs to conducting polymer materials field, particularly a kind of preparation method of spirane structure polyaniline and the spirane structure polyaniline and the purposes that are obtained by the method.
Background technology
Spirane structure is as the secondary conformation of molecule, ubiquity in biopolymer, and as protein, nucleic acid etc.The polymkeric substance of spirane structure is all widely used in a lot of fields because it has this special structure of chirality, if nano level spirane structure polyaniline is due to its unique chiral structure and special optics and electrology characteristic, at chemistry with biosensor, chiral recognition and separate, extensive concern that the aspect such as Surface Modified Electrodes, electrochromic material and absorbing material enjoys domestic and international scientist.
In the research field of spirane structure polyaniline, people use chemical polymerization and electrochemical polymerization method conventionally, be embodied in aniline monomer and chiral material are dissolved in organic solvent simultaneously and make aniline monomer under the impact of chiral material, be polymerized to the polymkeric substance of chirality, or direct polyaniline and chiral material are dissolved in organic solvent altogether, make polyaniline molecule chain generate spirane structure under the effect of chiral material.Under the condition that Li etc. (JACS, 2003,126,2278 ~ 2279) exist at chirality camphorsulfonic acid, the promotor using aniline oligomer as reaction system, prepares and has chiral helical structure polyaniline nanofiber.Wan etc. (Thin Solid Films, 2005,447,24 ~ 31) in the system of D-or L-camphorsulfonic acid, by self assembly spirane structure polyaniline nanotube.Yan etc. (Advanced Materials, 2007,19,3353 ~ 3357) adopt the method identical with Wan, by the ratio of chirality camphorsulfonic acid and aniline monomer in change building-up process, prepare and have spirane structure polyaniline nano fiber.Weng etc. (Elereochimica Acta, 2010,55,2727 ~ 2733) use chirality camphorsulfonic acid as doping agent, have prepared spirane structure polyaniline nano fiber by the method for Direct Electrochemistry polymerization.
At present, in reaction system, not adding the chiral materials such as chiral dopant, chiral template or chiral induction agent prepares the method for spirane structure polyaniline and does not still report, and the present invention prepares imitated vesicle structure by controlling reaction conditions in the reaction system without chiral material, prepare spirane structure polyaniline using vesica as soft template, method is simple and feasible; And this spirane structure polyaniline has good electromagnetic performance, can be used for preparing antistatic material, absorbing material and electrode materials and use.
Summary of the invention
One of object of the present invention is to provide a kind of method of utilizing vesica soft template to prepare spirane structure polyaniline.
Two of object of the present invention is to provide the spirane structure polyaniline being obtained by object one.
Three of object of the present invention is to provide the purposes of the spirane structure polyaniline being obtained by object two.
The reaction system that spirane structure polyaniline of the present invention is is soft template by vesica prepares, and does not need to add the chiral materials such as traditional chiral dopant, chiral template or chiral induction agent, and its preparation method comprises the following steps:
A) preparation surface active agent emulsions: tensio-active agent is dissolved in deionized water, and fully stirring (the general time of stirring is 0.5 ~ 2 hour), to obtain volumetric molar concentration be that 0.4 ~ 0.75mol/L(is preferably 0.5 ~ 0.6mol/L) surface active agent emulsions;
Described tensio-active agent is selected from one or more in alkyl benzene sulphonate (ABS), alkylbenzene sulfonate, alkylsulphonic acid, alkylsulfonate, alkylsurfuric acid, alkyl-sulphate; Wherein, the number of the carbon atom of described alkyl is 6 ~ 18;
B) preparation aniline solution: aniline is dissolved in organic solvent, and fully stirring and obtaining volumetric molar concentration is that 0.8 ~ 10mol/L(is preferably 1.5 ~ 7.5mol/L) aniline solution;
Described organic solvent is selected from one or more in benzene, toluene, ethylbenzene, propyl benzene, dimethylbenzene, diethylbenzene, sym-trimethylbenzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, oil of mirbane, dinitrobenzene;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the surface active agent emulsions that step a) obtains, and then add short chain fatty alcohol to obtain reaction system, wherein: in every liter of reaction system, the mol ratio of tensio-active agent and aniline is that 1:0.5 ~ 1:5(is preferably 1:0.5 ~ 1:2), the volumetric molar concentration of short chain fatty alcohol is that 0.4 ~ 1.2mol/L(is preferably 0.6 ~ 1mol/L); Continue to stir (the general time of stirring is 0.5 ~ 2 hour), obtain the reaction system that contains vesica soft template;
A kind of ordered structure that vesica in gained vesica soft template is made up of jointly tensio-active agent, water and organic phase, its pattern as shown in Figure 2.Described vesica soft template is that the vesica that is 1 ~ 10 layer by the number of plies of one deck cover one deck forms; The size of described vesica soft template is 100 ~ 300nm.
D) preparation oxidizing agent solution: oxygenant is dissolved in deionized water, and obtaining volumetric molar concentration is that 0.2 ~ 3mol/L(is preferably 0.5 ~ 1.5mol/L) oxidizing agent solution;
E) under continuing to stir, the oxidizing agent solution that step d) is obtained joins in the reaction system that contains vesica soft template that step c) obtains, and wherein the mol ratio of the aniline in oxygenant and step b) is that 1:0.5 ~ 1:5(is preferably 1:0.5 ~ 1:2); Continue to stir (the general time of stirring is 0.2 ~ 24 hour), obtain the blackish green mixed solution (the blackish green mixed solution that contains spirane structure polyaniline comprises composite structure polyaniline, left-handed structure polyaniline and/or the dextrorotation structure polyaniline that left-handed structure and dextrorotation structure are wound around mutually) that contains spirane structure polyaniline;
F) in the blackish green mixed solution that contains spirane structure polyaniline obtaining in step e), add short chain fatty alcohol to carry out washing and filtering (add-on of general short chain fatty alcohol is described 2 ~ 10 times of volumes of blackish green mixed solution), then gained filter cake being joined to (add-on of general deionized water is 2 ~ 10 times of volumes of gained filter cake) in deionized water washs, after filtration, be dried, obtain blackish green powder, be spirane structure polyaniline, its pattern as shown in Figure 1.
Temperature when continuation described in step e) is stirred is 0 ~ 60 ℃.
Described alkyl benzene sulphonate (ABS) is selected from one or more in the chain alkyl Phenylsulfonic acids such as six alkyl benzene sulphonate (ABS)s, ten alkyl benzene sulphonate (ABS)s, Witco 1298 Soft Acid, tetradecyl Phenylsulfonic acid, hexadecyl Phenylsulfonic acid, octadecyl Phenylsulfonic acid.
Described alkylbenzene sulfonate is selected from one or more in the long-chain alkyl benzene sulfonates such as six alkylbenzene sulfonates, ten alkylbenzene sulfonates, dodecylbenzene sulfonate, tetradecyl benzene sulfonate, hexadecyl benzene sulfonate, octadecyl benzene sulfonate.
Described alkylsulphonic acid is selected from one or more in the chain alkyl sulfonic acid such as ten alkylsulphonic acids, undecyl sulfonic acid, dodecyl sodium sulfonate, tridecyl sulfonic acid, tetradecyl sulfonic acid, pentadecyl sulfonic acid, hexadecyl sulfonic acid.
Described alkylsulfonate is selected from one or more in ten alkylsulfonates, undecyl sulfonate, dodecane sulfonate, tridecyl sulfonate, tetradecyl sulfonate, pentadecane sulfonate, the isometric chain alkyl sulfonate of hexadecyl sulfonate.
Described alkylsurfuric acid is selected from one or more in the chain alkyl sulfuric acid such as ten alkylsurfuric acids, undecyl sulfuric acid, dodecyl sulphate, tridecyl sulfuric acid, tetradecyl sulfuric acid, hexadecyl hydrosulfate, octadecyl sulfuric acid.
Described alkyl-sulphate is selected from one or more in the long chain alkyl sulfates such as ten alkyl-sulphates, undecyl sulfates, dodecyl sulfate, tridecyl vitriol, tetradecyl sulfate, cetyl sulfate, octadecyl vitriol.
Described short chain fatty alcohol is selected from one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol etc.
Described oxygenant is selected from one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Potassium Iodate, potassium bromate, Potcrate, iron trichloride, hydrogen peroxide etc.
The spirane structure polyaniline being obtained by the preparation method of spirane structure polyaniline of the present invention is to be entwined by an above polyaniline nano fiber, and described spirane structure is composite structure, left-handed structure or the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 100 ~ 300nm, and length is 0.5 ~ 5 μ m, and pitch is 40 ~ 100nm.
The diameter of described polyaniline nano fiber is 40 ~ 100nm, and length is 1 ~ 10 μ m.
The present invention is on the basis of traditional emulsion polymerisation process, in reaction system, introduce short chain fatty alcohol, and the concentration ratio conventional emulsion polymerization system that makes reactant wants high 5-10 doubly, thereby form special imitated vesicle structure, this is different from the micellar structure that conventional emulsion polymerization system obtains, and finally prepares spirane structure polyaniline.The present invention does not need to introduce the chiral materials such as traditional chiral dopant, chiral template or chiral induction agent can prepare spirane structure polyaniline, especially can obtain the composite structure polyaniline that left-handed structure and dextrorotation structure are wound around mutually.Antistatic and the absorbing property of spirane structure polyaniline of the present invention is better than non-helical structure polyaniline, and spirane structure polyaniline (spirane structure and polyaniline cause jointly) has good electromagnetic performance, can be used for preparing the uses such as antistatic material, absorbing material and electrode materials.
Accompanying drawing explanation
Fig. 1. scanning and the transmission electron microscope photo of the spirane structure polyaniline in the embodiment of the present invention 1.
Fig. 2. the freezing transmission electron microscope photo of the vesica soft template that the vesica layer overlaps by 2 ~ 6 layers in the embodiment of the present invention 1 forms.
Embodiment
Embodiment 1
A) preparation surface active agent emulsions: Witco 1298 Soft Acid is dissolved in deionized water, fully stirs 0.5 ~ 2 hour, obtaining volumetric molar concentration is the Witco 1298 Soft Acid emulsion of 0.5mol/L;
B) preparation aniline solution: aniline is dissolved in dimethylbenzene, fully stirs and obtain the aniline solution that volumetric molar concentration is 5mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the Witco 1298 Soft Acid emulsion that step a) obtains, and then add n-propyl alcohol to obtain reaction system, wherein: in every liter of reaction system, the mol ratio of Witco 1298 Soft Acid and aniline is 1:1.5, and the volumetric molar concentration of n-propyl alcohol is 1mol/L; At room temperature continue to stir 0.8 hour, obtain the reaction system that contains the vesica soft template being formed by the vesica layer overlaps of 2 ~ 6 layers; The size of described vesica soft template is 120 ~ 250nm; The freezing transmission electron microscope photo of vesica soft template as shown in Figure 2;
D) preparation oxidizing agent solution: ammonium persulphate is dissolved in deionized water, obtains the ammonium persulfate solution that volumetric molar concentration is 1.5mol/L;
E) continuing under stirring, the ammonium persulfate solution that step d) is obtained joins in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 2 ~ 6 layers that step c) obtains, the wherein Witco 1298 Soft Acid in step b): the aniline in step b): the mol ratio of ammonium persulphate is 1:1.5:1.5; At room temperature continue to stir 0.5 hour, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline, its pattern is as shown in Figure 1.Gained spirane structure polyaniline is to be 60 ~ 90nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 4 ~ 9 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 150 ~ 250nm, and length is 2 ~ 5 μ m, and pitch is 60 ~ 100nm.
Embodiment 2
A) preparation surface active agent emulsions: ten alkyl benzene sulphonate (ABS)s are dissolved in deionized water, by ice bath control temperature, make homo(io)thermism at 0 ℃, fully stir 0.5 ~ 2 hour, obtaining volumetric molar concentration is the ten alkyl benzene sulphonate (ABS) emulsions of 0.5mol/L;
B) preparation aniline solution: aniline is dissolved in propyl benzene, fully stirs and obtain the aniline solution that volumetric molar concentration is 3mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the ten alkyl benzene sulphonate (ABS) emulsions that step a) obtains, and then add propyl carbinol to obtain reaction system, wherein: in every liter of reaction system, the mol ratio of ten alkyl benzene sulphonate (ABS)s and aniline is 1:2, and the volumetric molar concentration of propyl carbinol is 1mol/L; At 0 ℃, continue to stir 1 hour, obtain the reaction system that contains the vesica soft template being formed by the vesica layer overlaps of 1 ~ 5 layer; The size of described vesica soft template is 100 ~ 200nm;
D) preparation oxidizing agent solution: Sodium Persulfate is dissolved in deionized water, and obtaining volumetric molar concentration is the Sodium Persulfate solution of 2mol/L;
E) continuing under stirring, the Sodium Persulfate solution that step d) is obtained joins in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 1 ~ 5 layer that step c) obtains, wherein ten alkyl benzene sulphonate (ABS)s in step b): the aniline in step b): the mol ratio of Sodium Persulfate is 1:2:3; At 0 ℃, continue to stir 2 hours, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline.Gained spirane structure polyaniline is to be 70 ~ 100nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 5 ~ 10 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 200 ~ 300nm, and length is 2 ~ 5 μ m, and pitch is 70 ~ 100nm.
Embodiment 3
A) preparation surface active agent emulsions: octadecyl sulfuric acid is dissolved in deionized water, fully stirs 0.5 ~ 2 hour, obtaining volumetric molar concentration is the octadecyl sulfuric acid emulsion of 0.75mol/L;
B) preparation aniline solution: aniline is dissolved in benzene, fully stirs and obtain the aniline solution that volumetric molar concentration is 1.5mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the octadecyl sulfuric acid emulsion that step a) obtains, and then add Pentyl alcohol to obtain reaction system, wherein: in every liter of reaction system, the mol ratio of octadecyl sulfuric acid and aniline is 1.5:1, and the volumetric molar concentration of Pentyl alcohol is 0.6mol/L; At room temperature continue to stir 1 hour, the vesica layer overlaps formation number of plies that obtains containing by 4 ~ 10 layers is the reaction system of the vesica soft template of 4 ~ 10 layers; The size of described vesica soft template is 150 ~ 300nm;
D) preparation oxidizing agent solution: Potassium Persulphate is dissolved in deionized water, obtains the potassium persulfate solution that volumetric molar concentration is 1mol/L;
E) continuing under stirring, the potassium persulfate solution that step d) is obtained joins in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 4 ~ 10 layers that step c) obtains, the wherein octadecyl sulfuric acid in step b): the aniline in step b): the mol ratio of Potassium Persulphate is 1.5:1:1; At room temperature continue to stir 1 hour, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline.Gained spirane structure polyaniline is to be 40 ~ 70nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 1 ~ 6 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 100 ~ 200nm, and length is 1 ~ 3 μ m, and pitch is 40 ~ 70nm.
Embodiment 4
A) preparation surface active agent emulsions: by octadecyl Phenylsulfonic acid and octadecyl benzene sulfonic acid sodium salt in molar ratio 1:1 be dissolved in deionized water, fully stir 0.5 ~ 2 hour, obtaining volumetric molar concentration is the octadecyl Phenylsulfonic acid of 0.4mol/L and the mixed emulsion of octadecyl benzene sulfonic acid sodium salt;
B) preparation aniline solution: aniline is dissolved in the dichlorobenzene and dibromobenzene that mol ratio is 1:1, fully stirs and obtain the aniline solution that volumetric molar concentration is 1.5mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the mixed emulsion of octadecyl Phenylsulfonic acid that step a) obtains and octadecyl benzene sulfonic acid sodium salt, and then add n-hexyl alcohol to obtain reaction system, wherein: in every liter of reaction system, mole total amount of octadecyl Phenylsulfonic acid and octadecyl benzene sulfonic acid sodium salt and the mol ratio of aniline are 1:1, and the volumetric molar concentration of n-hexyl alcohol is 0.6mol/L; At room temperature continue to stir 1.5 hours, obtain the reaction system that contains the vesica soft template being formed by the vesica layer overlaps of 3 ~ 8 layers; The size of described vesica soft template is 120 ~ 250nm;
D) preparation oxidizing agent solution: hydrogen peroxide is dissolved in deionized water, obtains the superoxol that volumetric molar concentration is 0.5mol/L;
E) continuing under stirring, the superoxol that step d) is obtained joins in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 3 ~ 8 layers that step c) obtains, the wherein mole total amount of the octadecyl Phenylsulfonic acid in step b) and octadecyl benzene sulfonic acid sodium salt: the aniline in step b): the mol ratio of hydrogen peroxide is 1:1:0.5; At room temperature continue to stir 24 hours, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline.Gained spirane structure polyaniline is to be 50 ~ 80nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 3 ~ 7 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 120 ~ 200nm, and length is 2 ~ 4 μ m, and pitch is 40 ~ 100nm.
Embodiment 5
A) preparation surface active agent emulsions: by six sodium alkyl benzene sulfonates, ten alkyl sodium sulfonates and ten sodium alkyl sulfates in molar ratio 1:1:1 be dissolved in deionized water, by ice bath control temperature, make homo(io)thermism at 60 ℃, fully stir 0.5 ~ 2 hour, obtaining volumetric molar concentration is the mixed emulsion of six sodium alkyl benzene sulfonates, ten alkyl sodium sulfonates and ten sodium alkyl sulfates of 0.6mol/L;
B) preparation aniline solution: aniline is dissolved in the chlorobenzene and bromobenzene of mol ratio 1:1, fully stirs and obtain the aniline solution that volumetric molar concentration is 3mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the mixed emulsion of six sodium alkyl benzene sulfonates, ten alkyl sodium sulfonates and ten sodium alkyl sulfates that step a) obtains, and then add the trimethyl carbinol of mol ratio 1:1 and isopropylcarbinol to obtain reaction system, wherein: in every liter of reaction system, mole total amount of six sodium alkyl benzene sulfonates, ten alkyl sodium sulfonates and ten sodium alkyl sulfates and the mol ratio of aniline are 1:1, and mole total concn of the trimethyl carbinol and isopropylcarbinol is 0.8mol/L; At 60 ℃, continue to stir 0.5 hour, obtain the reaction system that contains the vesica soft template being formed by the vesica layer overlaps of 3 ~ 9 layers; The size of described vesica soft template is 120 ~ 280nm;
D) preparation oxidizing agent solution: iron trichloride is dissolved in deionized water, obtains the liquor ferri trichloridi that volumetric molar concentration is 2mol/L;
E) continuing under stirring, the liquor ferri trichloridi that step d) is obtained joins in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 3 ~ 9 layers that step c) obtains, the wherein mole total amount of six sodium alkyl benzene sulfonates in step b), ten alkyl sodium sulfonates and ten sodium alkyl sulfates: the aniline in step b): the mol ratio of iron trichloride is 1:1:2; At 60 ℃, continue to stir 0.2 hour, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline.Gained spirane structure polyaniline is to be 40 ~ 80nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 2 ~ 7 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 100 ~ 220nm, and length is 1 ~ 4 μ m, and pitch is 40 ~ 80nm.
Embodiment 6
A) preparation surface active agent emulsions: by hexadecyl sulfonic acid and sodium cetanesulfonate in molar ratio 1:1 be dissolved in deionized water, fully stir 0.5 ~ 2 hour, obtaining volumetric molar concentration is the hexadecyl sulfonic acid of 0.5mol/L and the mixed emulsion of sodium cetanesulfonate;
B) preparation aniline solution: aniline is dissolved in the toluene and sym-trimethylbenzene of mol ratio 1:1, fully stirs and obtain the aniline solution that volumetric molar concentration is 7.5mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the mixed emulsion of hexadecyl sulfonic acid that step a) obtains and sodium cetanesulfonate, and then add Virahol to obtain reaction system, wherein: in every liter of reaction system, mole total amount of hexadecyl sulfonic acid and sodium cetanesulfonate and the mol ratio of aniline are 1:0.5, and the volumetric molar concentration of Virahol is 1mol/L; At room temperature continue to stir 0.5 hour, obtain the reaction system that contains the vesica soft template being formed by the vesica layer overlaps of 5 ~ 10 layers; The size of described vesica soft template is 180 ~ 300nm;
D) preparation oxidizing agent solution: Potcrate is dissolved in deionized water, obtains the potassium chlorate solution that volumetric molar concentration is 3mol/L;
E) continuing under stirring, the potassium chlorate solution that step d) is obtained joins in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 5 ~ 10 layers that step c) obtains, the wherein mole total amount of the hexadecyl sulfonic acid in step b) and sodium cetanesulfonate: the aniline in step b): the mol ratio of Potcrate is 1:0.5:0.5; At room temperature continue to stir 12 hours, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline.Gained spirane structure polyaniline is to be 40 ~ 60nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 1 ~ 5 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 100 ~ 150nm, and length is 1 ~ 3 μ m, and pitch is 40 ~ 60nm.
Embodiment 7
A) preparation surface active agent emulsions: by six alkyl benzene sulphonate (ABS)s, ten alkylsurfuric acids, hexadecyl benzene sulfonic acid sodium salt and sodium stearyl sulfate in molar ratio 1:1:1:1 be dissolved in deionized water, fully stir 0.5 ~ 2 hour, obtaining volumetric molar concentration is the mixed emulsion of six alkyl benzene sulphonate (ABS)s, ten alkylsurfuric acids, hexadecyl benzene sulfonic acid sodium salt and the sodium stearyl sulfate of 0.6mol/L;
B) preparation aniline solution: aniline is dissolved in the ethylbenzene and diethylbenzene of mol ratio 1:1, fully stirs and obtain the aniline solution that volumetric molar concentration is 5mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the mixed emulsion of six alkyl benzene sulphonate (ABS)s, ten alkylsurfuric acids, hexadecyl benzene sulfonic acid sodium salt and sodium stearyl sulfate that step a) obtains, and then add the methyl alcohol of mol ratio 1:1 and ethanol to obtain reaction system, wherein: in every liter of reaction system, mole total amount of six alkyl benzene sulphonate (ABS)s, ten alkylsurfuric acids, hexadecyl benzene sulfonic acid sodium salt and sodium stearyl sulfate and the mol ratio of aniline are 1:1.5, and mole total concn of methyl alcohol and ethanol is 0.7mol/L; At room temperature continue to stir 1 hour, obtain the reaction system that contains the vesica soft template being formed by the vesica layer overlaps of 2 ~ 7 layers; The size of described vesica soft template is 120 ~ 250nm;
D) preparation oxidizing agent solution: the Potassium Iodate of mol ratio 1:1 and potassium bromate are dissolved in deionized water, and obtaining volumetric molar concentration is the Potassium Iodate of 0.5mol/L and the mixing solutions of potassium bromate;
E) continuing under stirring, the Potassium Iodate that step d) is obtained and the mixing solutions of potassium bromate join in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 2 ~ 7 layers that step c) obtains, the wherein mole total amount of six alkyl benzene sulphonate (ABS)s in step b), ten alkylsurfuric acids, hexadecyl benzene sulfonic acid sodium salt and sodium stearyl sulfate: the aniline in step b): the mol ratio of mole total amount of Potassium Iodate and potassium bromate is 1:1.5:1.5; At room temperature continue to stir 1 hour, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline.Gained spirane structure polyaniline is to be 60 ~ 80nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 5 ~ 9 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 150 ~ 220nm, and length is 2 ~ 5 μ m, and pitch is 60 ~ 80nm.
Embodiment 8
A) preparation surface active agent emulsions: by ten alkylsulphonic acids, dodecyl sodium sulfonate and dodecyl sulphate in molar ratio 1:1:1 be dissolved in deionized water, fully stir 0.5 ~ 2 hour, obtaining volumetric molar concentration is the mixed emulsion of ten alkylsulphonic acids, dodecyl sodium sulfonate and the dodecyl sulphate of 0.4mol/L;
B) preparation aniline solution: aniline is dissolved in the oil of mirbane and dinitrobenzene of mol ratio 1:1, fully stirs and obtain the aniline solution that volumetric molar concentration is 5mol/L;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the mixed emulsion of ten alkylsulphonic acids, dodecyl sodium sulfonate and dodecyl sulphate that step a) obtains, and then add the n-propyl alcohol of mol ratio 1:1 and Virahol to obtain reaction system, wherein: in every liter of reaction system, mole total amount of ten alkylsulphonic acids, dodecyl sodium sulfonate and dodecyl sulphate and the mol ratio of aniline are 1:2, and mole total concn of n-propyl alcohol and Virahol is 0.8mol/L; At room temperature continue to stir 2 hours, obtain the reaction system that contains the vesica soft template being formed by the vesica layer overlaps of 1 ~ 6 layer; The size of described vesica soft template is 100 ~ 250nm;
D) preparation oxidizing agent solution: the Potassium Persulphate of mol ratio 1:1 and ammonium persulphate are dissolved in deionized water, and obtaining volumetric molar concentration is the Potassium Persulphate of 0.5mol/L and the mixing solutions of ammonium persulphate;
E) continuing under stirring, the Potassium Persulphate that step d) is obtained and the mixing solutions of ammonium persulphate join in the reaction system that contains the vesica soft template being made up of the vesica layer overlaps of 1 ~ 6 layer that step c) obtains, the wherein mole total amount of ten alkylsulphonic acids, dodecyl sodium sulfonate and the dodecyl sulphate in step b): the aniline in step b): the mol ratio of mole total amount of Potassium Persulphate and ammonium persulphate is 1:2:2; At room temperature continue to stir 0.5 hour, obtain containing the blackish green mixed solution of composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually;
F) in the blackish green mixed solution that contains composite structure polyaniline, left-handed structure polyaniline and dextrorotation structure polyaniline that left-handed structure and dextrorotation structure be wound around mutually obtaining in step e), add is that the ethanol of described 5 times of volumes of blackish green mixed solution washs, then blackish green gained filter cake being joined is to wash in the deionized water of 5 times of volumes of the blackish green filter cake of gained, obtains the blackish green filter cake of finished product after filtration; By the vacuum-drying 24 hours at 60 ℃ of blackish green finished product obtaining filter cake, obtain blackish green powder, be spirane structure polyaniline.Gained spirane structure polyaniline is to be 60 ~ 100nm by an above diameter, length is the spirane structure that the polyaniline nano fiber of 4 ~ 10 μ m is entwined, and described spirane structure is composite structure, left-handed structure and the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 120 ~ 250nm, and length is 2 ~ 5 μ m, and pitch is 60 ~ 100nm.
Comparative example 1
Preparation method and condition are identical with embodiment 1, just the Witco 1298 Soft Acid in step a) are replaced to p-methyl benzenesulfonic acid, and product is the polyaniline nano fiber that there is no spirane structure.
Comparative example 2
Preparation method and condition are identical with embodiment 1, just the dimethylbenzene in step b) are replaced to chloroform, and product is the broken polyaniline nano fiber fragment that there is no spirane structure.
Comparative example 3
Preparation method and condition are identical with embodiment 1, just the ammonium persulphate in step d) are replaced to potassium bichromate, and product is the polyaniline nano particle that there is no spirane structure.
Comparative example 4
Preparation method and condition are identical with embodiment 1, just the n-propyl alcohol in step c) are replaced to deionized water, and product is the polyaniline nano fiber group that there is no spirane structure.
Embodiment 9
By the non-helical structure polyaniline of the spirane structure polyaniline of embodiment 1 ~ 8 gained, comparative example 1 ~ 4 gained, mix with urethane resin (model: WPU2802, Zhuhai Ji Li chemical enterprise company limited) respectively, be mixed with antistatic coating.Wherein, the mass ratio of spirane structure polyaniline and non-helical structure polyaniline and urethane resin is respectively 1:5.Gained antistatic coating is adopted respectively to mode film on plastic base of the excellent film of silk, after drying, the thickness of rete is all 1.2 μ m, and the surface resistivity of testing them is as shown in table 1.Testing tool is DESCO19780 Weight type surface resistivity tester, and test specification is 10
3~ 10
12Ω/sq, measuring error 5%.The surface resistivity of antistatic coating prepared by the spirane structure polyaniline in the present invention is low to moderate 10
6Ω/sq, is better than antistatic coating prepared by the non-helical structure polyaniline in comparative example.
Antistatic coating Performance Ratio prepared by table 1 different polyaniline
| Embodiment | Surface resistivity (Ω/sq) | Comparative example | Surface resistivity (Ω/sq) |
| Embodiment 1 | 6.2×10 6 | Comparative example 1 | 7.4×10 7 |
| Embodiment 2 | 2.4×10 6 | Comparative example 2 | 2.3×10 9 |
| Embodiment 3 | 9.0×10 6 | Comparative example 3 | 3.1×10 8 |
| Embodiment 4 | 3.7×10 6 | Comparative example 4 | 5.6×10 7 |
| Embodiment 5 | 8.2×10 6 | ? | ? |
| Embodiment 6 | 1.3×10 7 | ? | ? |
| Embodiment 7 | 7.8×10 6 | ? | ? |
| Embodiment 8 | 3.5×10 6 | ? | ? |
Embodiment 10
After being dried respectively, the non-helical structure polyaniline of the spirane structure polyaniline of embodiment 1 ~ 8 gained, comparative example 1 ~ 4 gained is finely ground to powder, and by 120 object sieve, powder after sieving is dispersed in respectively to epoxy resin (Phoenix brand epoxy resin, standard No.: Q/320201NG047, Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd.) in, obtain absorbing material, wherein spirane structure polyaniline and non-helical structure polyaniline are all to account for 20% of solid content in absorbing material.It is on the aluminium sheet that the 3mm of 180 × 180mm is thick that the absorbing material obtaining is coated in respectively to size, all obtains the film that 2mm is thick after dry solidification, and test absorbing material is the absorbing property on 2 ~ 18GHz frequency band at hertzian wave, as shown in table 2.Testing tool is HP8722ES vector network analyzer, and this instrument is the electromagnetic parameter of measuring material by grid method.Absorbing material prepared by spirane structure polyaniline of the present invention is on 2 ~ 18GHz frequency band, to have good absorbing property at hertzian wave, is better than the absorbing material that in comparative example prepared by non-helical structure polyaniline.
Absorbing material performance comparison prepared by table 2 different polyaniline
Claims (10)
1. a preparation method for spirane structure polyaniline, is characterized in that, described preparation method comprises the following steps:
A) preparation surface active agent emulsions: tensio-active agent is dissolved in deionized water, fully stirs and obtain the surface active agent emulsions that volumetric molar concentration is 0.4 ~ 0.75mol/L;
Described tensio-active agent is selected from one or more in alkyl benzene sulphonate (ABS), alkylbenzene sulfonate, alkylsulphonic acid, alkylsulfonate, alkylsurfuric acid, alkyl-sulphate; Wherein, the number of the carbon atom of described alkyl is 6 ~ 18;
B) preparation aniline solution: aniline is dissolved in organic solvent, fully stirs and obtain the aniline solution that volumetric molar concentration is 0.8 ~ 10mol/L;
Described organic solvent is selected from one or more in benzene, toluene, ethylbenzene, propyl benzene, dimethylbenzene, diethylbenzene, sym-trimethylbenzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, oil of mirbane, dinitrobenzene;
C) continuing under stirring, the aniline solution that step b) is obtained joins in the surface active agent emulsions that step a) obtains, and then add short chain fatty alcohol to obtain reaction system, wherein: in every liter of reaction system, the mol ratio of tensio-active agent and aniline is 1:0.5 ~ 1:5, and the volumetric molar concentration of short chain fatty alcohol is 0.4 ~ 1.2mol/L; Continue to stir, obtain the reaction system that contains vesica soft template;
D) preparation oxidizing agent solution: oxygenant is dissolved in deionized water, obtains the oxidizing agent solution that volumetric molar concentration is 0.2 ~ 3mol/L;
E) under continuing to stir, the oxidizing agent solution that step d) is obtained joins in the reaction system that contains vesica soft template that step c) obtains, and wherein the mol ratio of the aniline in oxygenant and step b) is 1:0.5 ~ 1:5; Continue to stir, obtain the blackish green mixed solution that contains spirane structure polyaniline;
F) in the blackish green mixed solution that contains spirane structure polyaniline obtaining in step e), add short chain fatty alcohol to carry out washing and filtering, then gained filter cake is joined in deionized water and washed, after filtration, be dried, obtain spirane structure polyaniline.
2. preparation method according to claim 1, is characterized in that: described vesica soft template is that the vesica that is 1 ~ 10 layer by the number of plies of one deck cover one deck forms; The size of described vesica soft template is 100 ~ 300nm.
3. preparation method according to claim 1, is characterized in that: the tensio-active agent in every liter of reaction system described in step c) and the mol ratio of aniline are 1:0.5 ~ 1:2, and the volumetric molar concentration of short chain fatty alcohol is 0.6 ~ 1mol/L.
4. according to the preparation method described in claim 1 or 3, it is characterized in that: described short chain fatty alcohol is selected from one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol.
5. preparation method according to claim 1, is characterized in that: the temperature when continuation described in step e) is stirred is 0 ~ 60 ℃.
6. preparation method according to claim 1, is characterized in that: described alkyl benzene sulphonate (ABS) is selected from one or more in six alkyl benzene sulphonate (ABS)s, ten alkyl benzene sulphonate (ABS)s, Witco 1298 Soft Acid, tetradecyl Phenylsulfonic acid, hexadecyl Phenylsulfonic acid, octadecyl Phenylsulfonic acid;
Described alkylbenzene sulfonate is selected from one or more in six alkylbenzene sulfonates, ten alkylbenzene sulfonates, dodecylbenzene sulfonate, tetradecyl benzene sulfonate, hexadecyl benzene sulfonate, octadecyl benzene sulfonate;
Described alkylsulphonic acid is selected from one or more in ten alkylsulphonic acids, undecyl sulfonic acid, dodecyl sodium sulfonate, tridecyl sulfonic acid, tetradecyl sulfonic acid, pentadecyl sulfonic acid, hexadecyl sulfonic acid;
Described alkylsulfonate is selected from one or more in ten alkylsulfonates, undecyl sulfonate, dodecane sulfonate, tridecyl sulfonate, tetradecyl sulfonate, pentadecane sulfonate, hexadecyl sulfonate;
Described alkylsurfuric acid is selected from one or more in ten alkylsurfuric acids, undecyl sulfuric acid, dodecyl sulphate, tridecyl sulfuric acid, tetradecyl sulfuric acid, hexadecyl hydrosulfate, octadecyl sulfuric acid;
Described alkyl-sulphate is selected from one or more in ten alkyl-sulphates, undecyl sulfates, dodecyl sulfate, tridecyl vitriol, tetradecyl sulfate, cetyl sulfate, octadecyl vitriol.
7. preparation method according to claim 1, is characterized in that: described oxygenant is selected from one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Potassium Iodate, potassium bromate, Potcrate, iron trichloride, hydrogen peroxide.
8. the spirane structure polyaniline being obtained by the preparation method of the spirane structure polyaniline described in claim 1 ~ 7 any one, it is characterized in that: described spirane structure polyaniline is to be entwined by an above polyaniline nano fiber, and described spirane structure is composite structure, left-handed structure or the dextrorotation structure that left-handed structure and dextrorotation structure are wound around mutually; The diameter of described spirane structure is 100 ~ 300nm, and length is 0.5 ~ 5 μ m, and pitch is 40 ~ 100nm.
9. spirane structure polyaniline according to claim 8, is characterized in that: the diameter of described polyaniline nano fiber is 40 ~ 100nm, and length is 1 ~ 10 μ m.
10. a purposes for spirane structure polyaniline according to claim 9, is characterized in that: described spirane structure polyaniline uses for the preparation of antistatic material, absorbing material and electrode materials.
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| CN108729027A (en) * | 2018-05-31 | 2018-11-02 | 浙江理工大学 | A kind of polyaniline fiber wave-absorber system and preparation method thereof |
| CN112500564A (en) * | 2020-11-09 | 2021-03-16 | 武汉纺织大学 | Metal ion mediated chiral nano material, carbon-containing nano material and preparation method |
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| CN108729027B (en) * | 2018-05-31 | 2020-06-16 | 浙江理工大学 | Polyaniline fiber wave-absorbing system |
| CN112500564A (en) * | 2020-11-09 | 2021-03-16 | 武汉纺织大学 | Metal ion mediated chiral nano material, carbon-containing nano material and preparation method |
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