阅读说明：本技术 一种聚苯胺聚合物改性的方法 (Method for modifying polyaniline polymer ) 是由 许磊 张蓉 曹天天 杨雷 于 2020-12-14 设计创作，主要内容包括：本发明公开了一种聚苯胺聚合物改性的方法,包括以下步骤：S1：向苯胺中依次加入乳化剂、盐酸和纯净水,然后再加入富勒烯衍生物,冰水浴条件下剧烈搅拌2-3h,所述苯胺与所述C60或富勒烯衍生物的质量比为14-18:4-6；S2：将引发剂溶液加入所述步骤S1的混合溶液中,控制温度80-90℃继续反应3h,然后加入聚乳酸溶液,90-95℃剧烈搅拌反应3-5h之后,蒸发溶液得到产物,最后干燥得到聚苯胺的改性产物。本发明通过向聚苯胺中加入聚乳酸和富勒烯C-(60)或富勒烯衍生物能够增强其导电性能。(The invention discloses a method for modifying polyaniline polymer, which comprises the following steps: s1: sequentially adding an emulsifier, hydrochloric acid and purified water into aniline, then adding a fullerene derivative, and violently stirring for 2-3 hours under the condition of ice-water bath, wherein the mass ratio of the aniline to the C60 or the fullerene derivative is 14-18: 4-6; s2: and (4) adding an initiator solution into the mixed solution obtained in the step S1, controlling the temperature to be 80-90 ℃, continuing to react for 3 hours, then adding a polylactic acid solution, violently stirring at 90-95 ℃ for reacting for 3-5 hours, evaporating the solution to obtain a product, and finally drying to obtain a modified product of polyaniline. The invention adds polylactic acid and fullerene C into polyaniline 60 Or fullerene derivatives can enhance their conductive properties.)

1. A method for modifying polyaniline polymer, which is characterized by comprising the following steps:

s1: will be provided withPolyaniline and C₆₀Or mixing the fullerene derivatives, and violently stirring for 2-3h under the condition of ice-water bath;

s2: and adding an initiator into the mixed solution in the S1, reacting for 3 hours, then adding a polylactic acid solution, reacting for 3-5 hours, evaporating the solution to obtain a product, and finally drying to obtain a modified product of the polyaniline.

2. The method for modifying polyaniline polymer as described in claim 1, wherein in step S1, the polyaniline and the fullerene derivative are mixed and vigorously stirred in an ice-water bath for 2-3 h.

3. The method for modifying a polyaniline polymer according to claim 2, wherein the step S1 specifically comprises: adding an emulsifier, hydrochloric acid and purified water into aniline in sequence, then adding a fullerene derivative, and violently stirring for 2-3h under the condition of ice-water bath, wherein the mass ratio of the aniline to the C60 or the fullerene derivative is 14-18: 4-6.

4. The method of modifying a polyaniline polymer as described in claim 2 or 3, wherein the fullerene derivative is C₆₀(OH)₁₂。

5. The method for modifying a polyaniline polymer as described in claim 4, wherein C is₆₀(OH)₁₂The preparation method comprises the following steps: mixing 300mg of C₆₀Mixing with 3mL fuming sulfuric acid, heating to 55 ℃, reacting for 79h under the protection of nitrogen to obtain a suspension, cooling, adding the suspension into absolute ethyl alcohol under the condition of ice bath, centrifuging and standing to obtain an intermediate product, finally washing the intermediate product, and drying.

6. The method for modifying a polyaniline polymer according to claim 3, wherein the emulsifier is sodium dodecyl sulfate.

7. The method for modifying a polyaniline polymer as described in claim 1, wherein said step S2 is: preparing an initiator solution, adding the initiator solution into the mixed solution obtained in the step S1, controlling the temperature to be 80-90 ℃, continuing to react for 3 hours, then adding a polylactic acid solution, violently stirring at 90-95 ℃ for reacting for 3-5 hours, evaporating the solution to obtain a product, and finally drying to obtain a modified product of polyaniline.

8. The method for modifying a polyaniline polymer as described in claim 7, wherein the initiator solution is prepared by dissolving 0.4-0.7g of ammonium sulfate in 15mL of ultrapure water.

9. The method for modifying a polyaniline polymer according to claim 7, wherein the polylactic acid solution is a solution in which 1 to 1.6g of solid polylactic acid is dissolved in a chloroform solvent.

10. The method for modifying a polyaniline polymer according to claim 7, wherein in step S2: adding polylactic acid, reacting for 3-5h, washing the product with ethanol and purified water until the washing water is colorless, spin-drying the obtained product by using a rotary evaporator, and drying the spin-dried product in a vacuum drying oven to obtain the polyaniline modified product.

Technical Field

The invention belongs to the technical field of polyaniline modification, and particularly relates to a method for modifying polyaniline polymer.

Background

The conductive polymer has potential application prospect in the fields of photoelectron and biomedicine, and is more and more widely applied to high-end intelligent fabrics in recent years. Among conductive polymers, polyaniline monomers are widely used because of their low price, simple synthesis process, high conductivity, stability in air and solution, unique doping phenomenon and good electrochemical reversibility. However, when the polyaniline is used as a raw material of technical products, the conductivity of the polyaniline cannot meet the requirement, and therefore, the conductivity of the polyaniline needs to be improved.

Disclosure of Invention

The invention provides a method for modifying polyaniline polymer, which can improve the conductivity of polyaniline.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method for modifying a polyaniline polymer, comprising the steps of:

s1: mixing polyaniline with C₆₀Or mixing the fullerene derivatives, and violently stirring for 2-3h under the condition of ice-water bath;

s2: and adding an initiator into the mixed solution in the S1, reacting for 3 hours, then adding a polylactic acid solution, reacting for 3-5 hours, evaporating the solution to obtain a product, and finally drying to obtain a modified product of the polyaniline.

Preferably, in the step S1, polyaniline and the fullerene derivative are mixed and vigorously stirred for 2-3 hours under the ice-water bath condition.

The step S1 specifically includes: adding emulsifier, hydrochloric acid and purified water into aniline in sequence, then adding fullerene derivative, and violently stirring for 2-3h under the condition of ice-water bath, wherein the aniline and the C₆₀Or the mass ratio of the fullerene derivative is 14-18: 4-6.

Preferably, the fullerene derivative is C₆₀(OH)₁₂。

In particular, said C₆₀(OH)₁₂The preparation method comprises the following steps: mixing 300mg of C₆₀Mixing with 3mL fuming sulfuric acid, heating to 55 ℃, reacting for 79h under the protection of nitrogen to obtain a suspension, cooling, adding the suspension into absolute ethyl alcohol under the condition of ice bath, centrifuging and standing to obtain an intermediate product, finally washing the intermediate product, and drying.

Preferably, the emulsifier is sodium lauryl sulfate.

Specifically, the step S2 is: preparing an initiator solution, adding the initiator solution into the mixed solution obtained in the step S1, controlling the temperature to be 80-90 ℃, continuing to react for 3 hours, then adding a polylactic acid solution, violently stirring at 90-95 ℃ for reacting for 3-5 hours, evaporating the solution to obtain a product, and finally drying to obtain a modified product of polyaniline.

Preferably, the initiator solution is prepared by dissolving 0.4-0.7g of ammonium sulfate with 15mL of ultrapure water.

Preferably, the polylactic acid solution is a solution of 1 to 1.6g of solid polylactic acid dissolved in a chloroform solvent.

Preferably, in step S2: adding polylactic acid, reacting for 3-5h, washing the product with ethanol and purified water until the washing water is colorless to remove residual monomers, ammonium persulfate and the like, then spin-drying the obtained oil phase product by adopting a rotary evaporator to obtain a target product, and drying the spin-dried product in a vacuum drying oven to obtain the modified product of polyaniline.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:

the polyaniline has simple synthesis process and good chemical reversibility, and polylactic acid and fullerene C are added into the polyaniline₆₀Or fullerene derivatives can enhance their conductive properties. But more preferably a fullerene organism and a fullerene derivative thereof, C₆₀(OH)₁₂As a modified material, the modified material can better increase the conductivity, and the-OH groups on the surfaces of the fullerene carbon cages can increase the dispersibility of the modified material in polymers and improve the interface adhesion performance.

Detailed Description

The method for modifying polyaniline polymer according to the present invention is further described in detail with reference to the following specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims.

Example 1

A25 mL two-necked flask was charged with 300mg of C₆₀And 3mL of fuming sulfuric acid, heating to 55 ℃, and reacting for 70 hours under the protection of nitrogen to obtain a suspension; after cooling to room temperature, dropwise adding the suspension into absolute ethyl alcohol under an ice bath condition, and centrifugally standing to obtain an intermediate product;taking a 50mL round-bottom flask, adding ultrapure water into the intermediate product for hydrolysis reaction, and performing hydrolysis reaction on the intermediate product, wherein N is₂Heating to 85 ℃ and reacting for 8 h; the brown solid can be obtained by using a sand core filtering device, and is repeatedly washed for 3 times by using ultrapure water, and finally the fullerene derivative C can be obtained by placing the fullerene derivative in a vacuum drying oven₆₀(OH)₁₂。

170mg of aniline was charged into a two-necked flask, 100mg of sodium dodecylsulfate (as an emulsifier), 4mL of 2mol/L hydrochloric acid and 15mL of ultrapure water were sequentially added, and finally (0mg, 20mg, 100mg) of fullerene derivative C was added₆₀(OH)₁₂And vigorously stirring for 2 hours under the ice-water bath condition.

Dissolving 0.4g of ammonium persulfate in 15mL of ultrapure water, dropwise adding the solution into a reaction flask, controlling the temperature to be 80-90 ℃, and continuing to react for 3 hours; finally adding a polylactic acid solution (solution formed by dissolving 1.2g of polylactic acid solid in a chloroform solvent), violently stirring at 90-95 ℃ for reaction for 3 hours, and then cleaning a reaction product by using ethanol and ultrapure water until a water phase is in a colorless state so as to remove residual monomers, ammonium persulfate and the like; and (3) carrying out spin drying on the obtained oil phase product by using a rotary evaporator to obtain a target product, and placing the target product in a vacuum drying oven for drying for 12 hours to obtain about 0.95g of polyaniline modified product.

0mg, 20mg and 100mg of C were added to the reaction mixture, respectively₆₀(OH)₁₂Preparing the obtained polyaniline modified product into a sheet by using a hot press, wherein the hot pressing temperature is 150 ℃, and then measuring the resistivity of the obtained polymer composite system by using an RTS-9 type four-probe tester, wherein the obtained resistivity is shown in the following table 1:

TABLE 1C in various amounts₆₀(OH)₁₂Resistivity of the prepared polymer composite system

Modified material	Content (mg)	Resistivity (k omega cm)
			/	0	78.3
C60(OH)12	20	66.7
			C60(OH)12	100	69.2

Before the modified material is not used, the resistivity of the composite system is higher and is 78.3k omega cm, and a fullerene derivative C is added₆₀(OH)₁₂After the material is modified, the resistivity is reduced, and the conductivity is improved.

Example 2

170mg of aniline was added to a two-necked flask, and 100mg of sodium dodecylsulfate (as an emulsifier), 4mL of 2mol/L hydrochloric acid and 15mL of ultrapure water were sequentially added, and finally (0mg, 20mg, 100mg) of fullerene C was added₆₀And vigorously stirring for 2 hours under the ice-water bath condition.

Dissolving 0.4g of ammonium persulfate in 15mL of ultrapure water, dropwise adding the solution into a reaction flask, controlling the temperature to be 80-90 ℃, and continuing to react for 3 hours; finally adding a polylactic acid solution (solution formed by dissolving 1.2g of polylactic acid solid in a chloroform solvent), violently stirring at 90-95 ℃ for reaction for 3 hours, and then cleaning a reaction product by using ethanol and ultrapure water until a water phase is in a colorless state so as to remove residual monomers, ammonium persulfate and the like; and (3) carrying out spin drying on the obtained oil phase product by using a rotary evaporator to obtain a target product, and placing the target product in a vacuum drying oven for drying for 12 hours to obtain about 0.95g of polyaniline modified product.

0mg, 20mg and 100mg of C were added to the reaction mixture, respectively₆₀Preparing the obtained polyaniline modified product into a sheet by using a hot press, wherein the hot pressing temperature is 150 ℃, and then measuring the resistivity of the obtained polymer composite system by using an RTS-9 type four-probe tester, wherein the obtained resistivity is shown in the following table 2:

TABLE 2C in various amounts₆₀Resistivity of the prepared polymer composite system

From example 1 and example 2, it is possible to use a fullerene derivative C₆₀(OH)₁₂Compared with fullerene modification, the modification has good effect of improving the conductivity of a polyaniline composite system, which is caused by the fact that C is₆₀In the using process of (A), due to C₆₀The structure of the self-body belongs to a net structure, and the dissolution property and the dispersion property of the self-body are poor, so that C is ensured₆₀The agglomeration phenomenon is easy to occur, so that the dispersion is not uniform in the solution, and the electrical property is influenced. And the fullerene derivative C is subjected to functional modification₆₀(OH)₁₂As a modified material, the modified material can better increase the conductivity, and the-OH groups on the surfaces of the fullerene carbon cages can increase the dispersibility of the modified material in polymers and improve the interface adhesion performance.

Example 3

170mg of aniline was added to a two-necked flask, and 100mg of sodium dodecylsulfate (as an emulsifier), 4mL of 2mol/L hydrochloric acid and 15mL of ultrapure water were sequentially added, and finally (40mg, 60mg, 80mg) of fullerene C was added₆₀Or a fullerene derivative C₆₀(OH)₁₂And vigorously stirring for 2 hours under the ice-water bath condition.

Dissolving 0.4g of ammonium persulfate in 15mL of ultrapure water, dropwise adding the solution into a reaction flask, controlling the temperature to be 80-90 ℃, and continuing to react for 3 hours; finally adding a polylactic acid solution (solution formed by dissolving 1.2g of polylactic acid solid in a chloroform solvent), violently stirring at 90-95 ℃ for reaction for 3 hours, and then cleaning a reaction product by using ethanol and ultrapure water until a water phase is in a colorless state so as to remove residual monomers, ammonium persulfate and the like; and (3) carrying out spin drying on the obtained oil phase product by using a rotary evaporator to obtain a target product, and placing the target product in a vacuum drying oven for drying for 12 hours to obtain about 0.95g of polyaniline modified product.

The conductivity of the final product was also tested by the same test method. The results are shown in Table 3 below

TABLE 3 resistivity of Polymer composite systems prepared with different contents of modified Material Fullerene or Fullerene derivative

Modified material	Content (mg)	Resistivity (k omega cm)
			/	0	78.3
C60(OH)12	40	44.5
			C60(OH)12	60	32.1
C60(OH)12	80	53.8
			C60	40	60.2
C60	60	54.8
			C60	80	65.7

Through content optimization, fullerene derivative C is added into a reactant system₆₀(OH)₁₂When the modified material (60 mg) was used, the lowest resistivity of 32.1 k.OMEGA.cm could be obtained, and 40mg of C was added₆₀The resistivity of the composite system is 60.2k omega cm, and 60mg C is added₆₀The composite system resistivity of (2) was 54.8 k.OMEGA.cm. Thus, it is compared with the hollow fullerene C₆₀In particular to a fullerene derivative C subjected to functional modification₆₀(OH)₁₂As a modified material, the polyaniline composite material can reduce the resistivity of a polyaniline composite system, thereby improving the conductivity of the polyaniline composite system, and C₆₀(OH)₁₂The lowest resistivity was used in the range of 40mg to 60 mg.

Example 4

180mg of aniline was added to a two-necked flask, 100mg of sodium dodecylsulfate (as an emulsifier), 5mL of 2mol/L hydrochloric acid and 15mL of ultrapure water were sequentially added, and finally (40mg, 60mg, 80mg) of fullerene C was added₆₀Or a fullerene derivative C₆₀(OH)₁₂And vigorously stirring for 2 hours under the ice-water bath condition.

Dissolving 0.6g of ammonium persulfate in 15mL of ultrapure water, dropwise adding the solution into a reaction flask, controlling the temperature to be 80-90 ℃, and continuing to react for 3 hours; finally adding a polylactic acid solution (solution formed by dissolving 1.3g of polylactic acid solid in a chloroform solvent), violently stirring at 90-95 ℃ for reaction for 3 hours, and then cleaning a reaction product by using ethanol and ultrapure water until a water phase is in a colorless state so as to remove residual monomers, ammonium persulfate and the like; and (3) carrying out spin drying on the obtained oil phase product by using a rotary evaporator to obtain a target product, and placing the target product in a vacuum drying oven for drying for 12 hours to obtain about 1.05g of a polyaniline modified product.

The resistivity of the final polyaniline modified product was measured by the same measurement method, and the results are shown in table 4:

TABLE 4 resistivity of Polymer composite systems prepared with different contents of modified Material Fullerene or Fullerene derivative

Through content optimization, fullerene derivative C is added into a reactant system₆₀(OH)₁₂When the modified material (60 mg) was used, the lowest resistivity was obtained, 30.4 k.OMEGA.cm, and 40mg of C was added₆₀The resistivity of the composite system is 60.6k omega cm, and 60mg C is added₆₀The composite system resistivity of (2) was 56.4 k.OMEGA.cm. Thus, it is compared with the hollow fullerene C₆₀In particular to a fullerene derivative C subjected to functional modification₆₀(OH)₁₂As a modified material, the polyaniline composite material can reduce the resistivity of a polyaniline composite system, thereby improving the conductivity of the polyaniline composite system, and C₆₀(OH)₁₂The lowest resistivity is obtained when the dosage is in the range of 40mg-60 mg.

The embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.