CN101643544A - Sulfonated polyaniline and a preparation method thereof - Google Patents
Sulfonated polyaniline and a preparation method thereof Download PDFInfo
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- CN101643544A CN101643544A CN200910018334A CN200910018334A CN101643544A CN 101643544 A CN101643544 A CN 101643544A CN 200910018334 A CN200910018334 A CN 200910018334A CN 200910018334 A CN200910018334 A CN 200910018334A CN 101643544 A CN101643544 A CN 101643544A
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Abstract
The invention relates to sulfonated polyaniline which is a block copolymer with a sulfonated aniline chain segment and an aniline chain segment and has good electrical conductivity and heat resistance, heat decomposition temperature more than 400 DEG C and electrical conductivity higher than or equal to 10<-1> S/cm. A stepwise polymerization method is used for preparing the sulfonated polyanilinewith the electrical conductivity and the heat resistance and comprises the following steps: preparing a sulfonated aniline prepolymer under an alkaline condition; and then copolymerizing the sulfonated aniline prepolymer and an aniline monomer to obtain the sulfonated polyaniline in a block structure under an acidic condition. The invention has easy material obtaining, simple synthesis technology,little environment pollution and easy industrialized production; and in addition, the sulfonated polyaniline can be melted and mixed with thermoplastic resin with good mechanical property and processable property to form materials, i.e. an organic electromagnetic shielding polymer, coating, a special separation membrane, and the like.
Description
One, technical field
The invention belongs to the macromolecular material synthesis technical field, relate to conducting polymer composite, relate to heat-resisting conducting polymer composite simultaneously, also relate to heat-resisting conducting polymer composite preparation method.
Two, background technology
As conducting polymer composite, polyaniline is one of most important member.The general electroconductibility that adopts outer dopant acid to improve polyaniline, still the decomposition temperature of the electrically conductive polyaniline that obtains of this method about 120 ℃, poor heat stability, processibility is restricted.
The traditional relatively polyaniline of sulfonated polyaniline has excellent heat resisting, and the conventional method for preparing sulfonated polyaniline mainly contains the homopolymerization of polyaniline sulfonation and sulfonation aniline monomer, but the sulfonated polyaniline conductivity that ordinary method makes is relatively poor.
People such as Yue adopt oleum p-poly-phenyl amine to carry out sulfonation and obtain sulfonated polyaniline (Polymer, 1992,33:4410), imino-on the sulfonic acid group p-poly-phenyl amine chain mixes, its specific conductivity is about 0.1S/cm, thereby lose conductivity but lose to mix after its dissolving, using value is restricted greatly.
People such as Varela (Chem Soc, 2000,11:32) EB-PAN is carried out the alkane sulfonation reaction, obtain N-position propane sulfonic acid substituted polyaniline, electrical conductivity at room temperature is 10
-2S/cm begins to decompose dedoping at 170 ℃, and thermotolerance is unsatisfactory.
People (Kitani A et al.Synthetic Metals, 1995,69:129 such as Kitani A; Fan JH et al.Chinese Journal of Polymer Science, 1999,17:165) once reported sucting electronic effect because of sulfonic acid group, the monomer oxidation activity reduces, synthetic sulfonated polyaniline molecular weight is lower under general acidic conditions, product often disperses with nano-scale particle in reaction medium and forms colloid, is difficult to obtain separable solid product, does not have practical value.
People (Synthetic Metals such as A.Timothy Royappa, 2001,123:273) introduced a kind of homopolymerization sulfonated polyaniline, after below 10 ℃ 4-aminodiphenylamine-2-sulfonic acid being dissolved in sodium hydroxide solution, adding excessive hydrochloric acid solution and ammonium persulphate and issue biochemical oxidizing reaction for 0～10 ℃ at acidic conditions, is 1.3 * 10 with the sulfonated polyaniline specific conductivity that obtains after deionized water and the HCl solution washing product drying
- 5S/cm, thermotolerance is not quite clear.
Three, summary of the invention
The object of the present invention is to provide a kind of sulfonated polyaniline that has good heat resistance and electroconductibility concurrently and preparation method thereof.
The object of the present invention is achieved like this, from the molecular designing angle, adopt sulfonation aniline and aniline step-by-step polymerization to obtain having the sulfonated polyaniline of block structure, sulfonation aniline segment provides good thermotolerance, the aniline segment provides good electrical properties, thereby obtains having concurrently the sulfonated polyaniline of good thermal characteristics and conductivity.
The sulfonated polyaniline that the present invention relates to is for having sulfonation aniline segment and aniline segmental segmented copolymer, and sulfonation degree (the mol ratio S/N of sulphur nitrogen two elements) is 0.1～0.7, and heat decomposition temperature is not less than 400 ℃, and specific conductivity is not less than 10
-1S/cm.
The sulfonated polyaniline that the present invention relates to, described sulfonation aniline segment are selected from a kind of or wherein several mixture in ORTHO AMINO PHENOL SULPHONIC, m-sulfanilic acid, Sulphanilic Acid, the 4-aminodiphenylamine-2-sulfonic acid segment.
The preparation method of the sulfonated polyaniline that the present invention relates to, adopt the step-by-step polymerization mode, the pre-polymerization of sulfonation aniline monomer obtains sulfonation aniline performed polymer under alkaline condition, obtains having the sulfonated polyaniline of block structure then under acidic conditions with the aniline monomer copolymerization, and processing step comprises at least:
(1) with alkaline aqueous solution dissolving sulfonation aniline, obtains sulfonation aniline monomer solution A;
(2) under 0～20 ℃ of condition, use the acidic aqueous solution dissolved oxidant, obtain oxidizing agent solution B;
(3) under 0～20 ℃ of condition, the oxidizing agent solution B with 10%～80% is added drop-wise among the monomer solution A, uses alkaline aqueous solution regulation system pH value simultaneously, keeps pH value and react 1～5h between 7～9, obtains sulfonation aniline prepolymer solution C;
(4) under 0～20 ℃ of condition, the oxidizing agent solution B of surplus is added among the prepolymer solution C, drip aniline monomer, use acidic aqueous solution regulation system pH value simultaneously, keep pH value and between 4～6, react 2～8h, obtain multipolymer suspension system D, filter, filter cake obtains sulfonated polyaniline through washing, drying.
The sulfonated polyaniline synthetic method that the present invention relates to, the oxygenant that uses are selected from a kind of in ammonium persulphate, the potassium bichromate.
The sulfonated polyaniline synthetic method that the present invention relates to, the alkaline aqueous solution that uses are selected from a kind of in sodium hydroxide, the potassium hydroxide aqueous solution.
The sulfonated polyaniline synthetic method that the present invention relates to, the acidic solution that uses are selected from a kind of in hydrochloric acid, the sulfuric acid.
The sulfonated polyaniline synthetic method that the present invention relates to adopts sulfonation aniline monomer and aniline monomer block copolymerization to obtain, and raw material is easy to get, synthesis technique is simple, environmental pollution is little, be easy to suitability for industrialized production.
The sulfonated polyaniline of the synthetic method preparation that the present invention relates to has good electrical conductivity and thermotolerance, and specific conductivity is 10
-1More than the S/cm, heat decomposition temperature is higher than 410 ℃, can carry out melt blending by the thermoplastic resin that it is good with having excellent mechanical performances and processability, is formed with materials such as dynamo-electric magnetic shielding polymkeric substance, coating, special separatory membrane.
Four, specific implementation method
Embodiment one
The 1mo1 ORTHO AMINO PHENOL SULPHONIC is joined the 200mL deionized water and 0.8mL concentration is in the sodium hydroxide solution of 1.0mol/L, mechanical stirring is finished the dissolving to ORTHO AMINO PHENOL SULPHONIC, obtains solution A;
At 10～20 ℃, the 2mol ammonium persulphate is joined in the sulphuric acid soln that 20mL concentration is 0.8mol/L, mechanical stirring is finished the dissolving to ammonium persulphate, obtains solution B;
Get 80% solution B and be added dropwise in the solution A, transferring the solution pH value with 1.0mol/L potassium hydroxide simultaneously is between 7～8, and at 10～15 ℃, reaction 1h obtains ORTHO AMINO PHENOL SULPHONIC prepolymer solution C;
Under mechanical stirring at the uniform velocity, remaining 20%B drips of solution is added in the solution C, and dropping 8mol aniline monomer, transferring the solution pH value with 1.0mol/L hydrochloric acid simultaneously is between 5～6, continue reaction 6h, filter, behind deionized water and washing with acetone, 100 ℃ of dryings obtain the target product sulfonated polyaniline in vacuum drying oven.
The sulfonation degree of this sulfonated polyaniline is 0.10, and heat decomposition temperature is 415 ℃, and specific conductivity is 0.17S/cm.
Embodiment two
The 3mol m-sulfanilic acid is joined the 350mL deionized water and 1mL concentration is in the sodium hydroxide solution of 1.3mol/L, mechanical stirring is finished the dissolving to m-sulfanilic acid, obtains solution A;
At 5～10 ℃, the 5mol ammonium persulphate is joined in the hydrochloric acid soln that 30mL concentration is 1.0mol/L, mechanical stirring is finished the dissolving to ammonium persulphate, obtains solution B;
Get 50% solution B and be added dropwise in the solution A, transferring the solution pH value with 1.5mol/L sodium hydroxide simultaneously is 8～9, and at 0～5 ℃, reaction 2h obtains m-sulfanilic acid prepolymer solution C;
Under mechanical stirring at the uniform velocity, remaining 50% solution B is added drop-wise in the solution C, and be added dropwise to the 1mol aniline monomer, transferring the solution pH value with 1.0mol/L hydrochloric acid simultaneously is 5～6, continue reaction 4h, filter, behind deionized water and washing with acetone, 100 ℃ of dryings obtain the target product sulfonated polyaniline in vacuum drying oven.
The sulfonation degree of this sulfonated polyaniline is 0.71, and heat decomposition temperature is 439 ℃, and specific conductivity is 0.67S/cm.
Embodiment three
The 5mol Sulphanilic Acid is joined the 650mL deionized water and 3mL concentration is in the potassium hydroxide solution of 0.9mol/L, mechanical stirring is finished the dissolving to Sulphanilic Acid, obtains solution A;
At 0～5 ℃, 1mol potassium permanganate is joined in the hydrochloric acid soln that 25mL concentration is 1.2mol/L, mechanical stirring is finished the dissolving to potassium permanganate, obtains solution B;
Get 10% solution B and be added dropwise in the solution A, transferring the solution pH value with 0.9mol/L sodium hydroxide simultaneously is 7～8, and at 10～15 ℃, reaction 3h obtains Sulphanilic Acid prepolymer solution C;
Under mechanical stirring at the uniform velocity, remaining 90% solution B is added dropwise to solution C, and dropping 7mol aniline monomer, transferring the solution pH value with 1.0mol/L sulfuric acid simultaneously is 6～7, continue reaction 4.5h, filter, behind deionized water and washing with acetone, 100 ℃ of dryings obtain the target product sulfonated polyaniline in vacuum drying oven.
The sulfonation degree of this sulfonated polyaniline is 0.38, and heat decomposition temperature is 424 ℃, and specific conductivity is 0.13S/cm.
Embodiment four
8mol 4-aminodiphenylamine-2-sulfonic acid is joined the 800mL deionized water and 2.5mL concentration is in the sodium hydroxide solution of 1.3mol/L, mechanical stirring is finished the dissolving to 4-aminodiphenylamine-2-sulfonic acid, obtains solution A;
At 5～10 ℃, the 10mol ammonium persulphate is joined in the sulphuric acid soln that 120mL concentration is 0.5mol/L, mechanical stirring is finished the dissolving to ammonium persulphate, obtains solution B;
Get 70% solution B and be added dropwise in the solution A, transferring the solution pH value with 0.5mol/L potassium hydroxide simultaneously is 8～9, and at 0～5 ℃, reaction 2.5h obtains 4-aminodiphenylamine-2-sulfonic acid prepolymer solution C;
Under mechanical stirring at the uniform velocity, remaining 30% solution B is added dropwise to solution C, and dropping 2mol aniline monomer, transferring the solution pH value with 0.8mol/L sulfuric acid simultaneously is 4～5, continue reaction 2h, filter, behind deionized water and washing with acetone, 100 ℃ of dryings obtain the target product sulfonated polyaniline in vacuum drying oven.
The sulfonation degree of this sulfonated polyaniline is 0.43, and heat decomposition temperature is 427 ℃, and specific conductivity is 0.17S/cm.
Embodiment five
The 10mol m-sulfanilic acid is joined the 950mL deionized water and 3mL concentration is in the potassium hydroxide solution of 1.5mol/L, mechanical stirring is finished the dissolving to m-sulfanilic acid, obtains solution A;
At 10～15 ℃, 9mol potassium permanganate is joined in the sulphuric acid soln that 50mL concentration is 1.1mol/L, mechanical stirring is finished the dissolving to potassium permanganate, obtains solution B;
Get 60% solution B and be added dropwise in the solution A, transferring the solution pH value with 1.5mol/L potassium hydroxide simultaneously is 8～9, and at 10～15 ℃, reaction 5h obtains m-sulfanilic acid prepolymer solution C;
Under mechanical stirring at the uniform velocity, remaining 40% solution B is added dropwise to solution C, and dropping 10mol aniline monomer, transferring the solution pH value with 1.0mol/L hydrochloric acid simultaneously is 5～6, continue reaction 8h, filter, behind deionized water and washing with acetone, 100 ℃ of dryings obtain the target product sulfonated polyaniline in vacuum drying oven.
The sulfonation degree of this sulfonated polyaniline is 0.47, and heat decomposition temperature is 431 ℃, and specific conductivity is 0.16S/cm.
Embodiment six
With 1mol4-aminodiphenylamine-2-sulfonic acid with the 1mol m-sulfanilic acid joins the 400mL deionized water and 1.5ml concentration is in the potassium hydroxide solution of 0.5mol/L, mechanical stirring is finished the dissolving to 4-aminodiphenylamine-2-sulfonic acid and m-sulfanilic acid, obtains solution A;
At 15～20 ℃, the 6mol ammonium persulphate is joined in the sulphuric acid soln that 45mL concentration is 0.8mol/L, mechanical stirring is finished the dissolving to ammonium persulphate, obtains solution B;
Get 40% solution B and be added dropwise in the solution A, transferring the solution pH value with 0.8mol/L sodium hydroxide simultaneously is 8～9, and at 5～10 ℃, reaction 4h obtains 4-aminodiphenylamine-2-sulfonic acid and m-sulfanilic acid prepolymer solution C;
Under mechanical stirring at the uniform velocity, remaining 60% solution B is added dropwise to solution C, and dropping 9mol aniline monomer, transferring the solution pH value with 1.2mol/L hydrochloric acid simultaneously is 5～6, continue reaction 7h, filter, behind deionized water and washing with acetone, 100 ℃ of dryings obtain the target product sulfonated polyaniline in vacuum drying oven.
The sulfonation degree of this sulfonated polyaniline is 0.16, and heat decomposition temperature is 420 ℃, and specific conductivity is 0.12S/cm.
Claims (6)
1 one kinds of sulfonated polyanilines are for having sulfonation aniline segment and aniline segmental segmented copolymer, sulfonation degree 0.1～0.7, and heat decomposition temperature is not less than 400 ℃, and specific conductivity is not less than 10
-1S/cm.
The sulfonated polyaniline that 2 claims 1 relate to, described sulfonation aniline segment are selected from a kind of or wherein several mixture in ORTHO AMINO PHENOL SULPHONIC, m-sulfanilic acid, Sulphanilic Acid, the 4-aminodiphenylamine-2-sulfonic acid segment.
The preparation method of the sulfonated polyaniline that 3 claims 1 relate to, adopt the step-by-step polymerization mode, the pre-polymerization of sulfonation aniline monomer obtains sulfonation aniline performed polymer under alkaline condition, obtains having the sulfonated polyaniline of block structure then under acidic conditions with the aniline monomer copolymerization, and processing step comprises at least:
(1) with alkaline aqueous solution dissolving sulfonation aniline, obtains sulfonation aniline monomer solution A;
(2) under 0～20 ℃ of condition, use the acidic aqueous solution dissolved oxidant, obtain oxidizing agent solution B;
(3) under 0～20 ℃ of condition, the oxidizing agent solution B with 10%～80% is added drop-wise among the monomer solution A, uses alkaline aqueous solution regulation system pH value simultaneously, keeps pH value and react 1～5h between 7～9, obtains sulfonation aniline prepolymer solution C;
(4) under 0～20 ℃ of condition, the oxidizing agent solution B of surplus is added among the prepolymer solution C, drip aniline monomer, use acidic aqueous solution regulation system pH value simultaneously, keep pH value and between 4～6, react 2～8h, obtain multipolymer suspension system D, filter, filter cake obtains sulfonated polyaniline through washing, drying.
The sulfonated polyaniline synthetic method that 4 claims 3 relate to, the oxygenant that uses are selected from a kind of in ammonium persulphate, the potassium bichromate.
The sulfonated polyaniline synthetic method that 5 claims 3 relate to, the alkaline aqueous solution that uses are selected from a kind of in sodium hydroxide, the potassium hydroxide aqueous solution.
The sulfonated polyaniline synthetic method that 6 claims 3 relate to, the acidic solution that uses are selected from a kind of in hydrochloric acid, the sulfuric acid.
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