The preparation of full dissolubility different molecular weight polyaniline and derivative thereof
The invention belongs to the polyaniline (PAn) with different molecular weight and the technology of preparing of derivative thereof.
At present, the research of polyaniline has entered applicationization eve, but also there are some shortcomings in existing synthetic method: 1. the polyaniline powder of preparation always has the part insolubles usually; 2. control of polyaniline and derivative molecular amount thereof etc.People such as Chinese patent 87104602 Wang Li samples disclose a kind of method for preparing soluble polyaniline and derivative thereof, this method is with water as solvent, and in polymerization system, add former dose of FeSO4, CuSO4 etc., and products therefrom carried out acidolysis or alkaline hydrolysis, obtain the complete solvable or partly soluble polyaniline and the derivative thereof of eigenstate, its shortcoming is a complex technical process, effective controlling polymers molecular weight, and solvability is also not ideal enough.
The objective of the invention is to adopt water, organic solvent mixed solvent is reaction system, with oxygenant aromatic amine is carried out reductionoxidation polymerization, without the polyaniline with different molecular weight and the derivative thereof of the synthetic high resolution of any aftertreatment, and original conductivity that do not scatter and disappear.
Polymerization system of the present invention is made of following component: 1. aromatic amine, and its general formula is:
Wherein R is-H ,-CH
3,-C
2H
5,-C
6H
13,-OCH
3,-OC
2H
5,-Cl ,-NO
2
2. oxygenant can be H
2O
2, KClO
3, KIO
3, PbO
2, FeCl
3, (NH
4)
2S
2O
8, K
2Cr
2O
7, KMnO
4, HPtCl
6, HPtF
6Wherein with (NH
4)
2S
2O
8, KClO
3, KIO
3, H
2O
2Best.
3. acid comprises mineral acid: H
2SO
4, HCl, H
3PO
4, HClO
4Organic sulfonic acid: tosic acid, camphorsulfonic acid, methylsulphonic acid, Witco 1298 Soft Acid, 1,5-naphthalene disulfonic acid, sulfosalicylic acid; Organic phosphoric acid monoesters and dibasic acid esters: one or dialkyl phosphate, one or the dialkoxy phosphoric acid ester.Wherein with HCl and tosic acid the best.
4. organic solvent is an alcohol: methyl alcohol, ethanol, propyl alcohol, butanols, ketone: acetone, butanone, pimelinketone, aromatic hydrocarbon: benzene, toluene, dimethylbenzene, tetrahydrofuran (THF), N-Methyl pyrrolidone, the inferior phenol of diformazan, dimethyl formamide, trichloromethane, normal hexane, perhydronaphthalene.Wherein with ethanol, acetone, tetrahydrofuran (THF), dimethyl formamide the best.
Polymerization is mixed by a certain percentage by above component, and water/organic solvent ratio (V/V) is between 1/99-99/1, and aromatic amine concentration is 0.5mole/L, amine, oxygenant mol ratio are 1: 1, temperature of reaction-40-50 ℃, time 2-24 hour, the polymkeric substance that obtains thus was Powdered or emulsion.
Can regulate polymer molecular weight by following method:
1. change polymerization temperature, low temperature polymerization helps forming the high-molecular weight product
2. change the ratio of organic solvent/water, different organic solvents influences the trend difference to polymericular weight, but all can play the effect of regulating molecular weight
After polymerization is finished, miscellany is filtered (emulsion methanol extraction), be washed till the colourless and free from foreign meter ion of filtrate with polymerization with acidic aqueous solution and acetone respectively, then successively with 1mole/L, 0.5mole/L ammoniacal liquor be washed till the complete contra-doping of polymkeric substance and filtrate does not contain original acid ion and foreign ion, it is neutral being washed till filtrate with distilled water at last, and vacuum 40-50 ℃ was descended dry 72 hours, and obtained polyaniline in eigenstate and derivative thereof.This polymkeric substance is dissolved in N-Methyl pyrrolidone, and film forming under infrared lamp can make large-area self-supported membrane, through I
2, HCl, HClO
4, H
2SO
4, CF
3COOH, to first and Phenylsulfonic acid, camphorsulfonic acid, Na, after K etc. mix, conductivity=3.7 * 10
1~1.0 * 10
-3S/cm.
Method of the present invention is the controlling polymers molecular weight effectively, is not increasing Operating Complexity and need not carry out just can making the different polymkeric substance of molecular weight under the situation of aftertreatment.Reduced viscosity (η sp/C with the N-Methyl pyrrolidone solution of its 0.1wt%
0.1) do the criterion of molecular weight size, but reduced viscosity circle (it is standard that following polymericular weight all is worth with this) between 0.1-2.0.
The polymkeric substance of method preparation of the present invention dissolves in a series of organic solvent, is example with the polyaniline, has realized first that in the resulting polymers molecular weight ranges polyaniline can be dissolved in N-Methyl pyrrolidone entirely.The polyaniline of this method preparation or substituted aniline have identical structure with the polymkeric substance of usual way preparation, and the polymkeric substance that has than the usual way preparation through the sour adulterated film of difference equates or slightly excellent specific conductivity.
Method of the present invention not only can be prepared the polyaniline that is dissolved in N-Methyl pyrrolidone entirely, and can prepare and be dissolved in methyl-sulphoxide entirely, be partially soluble in acetone, chloroform, the polyaniline of weak polar solvents such as tetrahydrofuran (THF), and building-up process does not have additional step and aftertreatment, does not change the structure and the composition of polymkeric substance fully.
Method of the present invention is easy, easy to implement, as long as change the ratio between the each component, the controlled polymerization temperature, can synthesize full dissolubility polyaniline and derivative thereof with different molecular weight, and electroconductibility can not reduce, because temperature of reaction and component ratio are controlled easily, is applicable to production in enormous quantities, by changing the collocation between component and the each component, the granularity of going back the may command polymkeric substance.
The embodiment of the invention 1:
Use the acetone solution dilution to 200ml the dense HCl of 30ml, add 11.9ml aniline, this miscellany is injected three mouthfuls of vials of 500ml, under vigorous stirring, in 30 minutes, add 60ml (NH
4)
2S
2O
8The aqueous solution (contains 22.64g (NH
4)
2S
2O
8, continue reaction 6 hours.Whole process temperature is controlled at 15~20 ℃ with water-bath.After reaction finishes, miscellany week G
4Sand core funnel filters, and product is through 1mole/L hydrochloric acid, washing with acetone, 1mole/L, 0.5mole/L ammoniacal liquor contra-doping, after distilled water is washed till neutral and vacuum-drying, intrinsic can be dissolved in the polyaniline of N-Methyl pyrrolidone entirely, A wherein, B can be dissolved in the methyl-sulphoxide entirely.The performance of the different resulting polymers of acetone content is listed in the table below:
The parameter of polymkeric substance when table .1 acetone is solvent
Acetone/solution (V/V) η
Sp/ C
0.1Productive rate, (%) electrical conductivity, (S/cm) reaction temperature, (℃) A 1/1 0.273 62 2.5 20 B 2/3 0.167 56 2.0 20 C 1/2 0.329 75 10.7 20 D 1/3 0.396 76 14.5 20 E 1/4 0.462 74 21.0 20 F 1/4 1.225 67 25.2-40 embodiment of the invention 2:
Replace acetone with ethanol, other component is with embodiment 1, and under certain polymerization temperature, resulting polymers has following character (table 2):
Above method gained sample all dissolves in the N-Methyl pyrrolidone, sample A wherein, and E can be dissolved in the methyl-sulphoxide entirely.The embodiment of the invention 3:
Replace acetone with tetrahydrofuran (THF), other component changes tetrahydrofuran (THF)/water volume ratio, resulting polymers parameter such as table 3 with embodiment 1:
The parameter of polymkeric substance when table 2 ethanol/water is solvent
Ethanol/solution (V/V) η
Sp/ C
0.1Productive rate, (%) membrane conductivity, (S/cm) reaction temperature, (℃) A 1/1 0.302 70 5.0 20 B 2/3 0.350 71 7.8 20 C 1/2 0.457 75 6.3 20 D 1/4 0.480 73 9.2 20 E 1/1 0.253 60 0.79 50 F 1/3 0.669 70 20.0-20 G 1/4 1.523 65 27.1-40
The parameter of polymkeric substance when table 3 tetrahydrofuran (THF)/water is solvent
Tetrahydrofuran (THF)/solution (V/V) η
Sp/
C0.1Productive rate, (%) membrane conductivity, (S/cm) reaction temperature, (℃) A 1/1 0.223 65 1.72 20 B 2/3 0.200 60 7.79 20 C 1/2 0.392 72 11.4 20 D 1/3 0.349 69 11.8 20 E 1/4 0.400 71 22.7 20 F 1/4 1.027 64 31.3-40
Above method gained sample all can be dissolved in the N-Methyl pyrrolidone entirely, sample A wherein, and B can be dissolved in the methyl-sulphoxide entirely.The embodiment of the invention 4:
Adopt embodiment 2-F solvent system, acid is H
2SO
4, oxygenant KClO
3, add the 12ml o-toluidine and carry out polymerization, 10 hours reaction times, productive rate=72%, membrane conductivity σ=5 * 10
-3S/cm, η
Sp/ C
0.1=0.610.Polymkeric substance can be dissolved in N-methyl pyrrole alkane ketone, dimethyl formamide, methyl-sulphoxide, tetrahydrofuran (THF) entirely, and is complete molten or be partially soluble in chloroform.The embodiment of the invention 5:
Adopt embodiment 2-F solvent system, acid is camphorsulfonic acid, oxygenant H
2O
2, add the 15ml ORTHO ANISIDINE and carry out polymerization, 12 hours reaction times, productive rate=60%, membrane conductivity σ=1.7 * 10
-2S/cm, η
Sp/ C
0.1=0.550.Polymkeric substance can be dissolved in N-Methyl pyrrolidone, dimethyl formamide, methyl-sulphoxide, tetrahydrofuran (THF) entirely.The embodiment of the invention 6:
Replace acetone with dimethyl formamide, replace HCl with Witco 1298 Soft Acid, the component proportioning is with embodiment 2-D, and dimethyl formamide/solution (V/V) is 1/4, polymerization yield rate=74%, membrane conductivity σ=17.1S/cm, η
Sp/ C
0.1=0.717.Resulting polymers can be dissolved in N-Methyl pyrrolidone entirely, is partially soluble in dimethyl formamide, methyl-sulphoxide.The embodiment of the invention 7:
Replace HCl with tosic acid, in 18 hours reaction times, other is with embodiment 6, resulting polymers productive rate=70%, η
Sp/ C
0.1=0.654, membrane conductivity σ=20S/cm, solvability is with embodiment 6.The embodiment of the invention 8:
With KIO
3Make oxygenant, tosic acid is used in acid, and other is with embodiment 3-F, and in 24 hours reaction times, resulting polymers has identical solvability, productive rate=72%, membrane conductivity σ=15.6S/cm, η
Sp/ C
0.1=0.652.The embodiment of the invention 9:
With 1, the 5-naphthalene disulfonic acid replaces HCl, and in 2 hours reaction times, other is with embodiment 2-D, products therefrom productive rate=45%, η
Sp/ C
0.1=0.543, membrane conductivity σ=15S/cm, solvability is with embodiment 6.