TWI477532B - Phosphorous star-shaped polyaniline and its manufacturing method and composite material manufacturing method thereof - Google Patents

Description

Phosphine-containing stellate polyaniline, manufacturing method thereof and manufacturing method thereof

The present invention relates to a polyaniline and a method for producing the same, and more particularly to a phosphorus-containing polyaniline and a method for producing the same.

According to the past research, polyaniline, the main conductive polymer material of the main chain type, can be divided into external acid doping type and self-doping type polyaniline according to its acid doping method. The literature review is as follows:

Polyaniline powder can be synthesized in large quantities by chemical methods. The literature reports the use of ammonium oxydisulfate (APS; (NH ₄ ) ₂ S ₂ O ₈ ), potassium dichromate (K ₂ Cr ₂ O ₇ ), ferric chloride (FeCl ₃ ). Or an oxidizing agent such as hydrogen peroxide, added to an aqueous solution of a protonic acid (such as HCl or H ₂ SO ₄ ) in which an aniline (AN) monomer is dissolved, and the solution is gradually changed from a colorless transparent to a brown solution (starting to polymerize into two). The dimer finally produces a dark green doped polyethylamine (Emeraldine salt) powder precipitate. The precipitate is subjected to a dedoping reaction in an aqueous alkaline solution (such as NH ₄ OH or NaOH) to obtain an undoped polyaniline powder.

(1) Externally doped inorganic acid of polyaniline:

In 1997, XING-RONG et al. used potassium dichromate as an oxidant to oxidatively polymerize protonic acid (HCl) to obtain doped polyaniline, followed by alkaline aqueous solution (NH ₃ .H ₂ O). Polyaniline, which is doped with polyaniline, and then doped with iodine molecule (I ₂ ), can be used to increase the thermal stability and conductivity of the iodine molecule to 1.83x10 ^{- 3} S/cm.

In 2005, Jaroslav Stejskal et al. used protonic acid (HCl) to synthesize polyaniline and polyphenylene diamine to blend with fibers to measure their thermal stability and electrical conductivity. The conductivity value and the coke residual amount were found, and the doping type was higher than that of the dedoping type.

In 2007, Jing Luo et al. synthesized two kinds of phosphorus-containing inorganic acids and polyaniline for doping reaction. It is hoped that the solubility of the two phosphorus-containing inorganic acids can be changed by using different acid doping. The conductivity value (4 to 5 S/cm) is higher than that of the protonic acid (HCl), and the phosphorus-containing inorganic acid contains a hydrophilic group, and thus has good dispersibility in an aqueous solution.

(2) Externally doped organic acid of polyaniline:

In 2001, two scholars, Raji K Paul and CKS Pillai, used SPDP, SPDA and SPDPAA three organic acids (the structure is shown in the first figure) to be doped with polyaniline, and then discussed the use of emulsion polymerization and machinery. The polyaniline doped in two ways is compared to its electrical conductivity and thermal stability. SPDPAA was found to have the highest conductivity value, and the average emulsion polymerization of polyaniline was higher than that of mechanically agitated polyaniline and SPDPAA at 45 ° C, the conductivity can be as high as 65 S / cm.

The chemical structure of organic acid SPDP, SPDA and SPDPAA.

In 2002, V. Jousseaume et al. used Camphor sulfonic acid (CSA) and Bis(2-ethyl-hexyl)hydrogen phosphate (DiOHP) in combination with polyaniline. It was found that the polyaniline doped with CSA had a stable conductivity value before 450 ° C, but its thermal stability was not good, so the polyethylene was further blended to improve its thermal stability. And at different temperatures, the conductivity of polystyrene doped with CSA is slightly better than that of DiOHP doped polyaniline.

In 2004, Yongsheng Yang et al. used polyaniline and Acrylic acid for doping reaction and discussed the reaction time, the ratio of different oxidants to aniline and the reaction temperature from -10 °C to 90 °C. Rate impact. It was found that the reaction ratio was between 1-10 ° C and 18 ° C, the ratio of oxidant to aniline was between 1 and 2, and the reaction time was over 4 hours, and the optimum yield was 65%. Moreover, polyaniline doped with acrylic acid is soluble in water, thereby improving its poor solubility and its conductivity value can reach 3.61 x 10 ^-3 S/cm at room temperature.

(3) Self-doped polyaniline

In 1997, K. Watanabe et al. used Aniline sulfonic acid (ASA) and 2-Methoxyaniline-5-sulfonic acid (MAS) at 4 ° C. The polymerization was carried out by using ammonium persulfate (APS) as an oxidant. The synthesis of fully sulfonated polyaniline was found to be unsuitable for the formation of 2-sulfonic acid aniline (ASA) polymerization in an acidic environment. The fully sulfonated polyaniline has a yield of up to 96% and its product is also soluble in water, but the conductivity is only 0.04 S/cm.

In 2000, Hsien-Kuang et al. used o-sulfobenzoic anhydride ( O- Sulfobenzoic anhydride) to react with aniline (AN) to synthesize polyaniline which is soluble in water but its conductivity is only acceptable. Up to 4.7 x 10 _-4 S/cm.

In 2005, Chien-Hsin Yang et al. used different proportions of aniline (AN) and o -aminobenzenesulfonic acid (SAN) to polymerize self-doped polyaniline, and found that polyaniline will be due to the length of reaction time. The AN/SAN ratio changes while presenting a spherical or tubular pattern. And the conductivity value is also affected by the AN/SAN ratio. When the ratio is 1.0, the conductivity value is the highest.

In the application of polyaniline, it can be used in the following fields:

(1) Electrochromic components: Polyaniline exhibits different colors due to its redox state. Therefore, polyaniline and its derivatives are most commonly used to discuss components used in electrochromic devices (Electrochromic devices). ) or Smart Windows.

(2) Electrode material of battery: In a lithium battery, a conductive polymer is used as a suitable electrode material. Polyaniline has received high attention due to its high discharge capacity and good stability.

(3) Antistatic material: The insulator will accumulate charge, so the level of electrostatic accumulation is quite large, and the accumulated static electricity will eventually stay on the insulated plastic body. The problem of plastic static can be solved by the addition of ionic or intrinsically conductive plastics. Generally, some small molecular salts (amine salts, sulfonates) are added to help the plastics remove static electricity. However, small molecules are easy to migrate and aggregate, and have a certain life span. Therefore, conductive polymers can be added to improve the problem. Others such as: chemical sensing materials, conductive resins, microwave absorbers, etc., are also applications that have received much attention in recent years.

The main object of the present invention is to provide a phosphorus-containing star polyaniline and a method for producing the same The method for producing the composite material thereof is to provide a phosphorus-containing polyaniline doped with an external acid to help improve its thermal stability.

A secondary object of the present invention is to provide a phosphorus-containing stellate polyaniline, a method for producing the same, and a method for producing the same, which provide a self-doping type of phosphorus-containing stearyl polyaniline, which contributes to an improvement in thermal stability.

Still another object of the present invention is to provide a phosphorus-containing stellate polyaniline, a method for producing the same, and a method for producing the same, which provide a phosphorus-containing stellate polyaniline composite material, which can increase its thermal stability and enhance its conductivity. Moreover, it has good flame retardancy, and it can also improve the flame retardant quality by being added to the melamine resin.

In order to achieve the object, the present invention discloses a phosphorus-containing stellate polyaniline, a method for producing the same, and a method for producing the composite material, the phosphorus-centered star-shaped polyaniline, whether the grafted polyaniline is doped with an external acid or Self-doping can improve its thermal stability. The conductive polymer has good solubility in film formation, thermal properties and electrochemical properties to enhance the application range of the conductive polymer, and can be used for electrochromic elements, battery electrode materials and antistatic materials.

1 is a schematic diagram showing the reaction equation of an external acid-doped phosphorus-containing polyaniline according to a preferred embodiment of the present invention; and FIG. 2 is a MPANI of a preferred embodiment of the present invention. Schematic diagram of TGA diagram of HPANI under nitrogen and air environment; Fig. 3 is a schematic diagram of reaction equation of self-doped phosphorus-containing stearyl polyaniline according to another preferred embodiment of the present invention; Fig. 4: Self-doping polyaniline according to another preferred embodiment of the present invention TGA diagram of S-MPANI-011, S-MPANI-041, S-HPANI-155, S-HPANI-182 under nitrogen and air environment; Fig. 5: It is another preferred embodiment of the present invention TGA pattern of HPANI doped with melamine resin in different proportions under nitrogen; and Fig. 6: HPANI is another preferred embodiment of the invention in different proportions with melamine under air The T80 pattern of doping of the resin.

In order to provide a better understanding and understanding of the structural features and efficacies of the present invention, the preferred embodiments and detailed descriptions are provided as follows:

First, referring to Fig. 1, the present invention provides a phosphorus-containing stellate polyaniline which is an external acid-doped phosphorus-containing stearyl polyaniline having the following structural formula: Where R ₁ contains .

Referring to Fig. 1, a method for producing an external acid-doped phosphorus-containing polyaniline is a tris(3-aminophenyl)phosphine oxide (TAPPO) (0.7046 g, 2.2mmol) placed in the reaction bottle The solution was dissolved in 1 M aqueous hydrochloric acid (80 mL), and the reaction mixture was placed in an ice bath. The aniline liquid was purified by distillation under reduced pressure (6 mL, 66 mmol), and the aniline monomer was driven into a reaction flask using a needle, and Ammonium persulfate (3.464 g, 15.18 mmol) was added to the reaction flask. Used as an oxidant. The reaction was carried out in an ice bath environment for 1.5 hours, followed by a reaction at room temperature for 2.5 hours. After the reaction was completely filtered, a large amount of blue-green precipitate was produced, and then washed with ice water several times to remove salts and residual hydrochloric acid on the surface of the precipitate. The product, HPANI (0.5768 g), was obtained by drying the purple-black solid.

Among them, the method for producing tris(3-aminophenyl)phosphine oxide (TAPPO) is to put Tris(3-nitrophenyl)phosphine oxide (TNPPO) (3.1221 g, 7.5 mmol). Into a double-necked flask, add appropriate ethanol (Ethanol) (100mL) and hydrochloric acid (Hydrogen chloride) (100mL) to dissolve, then use tin (II) chloride (21.332g, 112.5mmol) when The catalyst was reacted at room temperature for 8 hours. After completion of the reaction, an aqueous solution of sodium hydroxide (48 g, 1.2 mol) was used for neutralization with a reaction solution, and the product was extracted three times with a solvent chloroform (Chloroform) to obtain a yellow-green precipitate. It was dissolved in ethyl acetate (Ethyl acetate), and hexane (Hexane) was re-sinked three times. A yellow-green crystalline solid was obtained as TAPPO (1.7844 g; yield = 72%). 1H NMR (600MHz, DMSO): δ 5.31~5.34(s,6H), 6.60~6.65(d,3H), 6.70~6.74(d,3H),6.77~6.81(s,3H),7.09~7.14(t , 3H).

Wherein the method for producing Tris(3-nitrophenyl)phosphine oxide (TNPPO) is a compound triphenylphospine (Triphenylphospine) Oxide) (3.6176 g, 13 mmol) was placed in a reaction flask, dissolved in sulfuric acid (60 mL), and the reaction mixture was placed in an ice bath and stirred. Prepare mixed acid of nitric acid (4.76mL, 71.5mmol) and sulfuric acid (Sulfuric acid) (20mL), and slowly mix the mixed acid into the reaction bottle by using the feeding tube, first maintain the ice bath for 5 hours, then heat The reaction was refluxed at 45 to 50 ° C for 16 hours. After the completion of the reaction, the solution was diluted with a large amount of water. At this time, a large amount of yellow-white precipitate was precipitated, and after filtration, it was washed with ice water several times to remove salts and residual hydrochloric acid on the surface of the precipitate. It was dissolved in ethyl acetate (Ethyl acetate), and hexane (Hexane) was re-sinked three times. A yellow-white crystalline solid was obtained as TNPPO (2.8711 g; yield = 53%). 1H NMR (600MHz, CDCl3) δ 7.804~7.836 (t, 3H), 8.085~8.090 (d, 3H), 8.515 (s, 3H), 8.53 to 8.537 (d, 3H).

Take a control group of main chain type external acid doped polyaniline (MPANI), distill the aniline liquid into aniline monomer (10mL, 110mmol) by vacuum distillation apparatus, and inject the aniline monomer into the reaction bottle by needle. 1 M hydrochloric acid (60 mL) was dissolved and the reaction flask was placed in an ice bath. Ammonium persulfate (5.741 g, 25 mmol) was further placed in the reaction flask as an oxidizing agent. The reaction was carried out in an ice bath environment for 1.5 hours, followed by a reaction at room temperature for 2.5 hours. After the reaction is completed. After filtration, a large amount of blue-green precipitate was produced, and then washed with ice water several times to remove salts and hydrochloric acid on the surface of the precipitate. The dark green precipitate was dried to give the product MPANI (0.477 g).

Please refer to Figure 2 for the TGA diagram of MPANI and HPANI under nitrogen and air. It is found that the slight weight loss before 150 °C is mainly caused by moisture and some aniline with poor polymerization degree. . Under nitrogen MPANI and HPANI have two distinct thermal weight losses at 200 ° C and 550 ° C. The thermal weight loss at 200 °C is caused by externally doped HCl. 550 ° C is the temperature at which the polyaniline backbone is cleaved. HPANI has better thermal stability than MPANI in air or nitrogen environment. This is because HPANI is a polymer centered on phosphorus. However, the phosphorus atom itself has good flame retardancy, so it can improve the heat of the polymer. stability. It can be found from the TGA diagram that the HPANI is between 200 and 600 °C, and the flame resistance in air is slightly better than that in the nitrogen atmosphere. This is because the specific properties of the phosphorus-containing compound are more likely to form polyphosphoric acid in the presence of oxygen (- POP) has a viscous protective film covering the surface of polyaniline to prevent flammable gas from overflowing.

Furthermore, the present invention provides a phosphorus-containing stellate polyaniline which is a self-doping type phosphorus-containing stellate polyaniline having the following structural formula: Where R ₂ contains .

Referring to FIG. 3, the self-doping type phosphorus-containing polyaniline is produced by placing TAPPO (0.7046 g, 2.2 mmmol) in a reaction flask, dissolving it in 200 mL of distilled water, and dissolving the reaction bottle. As for the ice bath. The aniline monomer (3.10 mL, 33 mmol), which was purified by distillation under reduced pressure, was injected into a reaction flask using a needle. Add p-aminobenzenesulfonic acid (5.71 g, 33 mmol) to the reaction flask, and finally persulfate Ammonium persulfate (3.464 g, 15.18 mmol) was added to the reaction flask as an oxidizing agent. The reaction was carried out for 96 hours in an environment of 4 °C. After the reaction is completely filtered, a blue-green precipitate is produced. The water was washed several times with ice water to remove salts on the surface of the precipitate. The phosphorus-containing polyaniline (S-HPANI) is obtained by drying the purple-black solid. According to the synthesis ratio of TAPPO, aniline and p-aminobenzenesulfonic acid, S-HPANI-155 (TAPPO: aniline: p-aminobenzenesulfonic acid = 1:5:5) and S-HPANI-182 (TAPPO) can be synthesized. : aniline: p-aminobenzenesulfonic acid = 1:8:2).

A control group was taken, 100 mL of distilled water was placed in the reaction flask, and the reaction flask was placed in an ice bath. The aniline liquid was subjected to distillation to purify the aniline monomer (1.022 g) by a vacuum distillation apparatus, and the aniline monomer was injected into the reaction flask. Further, p-aminobenzenesulfonic acid (SAN, 1.900 g) was added to the reaction flask, and finally ammonium persulfate (2.2820 g) was placed in a reaction flask as an oxidizing agent, and reacted at 4 ° C for 96 hours. After the reaction is completed. The blue-green precipitate was filtered off and washed with water several times to remove salts on the surface of the precipitate. The obtained purple-black solid product was dried to obtain polyaniline S-MPANI-011 (0.403 g). According to the ratio of aniline to p-aminobenzenesulfonic acid, S-MPANI-011 (aniline: p-aminobenzenesulfonic acid = 1:1) and S-MPANI-041 (aniline: p-aminobenzenesulfonic acid = 4: 1).

Figure 4 shows the TGA pattern of self-doped polyaniline S-MPANI-011, S-MPANI-041, S-HPANI-155, and S-HPANI-182 under nitrogen and air. It was found before 200 °C. Some of the slight thermal weight loss is mainly caused by moisture and some aniline oligopolymers. S-MPANI-011 and S-MPANI-041 have three distinct thermal weight losses under nitrogen. The thermal weight loss before 200 °C is caused by some water vapor and solvent. The second stage weight loss is caused by the cleavage of the dopant, and the third stage is the cleavage of the self-doped polyaniline backbone. S-HPANI-182 and S-HPANI-155 have four distinct thermal weight losses. The first three stages of thermal weight loss are the same as those of S-MPANI-011 and S-MPANI-041, while the fourth stage thermal weight loss of S-HPANI-182 and S-HPANI-155 is self-doped phosphorus-containing star shape. Caused by cracking of the polyaniline backbone. We found that the thermal stability of S-MPANI-011 is better than that of S-MPANI-041 before 400 °C in a nitrogen atmosphere. Because the sulfonate (-SO ₃ ) group in SAN has flame retardant properties, it can improve self-doping. Thermal stability of heteropolyaniline. In the air environment, sulfur and phosphorus have similar properties, forming a solid protective film when heated, which results in better thermal stability of S-MPANI-011 than S-MPANI-041. However, comparing the thermal stability of S-MPANI and S-HPANI, it is found that the thermal stability of S-MPANI series is not much different from that of S-HPANI series under nitrogen environment, because the conjugated segment of S-MPANI contains sulfur. Sulfur and phosphorus have similar properties. However, the thermal stability of the S-HPANI series is better than that of S-MPANI in the air environment, because the solid protective film formed by phosphorus can withstand higher temperatures than the protective film formed by sulfur.

The following table shows the resistance values of the S-MPANI and S-HPANI series by four-point probe. It can be observed from the table that the conductivity of the S-MPANI series material is superior to the series material S-HPANI, and it is found that in S- MPANI series materials or S-HPANI series materials, when the proportion of AN/SAN increases, reduce the degree of twist of the segments generated by the SAN, so the conductivity value also tends to rise.

Furthermore, the present invention provides a composite material containing phosphorus star-shaped polyaniline, wherein 1 gram of melamine resin is added to a reaction flask, and 0.02 g of an external acid is doped to dope the phosphorus-containing polyaniline, and then 0.2 g is added. Tetrahydrofuran, acetic acid and water in a bottle. Stirring at room temperature for 2 hours first gave a clear solution. Then, the reaction is heated at 140 ° C for three hours to carry out a sol-gel reaction such as hydrolysis and condensation to obtain a composite material in which an external acid-doped star-shaped polyaniline and a melamine resin are blended.

Please refer to Fig. 5 and Fig. 6, which are TGA diagrams of HPANI doped with melamine resin in different proportions under nitrogen and air, respectively. In the nitrogen environment between 200 and 400 ° C, when the amount of doped HPANI is less than 5 wt%, the flame retardant effect of phosphorus is not good, and the introduction of HPANI promotes the early cracking of the cyanuric resin, but When the proportion is increased to 10% by weight, the flame retardant mechanism of the phosphorus element begins to exert its effect, and its thermal stability is improved, and the residual amount also increases as the proportion of its doping increases.

Conductivity of polyaniline/melamine resin composites

According to the analysis of flame retardant characteristics, the measurement of the limiting oxygen index value (LOI) provides an indicator of the flame retardant property. The LOI value of the unblended cyanide resin at the beginning is about 29, which is the standard for achieving a flame retardant substance.

The LOI value of MPANI is as shown in the following table. If MPANI is blended with melamine resin in different proportions, the LOI value is measured. It is found that the LOI value decreases with the increase of MPANI, so it is judged that MPANI cannot be improved. Its flame retardant properties. However, when the amount of HPANI blended in the melamine resin is continuously increased, the LOI value is also significantly improved. The advantages and disadvantages of the flame retardant properties are related to the phosphorus content and the benzene ring content. From this table, it can be found that the control factor of the flame retardant property is phosphorus element when the phosphorus content is high, and the control factor is the structure of the benzene ring when the content is low.

According to the conclusion, the thermal stability of phosphorus-containing HPANI is better than MPANI in nitrogen or air environment. The LOI value of HPANI is also higher than that of MPANI, but the main chain MPANI has higher conductivity. Further, a polyaniline is further mixed with a melamine resin to prepare a composite. From the thermal properties analysis of the polymer material, it was found that the addition of MPANI to the cyanuric resin resulted in a decrease in the pyrolysis temperature, but the residue The amount increases. When the HPANI content is higher than 10wt%, the phosphorus atom flame retardant mechanism is activated, resulting in a decrease in thermal weight loss at 200~430°C, indicating that the flame retardant property is improved. In summary, the proper addition of polyaniline content to melamine resin can increase its thermal stability and increase its conductivity. The analysis of flame retardant properties shows that MPANI does not improve its flame retardant properties. HPANI has good flame retardancy and can be added to melamine to improve the flame retardant properties.

According to the thermal property analysis, the thermal stability of the S-MPANI and S-HPANI series in the nitrogen environment is better than that in the air environment before 400 °C, and the amount of SAN content also affects its thermal stability. The present invention has found that a phosphorus-centered star-shaped polyaniline can enhance its thermal stability regardless of whether the grafted polyaniline is doped with an external acid or self-doped. It is also found that self-doped polyaniline has better thermal stability and flame retardant properties than external acid doped polyaniline because it contains sulfur. However, the self-doping polyaniline has a lower conductivity than the external acid-doped polyaniline.

In summary, the present invention is a novelty, progressive and available for industrial use, and should conform to the patent application requirements stipulated in the Patent Law of China, and the invention patent application is filed according to law. Lee, the feeling is a prayer.

However, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the shapes, structures, features, and spirits described in the claims are equivalently changed. Modifications are intended to be included in the scope of the patent application of the present invention.

Claims (3)

A phosphorus-containing stearyl polyaniline which is an external acid-doped phosphorus-containing stearyl polyaniline having a structural formula comprising: Where R ₁ contains . A phosphorus-containing stellar polyaniline which is a self-doping type of phosphorus-containing stearyl polyaniline having a structural formula comprising: Where R ₂ contains . A method for producing a composite material containing phosphorus star polyaniline according to claim 1 or 2, wherein the main steps include: adding a melamine resin to the reaction bottle, and adding a phosphorus-containing star polyaniline Adding tetrahydrofuran, monoacetic acid and monohydrate to the bottle, stirring to obtain one solution; and heating and then performing sol-gel reaction such as hydrolysis and condensation to obtain a composite material.