TWI447141B - Conductive polymer and device thereof - Google Patents

Description

Conductive polymer and device thereof

The present invention relates to a conductive polymer and a device thereof, and more particularly to a conductive polymer having high conductivity and an apparatus therefor.

Plastic is a kind of high molecular polymer, which was originally a non-conductive material. However, scientists have found that if the electrons of the polymer can be achieved and the electrons in the metal can move freely, they are not bound to the atom. , can further achieve the effect of electricity. Recently, conductive polymer materials are rapidly developing, making it possible to apply conductive polymers to electronic and information products that generally utilize metal materials to further produce thinner, lighter and shorter products. Because conductive polymers have special photoelectric properties, they are widely used in applications such as light-emitting diodes (LEDs), field effect transistors (FETs), and electrochromic devices (Electrochromic). Device), rechargeable battery, solid capacitor, antistatic, and EMI shielding.

In the late 1980s, Bayer successfully developed a new polythiophene derivative, namely poly(3,4-ethylenedioxythiophene) (PEDOT). Among them, 3,4-ethylenedioxythiophene (EDOT) is a monomer of poly(3,4-ethylenedioxythiophene); scientists have found that PEDT exhibits some unique properties, such as: very high conductivity (about 300S) /cm) and film transparency, and not easy to be oxidized, etc., so it is widely used in solid electrolytic capacitors, plastic antistatic coatings and photographic film coatings and other fields.

However, with the demand for high density, high stability and high reliability of circuit design, how to improve the characteristics of capacitors has become one of the development priorities.

The inventor of the present invention has made a structure that is reasonable in design and effective in improving the above problems, in view of the lack of the above-mentioned conventional technology in actual application, and accumulating the experience of individuals engaged in relevant industry development practice for many years.

The main object of the present invention is to provide a novel conductive polymer which utilizes pyridine, acridine derivative, imidazole, imidazole derivative, alcohol amine compound or alcohol amine derivative and 3 , 4-vinyldioxythiophene forms a polymerization, so that the conductivity is improved by the characteristics of the above-mentioned pyridine, acridine derivative, imidazole, imidazole derivative, alcohol amine compound or alcohol amine derivative. The properties of the polymer.

In order to achieve the above object, the present invention provides a conductive polymer which is poly(3,4-ethylenedioxythiophene) ⁺ An ^- and the poly(3,4-ethylenedioxythiophene) ⁺ comprises the following formula ( a repeating unit of 1), wherein the poly(3,4-ethylenedioxythiophene) ⁺ has at least one of a pyridine, an acridine derivative, an imidazole, an imidazole derivative, and an alcohol in the main chain. a group selected from the group consisting of an amine compound and an alcohol amine derivative; at least a part of the repeating unit has a positive charge, and An ^- is a negatively charged iron (III) p-toluenesulfonate.

Where n=1 to 3.

In one embodiment, the molar ratio of acridine to iron (III) p-toluenesulfonate is about 0.3 to 1.5, followed by the addition of 3,4-ethylenedioxythiophene to acridine and 3,4. - Vinyl dioxythiophene polymerizes to form the conductive polymer of the present invention.

In another embodiment, the molar ratio of imidazole to iron (III) p-toluenesulfonate is about 0.3 to 1.5, followed by the addition of 3,4-ethylenedioxythiophene to the imidazole and 3,4- The vinyl dioxythiophene is polymerized to form the conductive polymer of the present invention.

In a more specific embodiment, the monoethanolamine is polymerized with 3,4-ethylenedioxythiophene to form the conductive polymer of the present invention, and the mixed molar ratio of monoethanolamine to iron(III) p-toluenesulfonate is about 0.3 to 1.5. .

The invention has the following beneficial effects: the invention adds acridine, acridine derivative, imidazole, imidazole derivative, alcohol amine compound or alcohol amine to the main chain of poly(3,4-ethylenedioxythiophene) ⁺ Derivatives increase the conductivity of conductive polymers. Furthermore, the conductive polymer of the present invention can be applied to a capacitor to reduce its ESR; and the above additive has good thermal stability, and thus can also be applied to an SMD element to improve the heat resistance of the element.

For a better understanding of the features and technical aspects of the present invention, reference should be made to the accompanying drawings.

The present invention provides a conductive polymer that can be applied to devices such as antistatic coatings, rechargeable batteries, and capacitive devices (including Dip and V-chip).

The conductive polymer of the present invention is poly(3,4-ethylenedioxythiophene) ⁺ An ^- , and the poly(3,4-ethylenedioxythiophene) ⁺ comprises a repeating unit of the following formula (1), and The chemical structure (eg, backbone, chelating or other bonding sites) of poly(3,4-ethylenedioxythiophene) ⁺ has at least one of pyridine, acridine derivatives, imidazole, a group selected from the group consisting of an imidazole derivative, an alcohol amine compound, and an alcohol amine derivative; at least a part of the repeating unit has a positive charge, and An ^- may be a negatively charged iron p-toluenesulfonate ( III), polystyrene sulfonate (PSS), etc.; formula (1) is as follows

Where n = 1 to 3, the symbol "⊕" indicates a positive charge.

In this embodiment, the 3,4-ethylenedioxythiophene (EDOT) represented by the formula (1) is a monomer material; and the monomer of the formula (1) is used as a repeat. The polymer formed by the unit is poly(3,4-ethylenedioxythiophene) (PEDOT). In addition, at least a part of the repeating unit has a positive charge, and An ^- is a negatively charged iron (III) p-toluenesulfonate, in other words, poly(3,4-ethylenedioxythiophene) is formed by the gravitational attraction of positive and negative charges. a doped form of iron (III) p-toluenesulfonate, therefore, the conductive polymer of the present invention is expressed in the form of poly(3,4-ethylenedioxythiophene) ⁺ An ^- ; p-toluenesulfonic acid Iron (III) is an oxidizing agent. The structural formula of iron (III) p-toluenesulfonate is as follows:

In a first embodiment of the present invention, the poly(3,4-ethylenedioxythiophene) ⁺ has at least one pyridine in its main chain, and the acridine has the structural formula shown in the following formula (2). :

In other words, the acridine system represented by the formula (2) is copolymerized with the 3,4-ethylenedioxythiophene represented by the formula (1), and the polymerization arrangement of the formula (1) and the formula (2) is a random (random) arrangement, that is, the acridine system represented by formula (2) appears randomly, and its position is not fixed, for example, formula (1) - formula (1) - formula (2) - formula (1) - formula (1) - Formula (2)-...; however, the polymerization arrangement of Formula (1) and Formula (2) may also be an alternating copolymerization arrangement, for example, Formula (1) - Formula (2) - Formula (1) - Formula (2) - Formula (1) - Formula (2) - ..., but not limited to the above.

Furthermore, in the specific embodiment, the conductive polymer is prepared by mixing the acridine represented by the formula (2) with iron (III) p-toluenesulfonate, and then introducing the 3,4- represented by the formula (1). The vinyl dioxythiophene is polymerized under normal pressure and heated to a temperature of 30 to 210 ° C for a reaction time of about 0.5 to 6 hours to complete the polymerization process to form the conductive polymer of the present invention. Further, the ratio of the acridine of the formula (2) to An ^- (the specific embodiment is iron (III) p-toluenesulfonate) is about 0.3 to 1.5, and the conductivity can be controlled by the adjustment of the above mixing ratio. The reaction rate of the polymer to adjust the conductivity of the conductive polymer.

In a variation of the first embodiment, the acridine represented by the formula (2) may be substituted by an acridine derivative, and the acridine derivative may be 2-picoline, 3- 3-picoline, 4-picoline or chloroacridine, and the like.

In a second embodiment of the present invention, the poly(3,4-ethylenedioxythiophene) ⁺ has at least one imidazole in its main chain, and the structural formula of the imidazole is as shown in the following formula (3):

In other words, the imidazole group represented by the formula (3) is copolymerized with the 3,4-ethylenedioxythiophene represented by the formula (1), and the polymerization arrangement of the formula (1) and the formula (3) is a random ( Arranged, that is, the imidazole group represented by the formula (3) appears randomly, and its position is not fixed, for example, the formula (1) - the formula (3) - the formula (3) - the formula (1) - the formula (1) - (3)-...; however, the polymerization arrangement of the formula (1) and the formula (3) may also be an alternating copolymerization arrangement, for example, the formula (1)-formula (3)-formula (1)-form (3) - Formula (1) - Formula (3) - ..., but not limited to the above.

Furthermore, in the specific embodiment, the conductive polymer is prepared by mixing the imidazole represented by the formula (3) with iron (III) p-toluenesulfonate, and then introducing the 3,4-ethylene represented by the formula (1). The bis(dioxythiophene) is polymerized under normal pressure and heated to a temperature of 30 to 210 ° C for a reaction time of about 0.5 to 6 hours to complete the polymerization process to form the conductive polymer of the present invention. Further, the mixed molar ratio of the imidazole represented by the formula (3) and An ^- (the specific embodiment is iron (III) p-toluenesulfonate) is about 0.3 to 1.5, and the conductive polymerization can be controlled by the adjustment of the above mixing ratio. The reaction rate of the substance to adjust the conductivity of the conductive polymer.

In the variation of the second embodiment, the imidazole represented by the formula (3) may be substituted with an imidazole derivative.

In a third embodiment of the present invention, the poly(3,4-ethylenedioxythiophene) ⁺ has at least one alcohol amine compound or an alcohol amine derivative in the main chain, for example, monoethanolamine is doped. mixed poly (3,4-ethylene dioxythiophene) ⁺ in the main chain, wherein the monoethanolamine and An ^- is 0.3 to 1.5 molar ratio based. The method for the polymerization arrangement and the manufacturing method in the first and second embodiments can be applied to the third embodiment, and details are not described herein.

In the embodiment of the present invention, the added pyridine, imidazole, and monoethanolamine function to lower the iron hydrochloric acid property and achieve the purpose of controlling the reaction rate, and the polymer structure copolymerized therein. Medium conductivity is better and impedance (ESR) is reduced.

Please refer to the table below, which shows the improvement in performance (voltage of 2.5 V) of the conductive polymer of the present invention and the conventional polymerization mode (ie, comparative example).

In terms of equivalent series resistance (ESR), the size of the ESR is related to the capacity, voltage, frequency, and temperature of the capacitor. When the rated voltage is fixed, the larger the capacitance, the lower the ESR. As shown in the above table, the conductive polymer of acridine added in the first embodiment, the conductive polymer added with imidazole in the second embodiment, and the conductive polymer added with monoethanolamine in the third embodiment can achieve lower than conventional polymerization. ESR is because the compound with a benzene ring can be embedded in the polymer during EDOT polymerization to achieve the function of conductivity enhancement.

In addition, the conductive polymer added with acridine in the first embodiment and the conductive polymer added with imidazole in the second embodiment can achieve a higher capacitance value than the conventional PEDOT; on the other hand, the dissipation factor (also known as the dissipation factor) From the viewpoint of the loss factor, the dispersing factor (DF), the conductive polymer added with acridine in the first embodiment and the conductive polymer added with imidazole in the second embodiment can achieve a smaller DF than the conventional PEDOT.

Hereinafter, a capacitor device using the conductive polymer of the present invention, for example, a wound type solid electrolytic capacitor, will be described. The wound solid electrolytic capacitor includes at least an anode, a cathode, and an isolation layer. The anode includes an etched conductive metal foil as an anode film, the surface of the anode film is anodized to form an oxide dielectric layer, and the anode film is connected with a wire; the cathode includes an unetched, a metal foil which has not been anodized, and another conductive wire is connected to the cathode film; the separation layer is interposed between the anode film and the cathode film; the above structure can be integrally wound into a cylindrical shape to be immersed in In the solution of the conductive polymer of the present invention, a conductive polymer electrolyte layer is formed between the anode film and the cathode film by a thermal polymerization reaction, and then subjected to an aging treatment and a selection process to complete the production of the solid electrolytic capacitor.

In addition, after the thermal polymerization step, the capacitor body may be further provided with an encapsulation layer which is completely adhered to and covered by the capacitor body. In a specific embodiment, the encapsulation layer may be encapsulated by an aluminum shell, or An epoxy resin (Epoxy, silicon, etc.) is used as a main material, and is molded on the outer periphery of the capacitor body by adhesion or coating.

The conductive polymer of the present invention can also be used for fabricating a wafer type solid electrolytic capacitor device comprising at least an anode; a cathode; and a conductive high molecular polymer electrolyte layer interposed between the anode and the cathode; wherein the conductive The polymer electrolyte electrolyte layer is formed by thermal polymerization of the conductive polymer.

The conductive polymer of the present invention is more applicable to an antistatic coating, a rechargeable battery, a capacitor device (including Dip and V-chip), for example, the conductive polymer of the present invention is applied to a capacitor device, and the conductive device of the present invention The polymer can reduce the ESR of the capacitor to improve the conductivity; and when the conductive polymer of the present invention is applied to the V-chip component, the conductive polymer of the present invention is added with acridine, acridine derivative, imidazole or imidazole. The alcohol, the amine amine compound or the alcohol amine derivative has good thermal stability, so that the SMD element has high temperature resistance characteristics, and the phenomenon that the element produces a convex rubber particle during reflow is avoided.

In summary, the present invention has the following advantages:

1. The conductive polymer of the present invention has at least one pyridine, an acridine derivative, imidazole, imidazole derivative, in the main chain of poly(3,4-ethylenedioxythiophene) ⁺ An alcohol amine compound and an alcohol amine derivative are used to enhance the conductive properties of the conductive polymer. Furthermore, the above-mentioned added compounds have good thermal stability and are advantageous for the production of V-chip components.

2. The invention can be applied to antistatic coatings, rechargeable batteries, capacitor devices (including Dip and V-chip) to improve the characteristics of the above devices, such as reducing the ESR of the capacitor, increasing the conductivity of the capacitor, and improving the components. High temperature resistance and so on.

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 equivalents of the present invention are intended to be included within the scope of the present invention.

Claims (10)

A conductive polymer which is poly(3,4-ethylenedioxythiophene) ⁺ An ^- , characterized in that the poly(3,4-ethylenedioxythiophene) ⁺ comprises a repeating unit of the following formula (1) And the poly(3,4-ethylenedioxythiophene) ⁺ is grafted with at least one selected from the group consisting of pyridine, imidazole and monoethanolamine. By, Where n=1 to 3. The conductive polymer according to claim 1, wherein the poly(3,4-ethylenedioxythiophene) ⁺ has at least one acridine of the following formula (2), and the formula (1) And the polymerization arrangement of the formula (2) is a random (Random) copolymerization arrangement; The conductive polymer according to claim 2, wherein An ^- is a negatively charged iron (III) p-toluenesulfonate or polystyrene sulfonate, acridine of the formula (2) and An ^- The molar ratio is from 0.3 to 1.5. The conductive polymer according to claim 1, wherein the poly(3,4-ethylenedioxythiophene) ⁺ has at least one imidazole of the following formula (3) in the main chain, and the formula (1) The polymerization arrangement with the formula (3) is a random copolymer arrangement; The conductive polymer according to claim 4, wherein An ^- is a negatively charged iron (III) p-toluenesulfonate or a polystyrene sulfonate, and the imidazole of the formula (3) and An ^- The ear ratio is 0.3 to 1.5. The conductive polymer according to claim 1, wherein the poly(3,4-ethylenedioxythiophene) ⁺ has at least one monoethanolamine in its main chain, and the polymerization arrangement is a random (Random) comonomer arrangement, monoethanolamine and An ^- is based molar ratio of 0.3 to 1.5. A device having a conductive polymer as described in claim 1 of the patent application. The device of claim 7, wherein the device is an antistatic coating, a rechargeable battery or a capacitor device. The device of claim 8, wherein the capacitor device is a wound type solid electrolytic capacitor comprising: an anode having an anode film; a cathode having a cathode film; and an inter a separator between the anode film and the cathode film; wherein the conductive polymer is thermally polymerized between the anode film and the cathode film to form a conductive polymer electrolyte electrolyte layer. The device of claim 8, wherein the capacitor device is a wafer type solid electrolytic capacitor device comprising: an anode; a cathode; and a conductive polymer interposed between the anode and the cathode a polymer electrolyte layer; wherein the conductive polymer electrolyte electrolyte layer is formed by thermal polymerization of the conductive polymer.