CN103275343B - Method for preparing polyaniline surface modified conductive polyester chips - Google Patents
Method for preparing polyaniline surface modified conductive polyester chips Download PDFInfo
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- CN103275343B CN103275343B CN201310189742.9A CN201310189742A CN103275343B CN 103275343 B CN103275343 B CN 103275343B CN 201310189742 A CN201310189742 A CN 201310189742A CN 103275343 B CN103275343 B CN 103275343B
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- polyester
- polyester chips
- aniline
- polyaniline
- hydrochloric acid
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Abstract
The invention relates to a method for preparing polyaniline surface modified conductive polyester chips. The method comprises the following steps of: performing oil removal treatment on polyester chips by using acetone, drying, and then hydrolyzing in a concentrated sulfuric acid solution; sequentially adding the hydrolyzed polyester chips, aniline and a hydrochloric acid solution into a reactor, mixing uniformly, adjusting the temperature to be 0 to 5 DEG C, slowly dripping an aqueous solution of ammonium persulfate, and continuously reacting for 1 to 6 hours after dripping; and cleaning the obtained polyester chips by using hydrochloric acid and water, and drying at room temperature. According to the method, the surfaces of the polyester chips are subjected to acid hydrolysis before aniline adsorption and polymerization, so that on the one hand, the surface area of polyester is enlarged, and a large place and a large anchor point are provided for aniline adsorption; and on the other hand, polar groups are increased after hydrolysis of the polyester surface, and the acting force between the polyester matrix and the polyaniline molecules is enhanced, so that the aniline can be firmly adsorbed to the polyester surface.
Description
Technical field
The present invention relates to conductive polymer composites preparing technical field, be specifically related to a kind of preparation method of conductive polyester sheet of polyaniline finishing.
Background technology
Polyester be by polyvalent alcohol and polyprotonic acid polycondensation and polymkeric substance general name, mainly refer to polyethylene terephthalate.It has superior physical and mechanical properties, as: good mechanical property, wear resistance, creep resistance etc., and chemical-resistant resistance therefore have certain application in industrial production.But polyester has very high ratio resistance, be electric poor conductor, this will limit to a certain extent polyester and apply more widely.In recent years, the polyester (sheet, fiber, fabric, film) that preparation has certain conductivity becomes the focus of domestic and international research.
At isolator surface of polyester absorption one deck conducting polymer, can obviously improve its specific conductivity as polypyrrole, polyaniline.In numerous conducting polymers, polyaniline with its raw material be easy to get, simple synthetic method, have good thermostability, chemical stability and electrochemical reversibility with and unique mechanism of doping effect become one of the fastest conducting polymer of progress.Therefore the electrically conductive composite of, preparing polyaniline and polyester becomes everybody and studies a many aspect.At surface of polyester absorption deposition one deck electrically conductive polyaniline, will expand it in the application in the fields such as ammonia gas sensor, electromagnetic shielding, antistatic, electrochemical device and precious metal recovery.
At present, can prepare by chemistry or electrochemical method the conductive polyester of polyaniline-coated, wherein chemical process is less many by everybody use to the requirement of specimen size.Gu Qingchao (Nanjing University's journal, 1994,30 (3), 458-462) adopt the method for chemical polymerization to prepare transparent polyaniline/polyester electroconductibility composite membrane, its resistivity can be down to 10
3-10
4Ω/.L.P.Salgaonkar (J.Appl.Polym.Sci., 2004,93,1981-1988) under sour environment, take ammonium persulphate as oxygenant, by polyaniline chemical graft, to polyester textile, the electrically conductive composite specific conductivity of preparation is 5 * 10
-3s/cm.Zhu Ying (Macromol.Rapid Commun., 2007,28,2230-2236) take perfluor SA as dopant acid, adopt the method for in-situ polymerization to prepare polyaniline/polyester textile electrically conductive composite, its specific conductivity is 1.25 * 10-
2s/cm.J.Molina (Eur.Polym.J., 2011,47,2003-2015) take Potassium Persulphate as oxygenant, make aniline on mylar, carry out chemical oxidising polymerisation, obtained the conductive polyester cloth of polyaniline-coated, under low frequency, the comparable polyester of its impedance factor reduces by 9 orders of magnitude.In above preparation process, aniline has played keying action in the absorption of surface of polyester, but this absorption only relies on Van der Waals force, and its Intermolecular Forces is more weak comparatively speaking.
Summary of the invention
The preparation method who the object of the invention is to overcome above-mentioned deficiency and the conductive polyester sheet of polyaniline finishing is provided.
The technical scheme that the present invention takes is:
The preparation method of the conductive polyester sheet of polyaniline finishing, comprises that step is as follows:
(1) polyester chips is deoiled and processes rear drying at room temperature with acetone, then hydrolysis 1-3min in concentrated sulfuric acid solution (sulfuric acid and water volume ratio are 4-5:1);
(2) polyester chips after hydrolysis treatment, aniline, hydrochloric acid soln are added in reactor successively, mix, temperature is adjusted to 0-5 ℃, under mechanical stirring, slowly drip ammonium persulfate aqueous solution, drip rear continuation reaction 1-6 hour;
(3) polyester chips obtaining is cleaned to the approaching neutrality to pH with hydrochloric acid and water, dry under room temperature.
The described polyester chips of above-mentioned steps (1) is polyethylene terephthalate.
In step (2), the mass ratio of polyester chips and aniline is 1:100, and the mol ratio of aniline and hydrochloric acid is 1:1-5, and the mol ratio of aniline and ammonium persulphate is 1:0.25-1.25.The concentration range of hydrochloric acid soln, ammonium persulfate aqueous solution is respectively 1-5mol/L, 0.015-0.075mol/L; Ammonium persulfate aqueous solution drips in 30min.
In step (3), first use the hydrochloric acid cleaning 3 times of 0.1mol/L, then water cleans 3 times.
The present invention to the surface of polyester processing that is hydrolyzed, makes aniline be adsorbed on surface of polyester under the acting in conjunction of Van der Waals force and hydrogen bond, thereby polyaniline and polyester that chemical polymerization obtains is combined more securely before aniline in-situ polymerization.
Compared with prior art, the present invention carried out acidolysis processing to polyester chips surface before aniline adsorpting polymerization, had increased on the one hand the surface-area of polyester, for aniline absorption provides larger place and anchor point; After surface of polyester hydrolysis, polar group increases on the other hand, and between polyester matrix and polyaniline molecule, reactive force strengthens, thereby can make aniline be adsorbed in more securely surface of polyester.
Based on surfaceness, increase and polar group increases, polyaniline adsorptive capacity is increased, after polymerization, polyester chips increases weight by 0.13%(polyester chips hydrolysis treatment not) rise to 1.98%(polyester chips hydrolysis treatment); Layer/polyaniline conductive layer thickness is by 2 μ m(polyester chipss hydrolysis treatment not) increase to 50 μ m(polyester chipss hydrolysis) left and right.The adhesivity of polyaniline and polyester matrix strengthens, ultrasonic in 1-Methyl-2-Pyrrolidone, larger without surface preparation colour-change, and substantially unchanged through surface preparation color.The electrically conductive composite that adopts the inventive method to prepare, adsorptive capacity and polyaniline and adhering while of polyester matrix increasing polyaniline, also make polyester there is certain electroconductibility, its specific conductivity maximum can reach 4.96 * 10
-3s/cm is only 1.01 * 10 and process specific conductivity without surface hydrolysis
-4s/cm.
Accompanying drawing explanation
Fig. 1 is the photo by the conductive polyester sheet of polyaniline finishing, wherein: (a), polyester chips is without surface hydrolysis; (b) in, polyester chips is through vitriol oil surface hydrolysis; (c) in, polyester chips is without surface hydrolysis, ultrasonic in 1-Methyl-2-Pyrrolidone after polymerization; (d) in, polyester chips is through vitriol oil surface hydrolysis, ultrasonic in 1-Methyl-2-Pyrrolidone after polymerization.
Fig. 2 FTIR-ATR collection of illustrative plates, wherein: (a) be polyester chips FTIR-ATR collection of illustrative plates; (b) be surface hydrolysis polyester chips FTIR-ATR collection of illustrative plates; (c) be that surface hydrolysis is by polyaniline finishing polyester chips FTIR-ATR collection of illustrative plates.
Fig. 3 EDX figure, wherein: (a) be polyester chips EDX figure; (b) be surface hydrolysis polyester chips EDX figure; (c) be that surface hydrolysis is schemed by polyaniline finishing polyester chips EDX.
Fig. 4 SEM figure, wherein: (a) be polyester chips SEM figure; (b) be surface hydrolysis polyester chips SEM figure; (c) be that surface hydrolysis is schemed by polyaniline finishing polyester chips SEM.
The conductive polyester sheet sectional view of Fig. 5 polyaniline finishing, (a): polyester chips is without surface hydrolysis; (b): polyester chips is through vitriol oil surface hydrolysis.
Embodiment
Below in conjunction with embodiment, further illustrate.
Embodiment 1
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 4:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL3M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Cool the temperature to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 0.25:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 3.34 * 10
-3s/cm.
Embodiment 2
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 4:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL2M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 0.5:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 3.33 * 10
-3s/cm.
Embodiment 3
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 5:1), be hydrolyzed 1min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL3M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 0.5:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 3.93 * 10
-3s/cm.
Embodiment 4
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 4:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL3M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 0.75:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 4.96 * 10
-3s/cm.
Embodiment 5
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 4:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL4M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 0.75:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 3.55 * 10
-3s/cm.
Embodiment 6
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 4:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL5M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 0.75:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 1.86 * 10
-3s/cm.
Embodiment 7
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 5:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL1M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 1:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 1.41 * 10
-3s/cm.
Embodiment 8
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 4:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (60mg), 6g aniline and the 60mL3M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 1:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 3.96 * 10
-3s/cm.
Embodiment 9
(1), by the acetone processing of deoiling for polyester chips, in the concentrated sulfuric acid solution of (sulfuric acid and water volume ratio are 4:1), be hydrolyzed 2min after dry.
(2) step (1) is processed to the polyester chips (1mm * 2mm), 6g aniline and the 60mL3M hydrochloric acid soln that obtain and join successively in four-hole boiling flask, start mechanical stirring it is fully mixed; Until temperature, be down to after 0-5 ℃, with dropping funnel slowly drip 50mL ammonium persulphate (with aniline mol ratio be 1.25:1) aqueous solution, 30min dropwises; After 5h, finish reaction.
(3) polyester chips step (2) being made cleans with the hydrochloric acid of 0.1mol/L and a large amount of water, dry under room temperature.
The specific conductivity of the polyester chips by polyaniline finishing of preparation is 1.97 * 10
-3s/cm.
Claims (4)
1. the preparation method of the conductive polyester sheet of polyaniline finishing, is characterized in that, comprises that step is as follows:
(1) polyester chips is deoiled and processes rear being dried with acetone, then in concentrated sulfuric acid solution, be hydrolyzed 1-3min;
(2) polyester chips after hydrolysis treatment, aniline, hydrochloric acid soln are added in reactor successively, mix, temperature is adjusted to 0-5 ℃, under mechanical stirring, slowly drip ammonium persulfate aqueous solution, drip rear continuation reaction 1-6 hour; The mass ratio of polyester chips and aniline is 1:100, and the mol ratio of aniline and hydrochloric acid is 1:1-5, and the mol ratio of aniline and ammonium persulphate is 1:0.25-1.25;
(3) polyester chips obtaining is cleaned to the approaching neutrality to pH with hydrochloric acid and water, dry under room temperature.
2. the preparation method of the conductive polyester sheet of polyaniline finishing according to claim 1, is characterized in that, the described polyester chips of step (1) is polyethylene terephthalate.
3. the preparation method of the conductive polyester sheet of polyaniline finishing according to claim 1, is characterized in that, the concentration range of step (2) hydrochloric acid soln, ammonium persulfate aqueous solution is respectively 1-5mol/L, 0.015-0.075mol/L.
4. the preparation method of the conductive polyester sheet of polyaniline finishing according to claim 1, is characterized in that, first uses the hydrochloric acid cleaning 3 times of 0.1mol/L in step (3), then water cleans 3 times.
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