TW200531983A - Thermally stable self-doped polyanilines - Google Patents

Abstract

Just like other conducting polymers, polyanilines are useful for many important electric and electrooptical applications. A self-doped polyaniline that contains a stable/immobile, covalently bonded acid moiety on the backbone is highly desired, due to their greater resistances to solvent-washing, rain-flushing, and thermal evaporation. The present invention discloses a new type of thermally stable self-doped functionalized polyanilines that are thermally much more stable than the previously reported sulfonated-polyaniline, which was believed to be the most thermally stable self-doped polyaniline known in the art. The present invention also discloses a new and effective method for making this new type of thermally stable self-doped functionalized polyanilines.

Description

200531983 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to polyaniline, especially a heat-stable self-doped functionalized polyaniline. [Previous technology] Polyaniline is a backbone-co-guide molecule, and it has a variety of applications in butterfly towels. Polyaniline and other types of conductive polymers can be used in electrical appliances, electro-optical components, rust prevention, semiconductors, and microelectronics. Due to its unique electric grade and market potential, polyaniline has been the focus of research in polymer electronics in recent years. The original polyaniline semi-oxidation base form can be easily doped with a simple protonic acid (prOtonic aci (0 (such as Ηπ)) to become a highly conductive emeraldinesalt. (Conductivity is 5 S / cm) (Angelopoulos, M .; Asturias, GE; Ermer, SP; Ray, A .; Scherr, EM; MacDiarmid, AG Mol. Cryst Liq. Cryst 1988, / ft 151). However, these disturbed proton acid dopants are detrimental to their long-term temperature and environmental stability due to their sensitivity to thermal evaporation or rain washout. Self-doping polyaniline contains π stable / immobile on its main chain π is a covalently bonded acid molecular group, so it has better solvent resistance, rain resistance, and potential for better thermal stability, so it has attracted much attention. Self-doping I This amine can pass through Ring-sulfonation reaction (ring_sulfonation) is obtained by directly covalently bonding an acid functional group to its ring, such as sulfonated-polyanilines. For example, acidified by terms reported by Yue and Epstein Polyamines are tested in the semi-oxidized state with fuminic acid (fumin g sulfonic 200531983 acid) reaction, its conductivity is 0.1 s / cm (Yue, J., Epstein, AJ / also 6 6 tear 1990, 2800 of self). The preparation of aniline can also allow acid functional groups to be grafted on nitrogen sites through alkyl groups, such as poly (aniline-co-N-propyl lutein sulfonate) (p〇iy (aniiine-co_ ^ pr〇panesuif 〇nic acid aniline)) (PAPSAH) and poly (aniline-co-N-propylbenzenesulfonic acid) (P〇ly (aniline-ca ~ ^ propylbenzensulfonic acid)) (PAPBSAH). For example, PAPSAH reported by Chen It is obtained by reacting deprotonated polyaniline with 1,3-propanesuitone (i, 3-propanesuitone), and its room temperature conductivity is about ΗΓ2 to 1 (T4S / cm (Chen, S · A Hwang, G · W · / · Version 5bc · 1995, Factory ?: 10055) For another example, PAPBSAH reported by Chen is the use of deprotonated polyaniline and p- (3- > styropropyl) benzene. It is obtained by the reaction of p_ (3-brom〇pr〇pyi) benzenesulfonic acidsodiumsalt, and its room temperature conductivity is about 8.5x Ws / cn ^ Hua, M · γ ·; Su, Υ_ Ν ·; Chen, S · A · / b // Fat Factory 2000 Heart, 813). All of these self-doped polyanilines do exhibit significantly improved resistance to solvents and water, and have higher thermal stability than polyanilines doped with HC1. Among the various self-doped polyanilines known in the literature, cyclosulfonated polyanilines are the most striking 'because they not only have the best electrical conductivity, but also are more heterogeneous than the nitrogen-grafted self-doped polyanilines (such as PAPSAH and PAPBSAH) have high thermal stability. When heat-treated at high temperatures, PAPSAH and PAPBSAH begin to lose their sulfonic acid functional groups in the lower temperature range (approximately no to 125 °), while sulfonated polyanilines only begin to gain higher (approximately 185 C) Produces the same inferior decomposition reaction. 200531983 Although this-ring hybrid self-doped polyaniline has more thermal stability than the nitrogen-grafted self-doped / raw polyaniline, its initial inferior decomposition temperature (⑽— ⑽. ㈡ may still not be high enough for many important applications, especially ㈣ applications that contain high-temperature soldering steps (usually must be heated to about seven or more) such as semiconductor circuit boards, electronic products, and "optical products." ~ The room temperature conductivity of acidified polyaniline will also slowly decrease with time. 'This-characteristic will seriously hinder its ability to be used in long-term applications such as solar cell applications. In a high temperature environment. Therefore, only self-doped polyaniline with high thermal stability is still being searched in the 7-gauge region, so that-not only the regular heat treatment of the month b, but also at room temperature It has long-term storage stability. [Summary of the Invention] This invention is related to neutral or conductive self-doped polybenzylamine. More specifically, this-invention is related to the thermally stable self-doped functional aniline. The repeating unit containing substituted and unsubstituted stupid amines is shown in the formula ⑴ in FIG. 1:

(F? L) n ^ 2), (R2), Ο) where: x and y may be the same or different at each occurrence, they may be integers equal to or greater than 0, and x + y >0; Z It can be the same or different every time it appears, it can be-an integer greater than G; 200531983

Where X can be the same or different at each occurrence, η can be the same or different at each occurrence, 1 can be the same or different at each exit, and it is a divalent atom or molecule Group (boat ㈣, and can be selected from a group consisting of s, ㈣5, mai (= 〇), NRs, etc .; R4 can be the same or similar when each person appears, which is a functional group containing an acid substituent The functional group may be selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkenynyl group, an allyl group, a benzyl group, and a cyclic group. Alkyl (cycloalkyl), cycloalkenyl (cycloalkenyl), cycloalkynyl (cycloalkynyl), cycloalkenynyl (cycloalkenynyl), alkanyl (arylkanyl), arylolyl (arylolyl), roasting (Mercaptoalkyl), mercaptoaryi, mercaptoalkylarylalkyl, mercaptoarylalkylaryl, hydroxyalkyl, hydroxyaryl, alkylsilyl ), Arylsilyl, alkoxysilyl, Aroxysilyl, amino acid, epoxyxy moieties, alkoxyalkyl, aryloxyalkyl, aryloxyalkyl alkoxycarbonyl), alkoxysilylalkyl, alkylsilylalkyl 200531983, alkoxysilylaryl, alkylsilylaryl, heteroaryl, alkylaryl (Alkylaryl), alkylheteroaryl, arylalkyl, heteroarylalkyl, alkylarylalkyl, alkylheteroarylalkyl, alicyclic A group consisting of alicyclic, heterocyclic, and the like, and the acid substituent may be selected from the group consisting of phosphonic acid, phosphonic acid, and pendant acid ( boric acid), carboxylic acid, sulfinic acid, sulfonic acid, sulfamic acid, amino acid, and derivatives such as acid esters and A group of salts. In addition to acid substituents, R4 can optionally contain one or more other substituents, which can be selected from the group containing deuterium or other privately-allowed functional groups. This invention is also related to a new and effective method that can be used to prepare the self-doped functionalized polybenzylamine. In particular, a specific embodiment of the present invention includes the following steps: (a) providing a solid polyaniline; and (b) combining the solid polyaniline (id state polyaniline) in a selected solvent or mixed solvent The reaction with reactive chemical reagent (s) containing reactive chemical reagents can be used to process Da-segment impurities. The solvent or mixed solvent is sufficient to dissolve or disperse chemical reagents and can affect the moisture. (SweiHng) or wetting tting solid polyaniline, and the chemical reagent is sufficient to functionalize 200531983 (functionalizing) the solid polyaniline and transform the backbone of the solid polyaniline into a higher reduced form. Another specific embodiment of the present invention includes the following steps: (a) providing a solid polyaniline; (i) subjecting the polyaniline to a type of redox treatment (her χ 丨 resistant to 0 to transform the solid The backbone of polyaniline becomes a desired oxidation state (QxidatiQnsta⑹; (c) reacting the obtained polyaniline in a selected solvent or mixed solvent with an active chemical reagent to reach a stage- The mixed solvent is sufficient to dissolve or disperse the chemical reagent and is able to _laishun_ fresh amine, and the touch is sufficient to functionalize the solid polyaniline and transform the backbone of the solid polyaniline into a higher reduced state; and (d) repeat the step ( b) "and / or" (c); the order of steps (b) and (c) may be fine, or the step ⑻ or step ⑹ may be performed from the first cycle or any subsequent repeated rounds as required ( The redox / react ion treatments of the yoke y) are narrowed down. [Embodiment] This example details specific examples of the best mode currently recognized by the inventors in the present invention. As for other practical details, —And described here. This invention is related to neutral or conductive self-doped polyaniline. More specifically, this invention is related to thermally stable self-doped functional polyaniline, which contains substituted and The repeating unit of unsubstituted aniline is shown in the molecular formula (I) in Fig. 1: 200531983

U can be the same or different at each major occurrence, it can be an integer equal to or greater than 0, x + y >0; the appearance date can be the same or different ', it can be an integer greater than 0; n at each time It can be the same or different when it appears' It can be an integer from 0 to 4; 1 can be the same or different when each person appears, it can be an integer from 0 to 4, as long as it meets Lu Zhi y there is a 1 Zero, and a condition of 2 4 in each repeating unit; the substituents may be the same or different at each occurrence, and may be selected from the group consisting of hydrogen, deuterium, and alkyl ( alkyl), alkenyl, alkynyl, aikenynyi, aryi, aikyiaryi, arylalkyl, allyl, benzyl (Benzyl), alkoxy (alkoxy), aryloxy (aryioxy), cycloalkyl (CyCioaikyi), cycloalkenyl (cycloalkenyl), cycloalkynyl (CyCioaikynyl), cycloalkenyl (cycloalkenynyl), alkanoyl, aryloyl, aryloyloxy, alkanoyloxy, and thiol ( alkythio), arylthio, alkylthioalkyl, alkylthioaryl, arylthioaryl, mercaptoalkoxy, mercaptoaryloxy, M aryloxy, Mercaptoalkyl, mercaptoaryl, mercaptoaryl 12 200531983

(mercaptoarylthio), mercaptoalkylthio, mercaptoalkylarylalkyl, mercaptoarylalkylaryl, halo, hydroxyl, hydroxyalkyl, hydroxyalkyl Aryl (hydroxyaryl), cyano, nitro, alkylsilyl, aryl aryl (81 ^ 13: [171), aryl aryl (311 ^ 〇 ^ 31 & gt 171), Shi Xi aryloxy group (31′〇 and: ^ 1171), amino acid, epoxy moieties, amino, aminoalkyl , Aminoaryl, amido, amidoalkyl, amidoaryl, arylamino, diarylamino, amido alkylamino), dialkylamino, alkylarylamino, alkoxyalkyl, aryloxyalkyl, alkoxycarbonyl, and oxoalkyl alkoxysilylalkyl), alkylsilylalkyl, alkoxysilylaryl ), Alkylsilylaryl, heterocyclic ring, heteroaromatic ring, alkylsulfinyl, arylsulfinyl, alkyl (Alkylsulfonyl), arylsulfonyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylcarboxylate, alkylsulfinate, A group consisting of alkylsulfonate, alkylphosphonate, ester derivatives of acid functional groups, etc., wherein the acid functional group is selected from the group consisting of phosphonic acid, hypophosphorous acid, boric acid, carboxylic acid Acid, sulfinic acid, acid, 13 200531983 the aromatic, the heteroaromatic, the fat

A group consisting of sulfamic acid or amino acid; the aromatic, family, and cycloaliphatic functional groups contain one or more functional groups consisting of phosphonic acid, hypophosphorous acid, boric acid, carboxylic acid, and sulfinic acid. Derivatives of acids, sulfonic acids, and acids such as esters and salts, alicyclic rings (alicyciic R! Combined or any of 4 and any of -M to form-a subline containing a substituent and alkylene containing a substituent) ), Alkenylene, or alkynyi㈣

Aromatic ring (heteroaromatic), heteroalicyclic ring (heteroalicyclic) or alicyciic ring (alicyciic ring), the ring may contain one or more non-carbon atoms „and / or, a 4 shell Molecular groups that bind to evil, such as nitrogen, sulfur, sulfur, sulfinyl, suifonyi, phosephrus, seienium, S purpose class (ester), carbonyl group (cari3onyi), and oxygen (oxygen), etc., and the allowable substituents are the aforementioned acids and other functional groups; or 仏 may also be an aliphatic molecular group , Whose molecular formula is-(〇CH2CH2) q〇CH3 ^-(OCH2CH (CH3)) q〇CH3,-(CH2) qCF3,-(CF2) qCF3, or-(CH2) qCH3 where q is a positive integer; or It is a derivative of the following molecular formula: 200531983-(ORlO) r0Rll where:

(Ru) a-> yell bond group of Asian silk molecules containing up to about 7 carbon atoms;

Ru is an alkyl group containing 1 to about 20 carbon atoms; r is a natural number from 1 to about 50; R2 may be the same or different at each occurrence and has the following molecular formula: -x-r4 where X It can be the same or different in each occurrence, it is a divalent atom or molecular group (mollet), and can be selected from a group consisting of SnNR5C㈣, NRs, etc .; R5 may be the same or different at each occurrence, and may be selected from a group consisting of hydrogen and other functional groups allowed by Ri; and R4 may be the same or different at each occurrence, which includes acid substitution A functional group of a radical, wherein the functional group may be selected from the group consisting of alkyl, aryl, alkenyl, alkynyl, diacyl, propyl, benzyl, cyclofilament, cycloalkenyl, cycloacyl, cycloalkenynyl , Burning base, aromatic brewing base, scorching base, Wei Fangji, Hangfang silk, scorching aromatic aryl, ship base, warp aryl, Shi Xi silk, Shi Xi aryl, Shi Xi alkoxy, Shi Xi fang Molecular groups of oxy, amino acids, epoxy groups, silk-based, fluorenyl, alkoxycarbonyl, alkoxysilyl, alkylsilyl, alkoxysilyl , Alkylsilyl, heterocyclic aryl, aryl aryl, aryl aryl, aryl & aryl, aryl aryl, & aryl aryl, heterocyclic aryl, aliphatic, and The group is scale-like, and the acid substituent may be selected from the group consisting of phosphonic acid, hypophosphorous acid, boric acid, carboxylic acid, sulfinic acid, sulfonic acid, sulfanilic acid, amino acid, and derivatives thereof such as acid 200531983. A group of vinegars and acid salts. In addition to acid substituents, three or more other optional substituents can be selected from groups containing fluorene or other functional groups permitted by &. -In a preferred embodiment of the present invention, the structure of the heat-stable self-heterophilic functionalized polyaniline of the present invention contains a repeating unit of the formula ⑴ in Figure 丨, where X y ζ, η, 1, Private, r3, r4, and r5 are as described above, and X may be the same or different at each occurrence, and may be selected from a group consisting of milk, clothing, occupation, and NRs. In a particularly preferred embodiment of the present invention, the structure of the thermally stable self-doping functionalized polyaniline of the present invention contains a repeating unit of the formula ⑴, such as: X, y, Z, n, Bu仏, R3, R4, and 仏 are as described above; X may be the same or different at each occurrence, and may be selected from a group consisting of 3 and 陬 £ (= 〇). In a preferred embodiment of the present invention, the structure of the thermally stable self-doped functionalized polyaniline of the present invention contains a repeating unit of the formula (1) shown in Figure 丨, wherein: X, y, ζ, η, Bu Si, R3, and Si are as described above; and \ is sulfur. This invention is also related to a new and effective method that can be used to prepare the self-exchanging heterofunctionally functionalized polyaniline. In particular, a specific embodiment of the present invention includes the following steps: (a) providing a solid polyaniline; and (b) combining the obtained polyaniline in a selected solvent or mixed solvent with an active The chemical reagent is subjected to a reaction treatment for a period of time. The solvent or mixed solvent is sufficient to dissolve or disperse the 16 200531983 chemical reagent and can brighten or moisturize the solid polyaniline, and the chemical reagent is sufficient to functionalize the solid polyphenylamine. The backbone of the solid polyaniline is transformed into a higher reduced state. ′ Refer to FIG. 2, another specific embodiment of the present invention, which includes the following steps: (a) providing a solid polybenzylamine; ⑻ subjecting the solid polyaniline to a redox treatment to convert the solid The backbone of polyaniline becomes a desired oxidation state; (c) The obtained polybenzylamine is reacted with a reactive chemical reagent in a selected solvent or mixed solvent for a period of time, the solvent or mixed The solvent is sufficient to dissolve or disperse the chemical reagent and to wet or wet the solid polyaniline, and the chemical reagent is sufficient to functionalize the solid polyaniline and transform the backbone of the solid polyaniline into a higher reduced state; and (d ) Repeat step (b) " and / or "(c); wherein the order of steps (b) and (c) can be reversed, or step (b) or step (c) can be performed from the first round or any It will be omitted in the subsequent "reduction / reaction" process. The reaction treatment here will be carried out for a period of time which is sufficient to convert the obtained polyaniline into a desired oxidation state which is different from the original solid polyaniline. · A preferred embodiment of the method of the present invention. The polybenzylamine provided in step (a) is a solid L-y formula such as 籾 powder (p0W (jer), coating layer (⑴, 丨)). , Film (1, 1), pressed powder, multi-layer coating (miQtuayer coaung), laminated film (laminated film), or any other known solid form, and a combination of the above types. The preferred polyaniline in the E1 state is a polybenzylamine coating layer, which can be a polyaniline solution through solution 17 200531983 solution casting, dipping coating, spray coating, rotation Spin coating, brush coating, and any other known methods to prepare it. Polyaniline film or coating layer can also be a solid polyaniline or a combination of traditional polymers Or a mixture of dopants, etc., prepared by melt casting, hot-pressing, thermal evaporation coating, or any other known method .Polyaniline film or coating layer can also be applied by reaction of related amine monomers. (Reaction coating), any suitable electrochemical polymerization method, or any other known method to prepare it. In step (b), the rhenium / tongue chemical agent can be any medium (Job Seal) As long as it can functionalize (or derivatize) the polyaniline in step ⑷, and transform the backbone of the solid polyaniline into a higher Gaulle form. Here, in the reaction treatment step, One or more active biochemical reagents can be used simultaneously or in stages, depending on the needs of a particular application. The preferred active chemical reagents are thiols (alcohols), alcohols (alcohs) ), Scales (phosphines), amines-), and amides (amides), or a combination of the above types. Any combination of active chemical reagents can be used, as long as it is used in any single reaction processing step or in a series of reaction processing steps, certain chemical reagents can be finally converted into the ones mentioned in the formula ⑴ in Figure 1 above. One of the substituents of the self-doping functionalized polyaniline is sufficient. These active chemicals can be in a pure liquid or solution state. If the solution used is a solution of an activated chemical reagent, any concentration can be used, as long as the reaction rate is a cross-link value at the temperature used. Any solvent or solvent mixture can be used to implement the method of the present invention, so long as it can dissolve or disperse the active chemical agent, and swell or wet the solid polyaniline, such as water (h2〇), methanol, Ethanol (ethan〇1), tetrahydrofuran (THF), a mixed solution of water and N-methylpyirolidone (NMP), a mixed solution of water and tetrahydrofuran, and the like. When the polarity of the polybenzylamine is too far from that of the chemical agent, a co-solvent (or solvent mixture) can be used to implement the method of the present invention. In this case, as long as the co-solvent mixture contains at least one component that can dissolve or disperse the chemical agent and another component that can pour or wet the surface of the solid polyaniline. The solvent or solvent mixture selected for the implementation of the method of the present invention should mainly depend on the polyaniline and the chemical reagents used. Polyanilines and chemicals with higher polarity usually require solvents with higher dielectric constants and dipole moments. In contrast, polyanilines and chemicals with lower polarity require solvents with lower dielectric constant and dipole moment. Generally, the selected solvent or solvent mixture is used to mix the solvent of polyaniline and the more polar chemical reagent, and has a dipole moment of about 0.3 to 5.0, and a dielectric constant of about 10 to about 190. In a preferred embodiment of the present invention, its dipole moment and dielectric constant are about 1.8 to 5.0 and about 20 to 100, respectively. Exemplary solvents are alcohols, ethers, chain or cyclic, halocarbons, amides, substituted aromatics, and nitriles ( nitriles), carbonates, sul fox ides and other sulfur-containing solvents, alkanes containing nitro substituents, and aromatic, water, or a mixture of the above types Wait. Examples include alcohols of 200531983, including methanol, ethanol, isopropanol (iSOpropanol), and the like. Examples of chain-like or ether-like ethers include tetrahydropyran, tetrahydropyran (tetrahydropyran), 2-methyltetrahydropf, 2-methyltetrahydrofuran, diethyl ether, di Glyme, diglyme, and so on. Examples of halogenated carbon compounds include chloroform, i, 2-dichlo: roethane, dichloromethane, and the like. Examples of amidines include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like. Examples of the aromatic group having a substituent include xylene, anisole, and toluene. Exemplary nitriles include acetonitrile, propionifriie, benzonitriie, butyronitrile, and the like. For example, Acer and other sulfur-containing solvents include dimethylsulfoxide and the like. Examples include nitro-substituted alkanes and aromatics including nitromethane, nitropropane, and nitrobenzene. Exemplary carbonic acids include propylene carbonate, ethyiene carbonic, and the like. Usually selected solvents or solvent mixtures used to compound polyaniline and less polar chemical spring reagents' have a dipole moment from about 0 to 3.0 (preferably 0 to about 2.5) and a medium The electrical constant is from about 2.0 to about 50 (preferably about 20 to about 35). Examples of such solvents are halogenated carbon compounds such as digascarin, etc., aromatic solvents such as toluene, xylene, and benzene, and the like and bonded compounds such as ethylene glycol dimethyl ether (dimethoxyethane). , And tetrahydrofuran and other 4 S species such as ethyiacetate and methyifomate etc. 20 200531983, etc., sub-maple species such as dioxoyl acer, etc., ring and Chain-like amidines such as diamidamine, N-methylpyrrole I, N, N-dimethylacetamide, etc., and ketones such as acetone, etc. Etc., and mixtures of the above. In general, the amount of solvent and solvent mixture used as the reaction medium is not important, as long as the chemical reagent is sufficiently dissolved or dispersed and the solid polyaniline can be moistened or moistened. A pure chemical reagent is also applicable, as long as it is a liquid at the reaction temperature and can swell or wet the solid polyaniline. The chemical reaction can be performed at any temperature as long as the reaction rate is acceptable, or the polyaniline or the chemical agent will not be destroyed by a large amount at this temperature. The chemical reaction can be performed under any gas, as long as the chemical reagent or polyaniline is not destroyed by a large amount, such as N2, Ar,

He, Ne, air, 02 and so on. If it is necessary to precisely control the degree and form of substitution, it is better to carry out under an inert gas, such as N2, Ar, He, or Ne. A catalytic amount of protonic acid or Lewis acid can also be added to accelerate the reaction rate. The duration of the reaction can vary widely, depending on the reaction rate between its reagents and polyaniline under the reaction conditions, and on the degree of derivatization desired. An important feature of this chemical reaction is that when the active chemical reacts with polyaniline, it will also be grafted onto the polyaniline backbone. The grafted polyaniline backbone is also transformed into a more reduced state. The backbone of polyaniline contains diiminoquinoid and diaminobenzenoid rings. A typical unsubstituted polyaniline has a backbone structure as shown in the molecular formula (II) in FIG. 3, where a and b are real numbers, a plus b is equal to 1, O ^ aSl, 0 21 200531983. Generally, the lower the a / b ratio, the higher the degree of oxidation of polybenzylamine. Conversely, the higher the a / b ratio, the higher the degree of reduction of polyaniline. Therefore, a higher reduced polyaniline backbone can be identified by a relative increase in the a / b ratio. The degree of reduction can generally be increased by infrared spectroscopy (IR) for undoped polyaniline samples and observed at 1500 cm1 (the c = c bond of the diaminobenzene ring). Stretching vibration mode) and the relative ratio of the vibration peak intensity at 1600 cm-1 (the stretching vibration mode of the c = c bond of the diiminoquinone ring). In another embodiment of the method of the present invention, a redox treatment step may be selectively added before or after the reaction treatment step. This redox treatment step can be used to adjust the redox degree of polyaniline to the desired heterogeneity, which can be suitable for subsequent reaction treatment or application. This redox treatment can be performed by chemical or electrochemical methods. The chemical method is to use the obtained solid polyaniline with oxidizing or reducing gases, such as &, air, melons, other oxidizing gases, etc., or with oxidizing or reducing chemicals, such as Aps (peroxy sulfuric acid Ammonium; Ammonium per0XySUifate), MCPBA (m-gas perbenzoic acid; tChloroperoXybenzoic acid), FeCh, chromic acid (chromimic acid), La Office,

Na2Cr2〇 ^ H2〇2 ^ ic ^^ ^ phenyl hydrazine _UA1H4, NaBH4, or any other known reducing agent, etc., for a period of time long enough to achieve the desired redox state. The redox treatment can be performed at any temperature as long as the reaction rate is acceptable or the polyaniline is not significantly damaged at that temperature. The redox treatment step can be performed by an electrochemical method. The electrochemical method is carried out by placing, attaching, or coating polyaniline on or to the conductive material of Table 22 200531983, and then connecting the λ I electrical material or surface to a typical electrochemical cell. Or, the polyaniline is converted into the desired redox state at the desired electrochemical potential. Preferred conductive materials or surfaces are metals (such as uranium, stainless steel, iron, gold, silver, and copper, etc.), alloys, conductive glass (ITQ; indium tin oxide), and p-type Or n-type doped stone wafers, conductive metal oxides, or any other known conductive surface or substance. In each process, the potential of the electrochemical reaction can vary widely, from about -0 · 2ν (relative to SCE or saturated calomel electrode) to about 0 · 9ν (relative to SCE), the value of which depends on the aided The type of polybenzylamine and the degree of substitution desired. Generally, the higher the applied potential, the higher the degree of oxidation of polyaniline. The higher the degree of oxidation of the polyaniline used to react with the chemical reagent, the higher the substitution amount of the obtained polyaniline. When the desired substitution amount is less than 25 mol% (based on the repeating unit of polyaniline) and when the substitution amount does not need to be accurately controlled, this redox process can also be omitted. In this case, if polyaniline is also in its most stable semi-oxidized state (that is, it contains about 25 mol% of the diiminoquinone ring), it can be directly used for the reaction treatment step with chemical reagents without the need of After this redox pretreatment step. If the relevant application requires a replacement amount greater than 25 m01% (based on the polyaniline repeat unit as the juice basis) "and / or '1 when the replacement amount must be accurately controlled, this redox treatment step must be used In any case, in any of the above cases, after the reaction treatment step, a redox post-treatment step can be selectively applied to convert the polyaniline into the desired oxidation state, so that it can be used in the desired application. The best performance is obtained. For example, after reacting with chemical reagents in step 200531983, we can force the obtained polyaniline to adjust its potential to 0.2 to 0.3 V (relative to SCE or saturated glycan). Mercury electrode) 'in order to quickly obtain its optimal conductive state. This kind of fast operation performance is extremely important in the application of semiconductor components, because the subsequent process is tight-closed. Some applications such as corrosion protection In terms of coating, the finished polyaniline product (which is in the form of a surface layer, a film, or a coating) is in the air and does not quickly transform into the best conductive state (ie, its semi-oxidized state). Demand. In this case, the obtained polybenzylamine can gradually reach its best conductivity and the most stable semi-oxidation state through the oxidation of the surrounding air. In addition, there are some applications that may require a specific oxidation state rather than its The semi-oxidized state, in which case this processing step must be adopted. These redox and reaction processing steps can also be applied to any desired combination order and repetition of the repetition. And in each repetition of the repetition, The chemical reagent used may be the same as or different from the chemical reagent used in the previous reaction treatment step. If the chemical reagent used in the repetition cycle is the same as that used in the previous reaction treatment step, it is derived from the chemical reagent The amount of substituents will increase. In this case, the method of the present invention can be used to prepare polyaniline with a specific degree of substitution, so that it has the desired properties for specific applications. For example, we will The non-substituted polyaniline film on the electrode can be dissolved in THF (tetrahydrogen) after three cycles of treatment as described below. Furan) ability: In each repeated treatment cycle, a redox treatment step is used to force the polybenzylamine film to 5 v (relative to a saturated glycine electrode in a 0.5 M sulfuric acid aqueous solution) and once reacted The treatment step is used to soak the I aniline film in a methanol-soluble 24 200531983 solution containing 0.2 M dodecane-1-thiol for 60 minutes. After the treatment, the resulting polyaniline contains About 45-50 mioi% of dodecylthio (based on the repeating unit of polyaniline) and become soluble in THF at the same time, it is not the original unsubstituted poly Solvents for aniline. If the chemicals used in the repetitive treatment cycle are different from those used in the previous reaction treatment cycle, the types of substituents on the same polyaniline backbone will increase. For example, if the non-substituted polyaniline film on the platinum electrode is given three rounds of reaction treatment similar to the above, but different thiols are used in each round, which are mercaptoacetic acid and dodecane- 1-thiol and mercaptoethanesulfonicacid. The resulting polyaniline can contain three different functional groups on the same polyaniline backbone, and is thus endowed with multiple functions, such as self-doping and strong solubility. It is surprising that the thermal stability of the self-doped polyaniline produced in the present invention is much higher than the self-doped sulfonated polyaniline reported in the literature. For example, when a powder of non-substituted polyaniline is reacted with an acid-functional thiol such as CmerxaptopiOpanesuifonicacid), the resulting polyaniline is reduced and simultaneously replaced with a sulfonium propylthiosulfonate (pr 〇pylthithiosulfonated) functional group contains one% acid functional group attached to the end of a propylthio substituent. The conductivity of this propylthiosulfonated polyaniline (MPS-Pans) shows that it is less susceptible to the influence of water washing solutions with different pH values, and exhibits the characteristic behavior of typical self-doped polyaniline. Thermogravimetric analysis (TG) can be used to test the thermal stability of this new type of self-doped Mps-Pans. Thermogravimetric analysis of MPS-Pan with a substitution amount of 20 mol% with 25 200531983 shows that in addition to a small amount of water lost below about 120t, a slightly lesser temperature was generated between 260 and 400 ° C. Weight loss (concerned by XPS research that this is related to the loss of acid functional groups), and then a major weight loss occurred at 524 (this is caused by polymer backbone cracking). The initial temperature for this slight weight loss event was about 260 ° C, and its starting and onset temperatures were about 270 ° C. As for the main weight loss event, the starting temperature is about 470 ° C, and its starting temperature is covered by its previous events. In order to facilitate comparison, we also use literature methods (Yue, J ·; Wang, ZH; Cromack, L R .; Epstein, AJ; MacDiarraid, AGJ Am. Chem. Soc. 1991, 2665) to prepare a 55.8 mol % Substituted amount of sulfonated polyaniline, and tested the same thermal stability using the same conditions. The results show that in addition to an initial dehydration event below 120 ° c, the weight loss of S-Pan exhibits a continuous multi-stage characteristic, and its initial temperature is about 185 ° C (this is the loss (Caused by the acid functional group), the starting temperature is about 23 ° t, and the initial major weight loss event is about 273 ° C. Chen et al. Also reported similar starting temperature (190 ° C) and main weight loss temperature (275 C) for an S-Pan containing 50 mol% substitution (Chen, S. A .; Hwang, GW ifecrofflo / ecw / es11996 but 3950). These results clearly show that the thermal stability of the novel self-doping polyaniline MPS-Pan obtained according to the present invention is indeed much higher than the example of the best self-doping polyaniline known in the literature, namely, sulfonated polyaniline S -Pan. A possible mechanism is proposed here to explain why Mps-pan has higher thermal stability than sulfonated polyaniline. When the S-Pan produced a poor solution, a reversible reaction occurred between the protonated imine and the acidified ortho carbon due to the intensification due to the temperature increase. 3_ 26 200531983 1'3-hydrogen shift reaction Then, a subsequent desulfonation reaction occurred, because its by-product s03 was evaporated at high temperature, resulting in irreversible changes. For MPS-Pan, although similarity may still occur between the protonated imide group and the ortho carbon substituted by _; [, 3—hydrogen shift reaction, but the gas in this ortho position will The -S03 functional group at the terminal is quickly removed in order to transform its unstable non-aromatic intermediate structure into a stable aromatic benzene structure, thereby dissolving its cleavage reaction. It is precisely because the cyclo-acidification and the delithization reaction are indeed-reversible equilibrium reactions, the same hypothesis also seems to explain why when hybrid polyaniline is bribed at room temperature, Jian will slowly lose its acid-renewing function. base. This desulfonation mechanism is adequate to explain why sulfonated polyaniline has long-term instability. ΐ! Enlightenable active chemical audition 丨 The chemical reagents usable in the present invention can be any medium as long as they can derivatize polyaniline and at the same time generate a more reduced polyaniline backbone. Examples of preferred active chemical reagents are thiols, alcohols, phosphines, amines, and amidines. For example, the preferred active chemical reagents are the molecular formulas II to X in FIG. 3, where: “R” or R8 and R9 may be the same or different at each occurrence, and may be selected from the group consisting of nitrogen, gas, “carbon, Alkenyl, alkynyl, alkenyl, aryl, aryl, aryl, alkynyl, propenyl, phenylfluorenyl, alkoxy, aryloxy, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkenyl Radical, alkylsulfenyl, arylfluorenyl, arylfluorenyloxy, alkynyloxy'alkylthio, arylthio, alkylsulfanyl, alkylthioaryl, arylthioaryl, sulfanyloxy, fresh oxygen Base, parent, aryl, sulfanyl, sulfanyl, sulfanyl, sulfanyl, mercaptoaryl, hydroxy, hydroxyalkyl, hydroxyaryl, silyl, silyl, silyloxy, 27 200531983 Shi Xi aryloxy group, amino acid, epoxy group, amine group, amine silk, amine aryl group, amino amine group, amidine silk, amine aryl group, aromatic amine group, double aromatic amine group, Amine group, Diamine group, Aromatic group · Aromatic group, Oxygen group, Aromatic group, Aoline group, Ao group, A group group, Ao group, Ao group, A group group Ring, heterocyclic aromatic ring, thiosulfinyl, Sulphur sulfite, burnt stilbene, aryl stilbene, sulphur sulphur, burnt sulphur sulphur, sour vinegar, burnt sulphur sulphur vinegar, burned sulphur acid, lysate etc.-groups ; Xianxiang family, the material fragrance family, the month of fat, and the cycloaliphatic and other functional groups contain one or more functional groups, the functional group is selected from the group consisting of phosphonic acid, hypophosphorous acid, boric acid, carboxylic acid, Sulfonic acid, sulfonic acid, sulfamic acid, amino acid, derivatives of the above acids such as esters and salts, alicyclic rings, heteroalicyclic rings, aromatic rings, heteroaromatic rings, halo, nitrates Radicals, cyano, thiol, hydroxy, epoxy groups, and other groups consisting of the aforementioned daggers, or hydrazone and R9 functional groups; or R ?, dagger and Rg can also be an aliphatic molecule Group, whose molecular formula is-(OCH2CH2) qoCH3,-(〇CH2CH (CH3)) qoCH3,-(CH2) qCF3,-(CF2) qCF3, or-(CH2) qCH3 where q is a positive integer; Or R ?, R8 and R9 are molecular group derivatives of the following formula: Lu Yi (ORlO) rORn where:

Rio is a divalent bonded alkylene group containing 1 to about 7 carbon atoms;

Ru is a alkynyl group containing 1 to about 20 carbon atoms; r is a natural number from 1 to about 50; or 28 200531983 private and combined form &-a sub-group with or without substituents A dilute, or alkynyl chain, and an aromatic ring, a heteroaromatic ring, a heteroalicyclic alicyclic ring, or a 3-, 4, 5, 6, 7, 8, 9, or 10-membered ring, The ring may contain one or more non-carbon atoms and / or divalent bonded molecular groups, such as nitrogen, sulfur, thiosulfenyl, hydrazone, disc, code, vinegar, Jk group, and Oxygen and the like, and the permissible substituents are the aforementioned acids and other functional groups; and M may be selected from the following groups, including non-metal cations such as BluN +, H +, No +, No2 +, nv, + N (CH3) 2H2, (: crystal melon, etc., or metal cations such as Na +, u +, κ +,% 2 +, ca2 +, 竑 +,

Ba + 2, Co + 3, A1 + 3, Fe + 3 and so on.

The available polyphenylene polyaniline is listed as a single polymer or co-polymer. Among them, at least 50% of the repeating backbone units are selected from the group consisting of consumables and amine lysyls containing substituents or prosthetic groups ( ―Leg—or NR—where R is a non-hydrogen substituent), a group of quinoid rings with or without substituents, and imine (_N =) linking groups, with different proportions To combine. Neutral or undoped polyaniline is characterized by an uncharged polyaniline backbone. Conductive or doped polyaniline is characterized by a charged main chain, which may be caused by partial or full protonation of the amine groups " and ^ or " imine lines. Any form of polyaniline can be easily applied in the practice of this invention. Examples of useful forms can be found in the following literature reports: (1) Green, A · G · and Woodhead, A · E., '' CXVII-Aniline-black and Allied Compounds, Part II, J · Chem · Soc · 101, pp. 1117 (1912) 'and (2) Kobayashi, et al ·, " Electrochemical 29 200531983

Reactions ... of Polyaniline Film-Coated Electrodes " j Electroanal · Chem. · 177, pp. 281 -91 (1984). · According to a preferred embodiment of the present invention, the useful polyaniline is a single polymer and a copolymer, which can be polymerized from a stupid amine without a substituent and a substituted amine as shown in the molecular formula (XI) in FIG. 3 And prepared, where: η is an integer from 0 to 5; m is an integer from 0 to 5 as long as it meets the condition that the sum of η and m is equal to 5 and that it has at least one position on the aniline ring (especially the para position) (Para) is preferably a substituent such as halogen, hydrogen, or other leaving group; etc .;

Ri2 may be the same or different at each occurrence, and may be selected from the group consisting of deuterium, alkyl, dilute, alkynyl, alkenyl, aryl, alkaryl, aralkyl, propenyl, benzyl , Alkoxy, aryloxy, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkenyl, alkylfluorenyl, arylfluorenyl, arylfluorenyl, alkoxyl, alkylthio, arylthio Alkyl, alkylthioalkyl, alkylthioaryl, arylthioaryl, fluorenyloxy, mercaptoaryloxy, mercaptoalkyl, mercaptoaryl, mercaptoarylthio, mercaptothio, pinanearyl , Mercaptoaryl, halo, mesityl, hydroxyalkyl, hydroxyaryl, cyano, nitro, sylalkyl, silyl, sylalkoxy, silyloxy, amino acid , Molecular groups of epoxy groups, amine groups, amine alkyl groups, amine aryl groups, · amine groups, amine groups, amine groups, amine groups, aromatic amine groups, diaromatic amine groups, alkylamine groups, dialkylamines Alkyl, alkarylamino, alkoxyalkyl, aryloxyalkyl, alkoxycarbonyl, alkoxysilyl, alksilyl, alkoxysilyl, alkylsilyl, heterocycle, heterocyclic aromatic ring, Alkylenesulfinyl, arylsulfinyl, alkylsulfinyl, aromatic Composed of sulfonyl, alkylsulfinyl alkyl, alkylsulfinyl alkyl, alkyl carboxylic acid ester, alkyl sulfinate, alkyl sulfonate, alkyl phosphonate, acid functional ester derivatives, etc. A 30 200531983 group, in which the acid functional group is selected from the group consisting of 臆 _ u ^ 疋 U in paste, sub-Wei, acid, retarded acid, arsenic acid, acetic acid, acetic acid, or amino acid The group consisting of: the aromatic group, the heteroaromatic 1 aliphatic group, and the cycloaliphatic group contains _ or more functional groups, and the official group is selected from the group consisting of phosphonic acid, sub-acid, Professional, laboratory, linoleic acid, luteinic acid, amine acid, amino acid, derivatives of the above acids such as vinegars and salts, alicyclic rings, heteroalicyclic rings, aromatic rings, heteroaromatics A group consisting of a ring, a halo group, a nitro group, a cyano group, a fluorenyl group, a hydroxyl group, a cyclic octyl group of 8% 丞% oxygen, and other aforementioned heart functional groups; any two R12 together or Ren—R12 and Ren—combined together to form a Weiji, extension, or ship-based chain with or without substituents and surrounded by =, 4, 5, 6, 7, 8, 9, or 10 members Aromatic ring , Heteroaromatic ring, heteroalicyclic ring or alicyclic ring 'whose ring may contain one or more non-carbon atoms, and / or, ι divalent bonded molecular groups, such as nitrogen, sulfur, Thionyl, sulfofluorenyl, phosphorus, selenium, esters, carbonyl, and oxygen, etc., and the permissible substituents thereon are the acids and other functional groups mentioned above; or

Ri2 can also be an aliphatic molecular group. Its molecular formula is-(〇CH2CH2) q〇CH3,-(〇CH2CH (CH3)) q〇CH3,-(CHACF3,-(CF2) qCF3, or-(CH2) qCH3 where Q is a positive integer; or R12 is a molecular group derivative of the following formula:-(ORio) rORn where: the heart is a divalent bonded alkylene group containing 丨 to about 7 carbon atoms. Rn is an alkyl group containing from 1 to about 20 carbon atoms; 31 200531983 ^ a natural number from 1 to about 50; & may be the same or different at each occurrence, and may be selected from substitutions permitted by hydrogen and hydrogen The group consisting of groups, etc. When the present invention is known, the preferred polybenzylamine is the molecular formula 叩 in Figure 4; where: η may be the same or different in each occurrence, and it may be-the integer from ㈣ About 4;

Ri and R3 are the ones described above; continued y may be different from each other in each occurrence, it may be a round or thin integer, and x + y >〇; 2 may be the same or different in each occurrence, It may be an integer-greater than 0. Just so. The number of repeating units of the aniline mono-polymer or co-polymer is not very large, and can be sickened with considerable radiance. If the number of heavy fresh elements is larger, the degree and molecular weight of the polyaniline early-polymer or silk compound are also simply larger. For example, when polyaniline mono-polymers or silk compounds with smaller molecular weight and viscosity are required, materials with such characteristics are prepared; if polyaniline mono-polymers or copolymers with high molecular weight and high viscosity are required for applications It can also be used as required. The number of repeating units is at least 3, and the upper limit can have a great degree of change, depending on the required molecular weight, viscosity, and processability, such as melt processability, solution processability, and the like. In a preferred embodiment of the present invention, the number of repeating units is at least < 10 • In a particularly good embodiment, it is at least 30. The best of those _good specific real # is at least 40. Polyaniline mono-polymers and copolymers can be conveniently synthesized using known procedures. These 32 200531983 steps are familiar in the relevant field and will not be described in detail here. Please refer to the literature as follows: £ μ ^ es,, 〇yIe, M. owskland C. Tslntav1S) synthet1cMe ^^ 1990, 36, 139. The amines can be prepared by donating any known chemical and orthodox synthetic steps. For example, a polyaniline in a redox state can be prepared by using sulfonium persulfate (leg noodles) in an excessive amount of orbital i aqueous solution. The polyaniline in powder state is blue-green. After methanol washing and air drying, its conductivity is about 5 ^. This polyaniline in a conductive state can be treated with an ethanol solution of hydrogen peroxide to form a non-conductive polyaniline, which is purple and has a conductivity lower than that of a claw. s heart. Other chemical processes can be used to solve the assimilation of polyphenylene. It is also described in detail in the thesis (such as those cited by Caffe et al.). Polyaniline in useful forms can also be prepared by electrochemical methods. For example, polyaniline in a useful form can be prepared by electrochemically polymerizing aniline on a platinum sheet anode using an aqueous solution of fluoroboricacid as an electrolyte. Other possible new and existing chemical and electrochemical methods that can be used to synthesize and convert polyaniline are all available methods. In addition, other new forms or types of polybenzylamine may be revealed in the future. Therefore, within the scope of the attached patent rights or the equivalents thereof, there is no restriction on any synthetic method, form-change method, or structure described or conceived herein. As long as all the polyaniline synthesized above is in a non-completely reduced state (leucoemeraldineforms), the polybenzylamine can be reacted with the active reaction reagent of the present invention to synthesize the thermal stability of the present invention according to the method of the present invention described above. Type self-doping functionalized polyaniline. As for the prepared fully reduced polyanilines, as long as they can undergo an additional 33 200531983 simultaneous or separate or serial oxidation treatment to generate oxidation state units, that is, diimino ring, can also be used to prepare the thermal stability of the present invention Type self-doping functionalized polyaniline. In addition, the thermally stable self-doped functionalized polyaniline single polymer of the present invention can also be prepared directly from any aniline unit containing at least 1 fluorene substituent by any known chemical or electrochemical method, as shown in the figure. 5 in the molecular formula ⑼n. The thermally stable self-doped official polyaniline filaments of the present invention can be prepared from a mixture containing aniline units as shown in the molecular formula (XIII) in FIG. 5 and the molecular formula (3) in FIG. 3. Since the thermally stable self-doped functionalized polyaniline prepared directly from polybenzylamine via the method of the present invention has a conductivity that is generally much higher than similar products made by other known synthetic methods, if When the relevant requirements also require high conductivity, the method of the present invention is a better choice. If related applications do not necessarily require high electrical conductivity, traditional chemical and electrochemical methods can also be used to prepare the heat-stable self-doped functional polyaniline of the present invention. The thermally stable self-doped functional polyaniline single polymer or copolymer of the present invention may be in a neutral undoped (non-conductive state) form or a conductive state having different doping degrees. In the neutral undoped (non-conductive) state, the covalently bonded acid functional groups of the self-doped functionalized polyaniline are in the form of their salt compounds or vinegar compounds. In the conductive state, the covalently bonded acid functional group of the self-doped functionalized polyaniline is in the form of its acid compound. As for the degree of doping, it can be controlled by the amount of R2 functional group and the acid form of the covalently bonded acid functional group. The amount of covalently bonded acid functional groups and the degree of doping are not important, and can vary widely depending on the requirements of individual applications. In general, the greater the number of & functional groups and the higher the covalently bonded acid functional group in the acid form, the higher the conductivity of the self-doped functionalized polyaniline. Generally, a sufficient amount of acid functional groups are grafted on the polyaniline backbone to generate a semiconducting doped polymer, so that it has a conductivity of 12 s / _. It doesn't matter what the upper limit of conductivity is, it depends on the single polymer or co-polymer used. Generally, for applications related to electrical conductivity, the highest possible electrical conductivity is provided as long as it does not unduly impair the environmental stability of the polyphenylene: mono-Ia or co-I. In various special embodiments of the present invention, the grafted acid functional group f is sufficient to provide a conductivity of at least 101 / (: 111. In a more specific embodiment of the present invention, the grafted acid functional group has The amount is sufficient to provide a conductivity of about 10-2 s / cn ^, jl0 + 2 § /]. According to the needs and purposes of specific applications, the external dopant can be optionally added as compensation. Suppiementai dopant. Useful additive dopants can be an oxidative dopant. Examples of useful oxidative dopants are AsF5, Nitric Oxide (N0 +), and Nitric oxide (NO /) salts (for example, noBF4, NOPFe, NOSbF6, NOAsF6, NO2BF4, NO2PF6, No2AsFe, No2SbFe, etc.), peroxyacid (HCl〇4), lithocholic acid (HN〇3 ), Sulfuric acid (Η504), sulfur trioxide (SO3), iodine (I2), and trivalent iron salts (Fe (in) saits) (e.g. FeCh, Fe (OTs) 3, Fe (CF3S〇3) 3 Etc.). Other useful dopants can be proton-acid dopants, including inorganic acids such as hydrofluoric acid (hydrof 1 uor ic ac id), hydrogen s (hydroi od ic acid), phosphoric acid, Nitric acid, boric acid, sulfuric acid, etc. Other useful protonic acids are organic acids, such as compounds containing aryl or alkyl groups with sulfonic acid, sulfinic acid, sulfamic acid, amino acid, Molecular groups such as carboxylic acid, phosphonic acid, hypophosphorous acid, or boric acid. The thermally stable self-doped functionalized polyaniline prepared according to the present invention can be used in any application where 35 200531983 conductive polymers are available. For example, itself Doped functionalized polyaniline can be mixed with one or more traditional polymers to form conductive blends to make articles containing both conductive and non-conductive Portions, and containing Finished products with fully conductive components. List these finished products, including conductive polymer housings as shields against electromagnetic interference from sensitive electronic equipment such as microprocessors; infrared, radio waves, and microwaves Absorptive shields; conductive wiring that can be wound around electrical appliances; conductive bearings and brushes; semi-conductive optocouplers; electrodes; capacitors; suitable for use on rotting materials such as steel Light-transparent or opaque anticorrosive materials; antistatic materials suitable for packaging electronic components and light-transparent or opaque conductive coatings; conductive carpet fibers; thinner conductive flooring than computer rooms; _ on CRT screens, Lai and automotive glass Anti-static Wei, etc. Various other possibilities to the shop of the invention " self-doped functionalized polyaniline guide painters, including fine capacitors for capacitors ^ (eliao); solar cells; fuel cells ; Conductive plastic gasoline tank; shading glass window coating; meaning conductive parts suitable for heating windows and heating LCD display; electrochromic display ^ suitable for electroluminescence display or electro-current contactor or electro-feeding Layers; current connection of piezoelectric film suitable for transparent speakers; transparent conductive coatings suitable for anti-theft alarm systems; coatings suitable for chemical separation (such as separating oxygen and nitrogen) films; conductive properties for membrane switches Coatings; and axes as described in β τ, which are suitable for use in the antistatic layer or photoresist layer of Qi Cheng, are for further illustration of the present invention, and should not be scaled to the limit of the spirit of the present invention. Example 1: Aniline (50 g, 0.54 polyaniline powder can be prepared by the chemical method of the following process: 36 200531983 Moore) and 204.4 g of p-toluene acid (mouth-1; 〇1111681111 " 〇11] ^ 3 (: 丨 (1) Monohydrate (1.08 mol, Aldrich Chemical) is dissolved in 1750 ml of water, and placed in a three-necked round-bottomed bottle. It is equipped with a mechanical stirrer and a dosing solution. Funnel. After cooling the reaction mixture to 15 ° C, use an addition funnel to dropwise add ammonium peroxysulfate as an aqueous solution (157 g in 270 ml of water). The time for all additions is 2 hours and 50 minutes. After the addition is complete, the reaction mixture is stirred for 30 minutes. The solid obtained is collected by filtration, and the filter is dispersed in 1.5 liters of a 12 wt% aqueous solution of p-toluene acid for 30 minutes for 4 times. In each round The solid was recollected and re-dispersed in a fresh p-toluenesulfonic acid solution. After the above treatment, the filter was dispersed in 1.5 liters of 8 wt% p-toluene acid in ethanol / cereal. The Chinese Communist Party twice, every time use new to para-toluene yellow The solution was first dried in air at 25 ° C for 15 hours, and then dried under continuous vacuum at 80 ° C for 3 hours. The yield of polyaniline doped with toluenesulfonicacid was 83 g. The results of elemental analysis (weight percent (wt%)) are c (63.17), osmium (4 · 卯), Ν (8 · 30), S (8. 88), 0 (13.87). Heterogeneous neutral polyaniline can be doped with polyaniline (i.e., poly (aniline tosylate); poly (aniliniumtosylate)) doped with the above-mentioned p-toluenesulfonic acid. It was prepared by heterogeneous treatment. The poly (aniline p-toluate) (50 g) obtained in Example 1 was dispersed in 500 ml of water and stirred with 30 g of sodium carbonate at room temperature for 20 hours. The resulting solution was collected by filtration. The solid was washed with 2 liters of deionized water. The filter was dispersed in 5 liters of deionized water. 37 200531983 Run for 4 hours to remove residual carbonated fish. Collect the solids again and collect with 2 liters of deionized water. After washing with water, the obtained permeate was first dried in air at 25 t for 20 hours, and then dried under vacuum for 3 hours. · The results of elemental analysis showed that the TF was not present-the sample did not contain selenium (because the sulfur content was less than & 〇3㈣) and sodium invertite (because the sodium was not measured). Example 3 A single-ion film with a thickness of about 10 μm can be obtained from Example 2. An NMp (N-methylpyrrolidinone) solution of the obtained neutral polyaniline powder was prepared by the following steps. The above-dedoped polyaniline powder (about 0.1 g) was dissolved in 25 ml of the solution to prepare a 0.48 blue color solution. After filtering a small amount of insoluble solids, take 1.5-2. 0 ml of the solution carefully onto a clean glass slide (7.5x2.5 cm in size), and dry it in a vacuum oven for about 24 hours. The blue glass film having metallic luster was peeled by soaking the obtained glass slide in methanol for 2 to 3 hours'. Example 4 Using a smaller amount of the same polyaniline solution as in Example 3 for casting on conductive IT0 glass or stainless steel, a polyaniline coating film having a thickness of about 0.5 was obtained. Example 5 Φ A polyaniline film (or coating layer) can be prepared from a 0.1 M aniline solution on a platinum electrode by the electrochemical method through the following steps. The growth of the polyaniline film was performed in a three-electrode electrochemical device, and platinum or platinum wire was used as the working electrode and the corresponding electrode, and a saturated sweet fruit electrode (⑽) was used as the reference electrode. All polymerization reactions were performed using electrochemical instruments. (Wei Wei controlled it. 38 200531983. The solid-state current density was 13.3 x 1G6 A / αη2. They were grown for a total of 25 minutes in an aqueous solution of 0.5 M acid containing 0.001 M aniline. The thickness of the obtained polyunsaturated lumps was obtained by using a (second-reader mass spectrometer) to make a deep contour sketch and using a thickness measuring instrument (a-step) to measure the thickness. About Η) μm thick, isolated polyaniline membrane was immersed in a methanol solution of mercaptopropanesulfonic acid sodium salt (MPS-Na) of 0.1 μM for 6 hours, and placed in a catalytic amount of A protonic acid such as 0.001 M acetic acid to increase the reaction rate. The resulting polyaniline film was carefully washed and soaked in methanol (to remove any residual MPS-Na), followed by an aqueous sodium carbonate solution (to remove the acetic acid catalyst " and / or "any residual non-bound 3-mercapto groups 1-propanesulfonic acid (3-mercapto-I-propanesulfonicacid)), deionized water (to remove sodium carbonate) and acetone (to remove water), and dried with nitrogen to remove the cleaning solvent. After contacting with MPS -After the action of Na, the backbone of polyaniline is highly reduced and replaces the alkylthio group containing a sulfonic acid molecular group. When polyaniline interacts with other thiols, a similar reaction pattern also occurs. After treatment The reduction and substitution phenomena occurring on the MPS-Na film can be confirmed by surface total reflection infrared spectroscopy (ATRIR). The atrir spectrum of the obtained polyaniline shows all absorption peaks related to diimine such as 1600 cm- 1 (the OC bond tensile vibration of the diimine ring), 1169 cm1 (the vibration mode related to the diiminoquinone ring), and 820on1 (the CH off-plane of the 1,4-ring (out- of-plane (vibration). When the polyoxamine semi-oxidized state is reduced by hydrazine In the fully reduced state (leucoemeraldine) test, the intensity of these three absorption peaks also similarly weakened. The above-mentioned ATRIR spectrum also showed that a new 39 200531983 absorption bee appeared at 1041 cm1, which is a newly introduced " base- The malonic acid substituent (referred to as Mps_substituent) is a functional M called pottery. The spectrum of Keshi ir shows that three new absorption peaks appear at Jane, Gang, and 28W, which are the newly introduced MPS. -The asymmetry of the CH2 functional group on the substituent 龟 and the tortoise ... and the symmetry (28W) tensile vibration mode. On the MPS-Na compound, the Η bond tensile vibration peak of _ was also observed, and At 286 (W, its intensity is about one-tenth of the asymmetry tensile peak strength of the so3 functional group at · cm1. The obtained polyaniline contains two sulfur substituents and can also be used.) Photoelectron spectroscopy (xps) to confirm. The XPS all-round spectrum of the film treated with MPS_Na shows that except for the original C Is (with a binding energy of 284.6 eV) and N ls (399. 2 eV) peaks A new 0Is peak appears at 531.5 eV and s 2pJ | r is near 160 to 170 eV ^ More detailed chemical energy states of S 2p It shows that there are 2 new peaks of s ¥ appearing at i63. 5 # and ΐ67 · 6 eV ', which represent sulfide linkers (instead of disulfide bonds such as hydrazone or thiol) and sulfonate tails, respectively. The obtained propylthio-based polyaniline (MPS-Pan) film has a conductivity of 0.2 S / cm without any external dopant. Just like typical self-doped polyaniline, its own doped conductivity is less sensitive to changes in pH in the pH range 1 to 7. In terms of the conductivity of the sulfonated polyaniline (with 26 mol% self-doping) reported in previous literatures at 105 S / cm, this new type of self-doped polyaniline (with only 20 mol%) Of its own doping level), the high conductivity is particularly noteworthy. This thiol propionate substituent (that is, prOpyl and iSOsulfonate) 200531983 The distribution in the polyaniline membrane can be obtained by using the depth wheel of 5 (secondary ion f-spectroscopy). Gallery research to detect. The results clearly show that the sulfur atoms (the propylthio luteinic acid substituent is the sole source of sulfur atoms) are very uniformly distributed in the thickness direction within the polyaniline-controlled sample. Obviously, this-substitution reaction can be effectively performed in the solid polyaniline body (about 1 () μιη #), instead of only on the surface of the membrane. Example 7 The self-doped MPS-Pans prepared in Example 6 were tested by thermogravimetry (TG). The thermogravimetric analysis results of MPS-Pan with a 20m0l »generation amount show that in addition to a small amount of water lost below about 120%, a slight weight loss was generated between 260 and 2000t. (It was confirmed by the xps study that this is related to the loss of the sulfonic acid functional group), and then it produced a major weight loss at 524 (this is caused by the lysis of the polymer backbone). The initial temperature of this slight weight loss event was about 260 ° C, and its onset temperature was about 270 ° C. As for the main weight loss event, the starting temperature is about 470 ° C, and its starting temperature is covered by its previous events. In order to facilitate comparison ’, we also use literature methods (Yue, j ·; Wang, ζ · Η ·; Cromack, κ · R ·;

Epstein, A. J .; MacDiarmid, A. G. 1 Am. Chem. Soc. 1991, J] 3y 2665) A sulfonated polyaniline with a substitution amount of 55.8 mol% was prepared and tested for thermal stability using the same fastener conditions. The results show that in addition to an initial dehydration event below 120, the weight loss of S-Pan exhibits a continuous multi-stage characteristic, and its initial temperature is about 185 ° C (this is the loss of sulfur (Caused by acid functional groups), the starting temperature is about 230 ° c, and the initial major weight loss event is about 273 ° C. Chen et al. Also reported similar starting temperatures (1900 and major weight loss 200531983 loss / dish degree (275 C) for a S-pan containing 50 mol% substitution) (Chen, S · A ·; Hwang, GW ·% 3950). 'We also tried to explain the observed TG weight loss through the XPS study to understand the thermal degradation chemistry of different samples. The MPS_Pan and s_pan samples mentioned above were first A predetermined temperature (for example, 30, 100, 210, 240, 270, 340, and 420 ° C) is heated under gas for 1 hour, and then the S / N atomic ratio is checked by XPS. The results show that at 240 ° c The s / N ratio of MPS-Pan samples after heating is almost unchanged within the experimental error range, which is 0 · 392 ± 0 · 02. However, under the same temperature heating, the s / n atom of s-Pan samples The ratio was significantly reduced from 0.558 (30 ° C sample) to 382 (21 ° C sample), and 224 (240 ° C Lu sample). These results show at least 2400 ° C] ^ 8_1 ^ 11 The structure can be maintained. However, the sulfonic acid on S-Pan has been significantly cleaved off at 210 ° C. The results from Table 丨It is shown that at higher heating temperatures, the S / N atomic ratio will gradually decrease, indicating that the sulfur-containing molecular groups continue to detach from the polyaniline. A more detailed study of the chemical energy state of XPS shows that the MPS- The decrease in S / N _ of Pan is mainly caused by the loss of the S (V functional group at the tail end. As for its sulfanium group, it remains intact to more than 300. Therefore, from the research results of redundant and heat treatment, The thermal degradation reaction of S-Pan includes the loss of the acidic functional group (starting from the clear and possibly accompanied by the decomposition of its backbone. ❿ MPS_Pan cleavage, although the loss of the acidic functional group also includes, but its starting point is more High temperature of 260 ° C. These results clearly show that the thermal stability of the novel self-doped polyaniline brain of the present invention is indeed much higher than the example of the best self-doped polyaniline known in the literature (ie, acidification). Polyaniline, S-Pan). 42 200531983 Table 1 S / N atomic ratio heating temperature of MPS-Pan and S-Pan samples after heating at different temperatures (° MPS-Pan (S / N) S-Pan (S / N) 30 0.395 0.558 100 0.393 0.540 210 0.388 0.382 240 0.391 0.224 270 0.29 8 0.182 340 0.153 0.089 420 0.136 0.038 Although the present invention specifically describes some preferred specific embodiments, these specific embodiments are not intended to represent the entire picture, nor are they intended to limit the present invention to the forms disclosed above. As recognized by experts in the relevant field, the above-mentioned various forms and details can still be changed differently without departing from the spirit and scope of the present invention. Any similar process steps can be interchanged with each other to obtain the same result. The scope of the present invention is defined by the scope of the following patent rights or its equivalents. [Brief description of the drawings] The color and color of the present invention can be expressed through the following text descriptions and displayed in conjunction with the accompanying drawings. In all examples, similar __ represents similar meaning. 43 200531983 The principle of the drawings is not clear unless specifically stated otherwise. In the figure below: 'The price is for the purpose of illustration of the present invention only. Figure 1 is an example of the heat-stable self-doped functional polyaniline of the present invention. Figure 2 is a _following type self-doped functionalized polyaniline. Figure 3 shows the general chemical structure of the substances that can be used in the present invention. The general molecular structure includes: • Dividing ancient formulas; transferring marriages;; Aniline units can be used to make the polybenzylamines useful in the preferred embodiments of the present invention. Fig. 4 illustrates the molecular formula (xm) as an example of the polyaniline used in the preferred embodiment of the present invention. Figure 5 illustrates a useful aniline unit using the molecular formula (χιπ) as an example, which is suitable for using another specific embodiment of this test to prepare a thermally stable self-doped functional polyaniline. 【Symbol Description】

Ri and R3 are hydrogen or a non-hydrogen substituent R2 is an acid functional group-containing substituent n and 1 are the number of private and R2 recurrences x, y, and z are the number of unit recurrences N is a nitrogen atom Scope of patent application:

Claims (1)

200531983 Unless explicitly stated otherwise, the principle is not clear. In the figure below: 'The price is for the purpose of illustration of the present invention only. Figure 1 is an example of the heat-stable self-doped functional polyaniline of the present invention. Figure 2 is a _following type self-doped functionalized polyaniline. Figure 3 shows the general chemical structure of the substances that can be used in the present invention. The general molecular structure includes: • Dividing ancient formulas; transferring marriages;; Aniline units can be used to make the polybenzylamines useful in the preferred embodiments of the present invention. Fig. 4 illustrates the molecular formula (xm) as an example of the polyaniline used in the preferred embodiment of the present invention. Figure 5 illustrates a useful aniline unit using the molecular formula (χιπ) as an example, which is suitable for using another specific embodiment of this test to prepare a thermally stable self-doped functional polyaniline. [Symbol description] Ri and R3 are hydrogen or a non-hydrogen substituent R2 is an acid functional group-containing substituent n and 1 are the number of private and R2 recurrences x, y and z are the number of unit recurrences N is a nitrogen atom, and the scope of patent application is: 200531983 1. A (I) type self-doped functionalized polyaniline, which contains a repeating unit such as a molecular formula Where: "Each person may be the same or different when they appear, it may be an integer equal to or greater than Daiso, and x + y >0; In: When people appear, they can be butterfly or alone, which can be-an integer greater than G, · In: When people appear, they can be the same or different They can be an integer from 0 to 4;-When they see, they can be the same or different They can be — Integers from ㈣ (as long as at least one 1 is not equal to zero, and the condition of n + 1_ < 4 in each repeating military unit; ㈣3 may be the same or different at each occurrence, it may be hydrogen or- Non-hydrogen substituents; R2 may be the same or different at the parent occurrence, and has the following molecular formula ... The group X may be the same or different at each occurrence 'It is an atom or molecule in a divalent bond state Yi and 吣 can be the same ^ 4 when the parent and child appear, it can be selected from the group consisting of hydrogen, gas, alkyl, alkenyl, alkynyl, alkenyl, aryl, alkylaryl, alkyl, propenyl , Benzyl, alkoxy, 45 200531983 aryloxy, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkenynyl, alkylfluorenyl, arylfluorenyl, arylfluorenyloxy, alkynyloxy, Alkylthio, arylthio, alkylthioalkyl, alkylthioaryl, arylthioaryl, fluorenyloxy, arylaryloxy, mercaptoalkyl, fluorenylaryl, mercaptoarylthio, sulfanylthio , Aralkyl, aryl, aryl, i, hydroxy, hydroxy, hydroxy, aryl, cyano, nitro, silyl, silyl, silyloxy, silaryloxy, amine Acid group, epoxy group, amine group, amine alkyl group, amine aryl group, amine group, amine group, amine group, aryl amine group, aromatic amine group, double aromatic amine group, alkyl amine group, dioxane Amine, alkarylamino, alkoxyalkyl, aryloxyalkyl, alkoxycarbonyl, alkoxysilyl, alkylsilyl, alkoxysilyl, arylsilyl, heterocyclic, heterocyclic aromatic Cyclic, alkylthiosulfenyl, aromatic Alkylsulfinyl, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, alkylsulfinyl, alkylcarboxylate, alkylsulfinate, alkylsulfonate, alkylphosphonate A red group consisting of ester derivatives of acid-functional groups, wherein the acid-functional group is selected from the group consisting of phosphonic acid, sub-acid acid, butterfly Ziman, slow acid, sub-% acid,% acid, and amine Acids, or amino acids; the aromatic, the heteroaromatic, The aliphatic and cycloaliphatic functional groups contain one & functional group selected from the group consisting of phosphonic acid, hypophosphorous acid, boric acid, carboxylic acid, sulfinic acid, sulfonic acid, sulfanilic acid, and amine group Acids, derivatives and salts of the above acids, cycloaliphatic rings, alicyclic rings, aromatic rings, heteroaromatic rings, mysterious, Wei, cyano, vinyl, weaving, and Weiji molecular groups, and The other groups consisting of the aforementioned R heterosynthetic groups; any two Ri together or any-_ 任 _① together to form a Wei group with or without substituents, extension, reading chain and Surrounded by — aromatic rings, heteroaromatic rings, heteroalicyclic rings or alicyclic rings of 3, 4, 5, 6, 7, 8, 9 or 10-membered rings, the ring may be 嶋-or more Non-carbon atoms " and / or " eight subgroups of bivalent bonds, such as nitrogen, sulfur, sulfinyl, Gu Ji, dish, code, _, county, and oxygen, etc. 2 46 200531983 The permissible substituents are the acids and other functional groups mentioned in R2 in each occurrence; they are the same or different, and have the following molecular formula: -X-R4 X appears in everyone t may be the same or different, and may be selected from a group consisting of SH ㈣), and NR5. At present, each aiH may be the same or different, and may be selected from hydrogen and other functional groups allowed by & A group consisting of; daggers may be the same or different when each person appears, which is a functional group containing an acid substituent, wherein the functional group may be selected from the group consisting of silk, silk, alkenyl, alkynyl, alkenyl, Propyl, benzyl, «cycloalkenyl, cycloalkenyl, cyclic silk, cycloalkenynyl, radical, silk radical, sylylene, weifang aryl radical, kalium aromatic radical, domain burned silk, sharp radical, fresh radical, Filament silk, Shixi silk, Sulfuroxyl, Shixiaryloxy, Amino acid, Epoxy group, Silk, Aromatic silk, Yujiji, Sulfuryl, Xisiyuan , Oxidic oxalate, oxidized aryl, heterocyclic aryl, aryl, alkane heteroaryl, aryl, heterocyclic aromatic silk, silk, green ring, alicyclic, and A group consisting of heterocycles, and the acid substituents may be selected from the group consisting of phosphonic acid, hypophosphonic acid, butterfly acid, meta-acid, subacid, acid, amino acid, amino acid, and the like Organisms such as esters and acid salts, etc. One of the group consisting of repair. 3. The thermally stable self-doping functionalized polyaniline as described in item 2 of the scope of the patent application, wherein: X is NR £ (= 0). 4. The heat-stable self-doping functionalized polyaniline as described in item 2 of the scope of the patent application, wherein: X is S 〇 47 200531983 5. The heat-type self-doping as described in item 2 of the application Heterofunctional polyaniline, where: Rl is an aliphatic molecular group, its molecular formula is-(〇CH2CH2) q〇CH3 '-' 2CH (CH3)) 3, -3-(CH2) QCH3, q 0_ is a positive integer. 6. The thermally stable self-doped functionalized polybenzylamine as described in item 2 of the scope of the patent application, wherein: Ri is an aliphatic molecular group having a molecular formula of _ — (ORl0) r0Rll R1〇 Is a divalent bonded alkylene group containing from 1 to 7 carbon atoms; Ru is an alkyl group containing 1 to 20 carbon atoms; r is a natural number from 1 to other. 7. A method for manufacturing a thermally stable self-doped functionalized polyaniline, the steps comprising: (a) providing a solid polyaniline, and ⑹ combining the solid polyaniline in a selected solvent or mixed solvent with The active chemical reagents undergo reaction treatment for a period of time. The solvent or mixed solvent is sufficient to dissolve or disperse the chemical reagents and to dissolve the solid polyaniline, and the chemical reagents are sufficient to functionalize the Guxian aniline system. The state of the amine impurity becomes a higher reduced state. 8. The method as described in item 7 of the scope of patent application, wherein ... at least one active chemical reagent is used in the reaction treatment step. 9. A method for manufacturing a thermally stable self-doped functionalized polyaniline, the steps comprising: 48 200531983 (a) providing a solid polyaniline; 进行 subjecting the solid polyaniline to a redox treatment to convert the solid polyaniline The backbone of the amine becomes a desired oxidation state; (C) The obtained polyaniline is reacted with a selected solvent or mixed solvent for a period of time in a selected solvent or mixed solvent, and the solvent or mixed solvent is sufficient Dissolve or disperse the chemical reagent and can run or hydrate the solid polyaniline, and the chemical reagent is sufficient to functionalize the solid polyaniline and transform the backbone of the solid polyaniline into a higher reduced state; and repeat step (b) ), And / or, (c). 10. The method according to item 9 of the scope of patent application, wherein the order of step ⑹ and step _ is reversed from each other. 11. The method according to item 9 of the scope of patent application, wherein: step (b) and step ⑹ are performed simultaneously. 12. The method according to item 9 of the scope of patent application, wherein: step (b) or step ⑷ is repeated at least one round. I3. The method as described in item 9 of the scope of patent application, wherein steps ⑻ and ⑷ are repeated at least one round. 14. The method according to item 9 of the scope of patent application, wherein at least one active chemical reagent is used in each reaction treatment step. 15. The method as described in item 9 of the patent scope, wherein the same active chemical reagents are used in each round of redox and reaction treatment steps. 49 200531983 讥 "Please request the method and reaction treatment step described in the scope of the patent for the use of different active chemical reagents /,-round of redox 17. The method described in the scope of the loss of the seventh paragraph, which: The active chemical test sword can be selected from the group consisting of sulfur, _, yi, _, qing, and shirt combinations. 18. The method described in item 9 of the scope of patent application, wherein: the active chemical reagent is optional From the group consisting of thiols, alcohols, phosphines, amines, and amines, or a combination of the above types. 50