JPH06505038A - Method for processing conductive polyaniline in solvent mixtures - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Background of the invention Process for treating conductive polyaniline in solvent mixtures 1. Field of invention The present invention provides solutions of conductive substituted or unsubstituted polyanilines and solutions of such solutions. Regarding the forming method. Another aspect of the invention is to use such solutions to prepare films, prints, etc. The present invention relates to methods of forming polymeric articles such as lint, coatings and parts.

2. Conventional technology Recently, there has been increasing interest in the electrochemistry and electrical phenomena of polymer systems.

Recently, research on polymers with extended conjugated bonds in at least one main chain Emphasis is being placed on

One bonding polymer system under investigation is polyaniline. Kobayashi et al., J. Elec. troanal, Chem, +e Electrochemical Re actions Concerned With Electrochromi smof Polyaniline Film-Coated Electro deS”, 177 (1984) 281-291, polyaniline film Various experiments are described in which spectroelectrochemical measurements were performed on electrodes coated with . centre Reims Patent No. 1.519.729: Additional French Patent! No. 94.536: English National Patent No. 1.216,549; “Direct Current Condu activity of Po1yaniline 5ulfate”, M, Do nomedoff, F., Kautier-Cristoj ini, R., De. 5urv71);”Continuous Current Conducti Vity of Macromolecular Materials”, L-T , Yu.

, 1.469 61970);”Polyaniline Ba5ed Fit mogenic Organic Conductive Polymers” .

D, LaBarre and M, Josefowicz, C, R, Read, S.

i, Ser, C, 269, 964 (1969); “Recently Di discovered Properties of Semiconductin gPolyme r”, M, Joze fowicz, L-T, Yu and and R, Buvet, J, Polym, Sci, Part C, 221187 -1195 (1969);” Electrochemical Proper ties of Polyaniline 5ulfates-1F, Cr1st ojini, R.

De 5urville and M., Jozefowicz, Cr., Read, S. ci, Ser, C, 268, 1346 (1979);”Electroc chemical Ce1l Using ProtoLytic Organi cSemiconductors'', R, De 5urville, M, Joz efowicz, L-T., YuS.J., Perichon, R., Buvet, E. lectrochem, Ditn, 13.1451 (1986);”O Ligomers and Polymers Produced by 0x idation of Aromatic Am1nes”, R, De 5ur yille.

M, Josefowicz and R, Buvet, Ann, Chem, (Paris) , 2.5 (1967); - Experimental 5 study of t heDirect Current Conductivity of Mac r.

molecular Compounds”, L-T, YusM, Barred on, M., Jozefowicz, G., Belorgey and R. Buvet. .

J. Polym. Sci. Part C, 16, 2931 (1967);

nductivity and Chemical Properties.

f　Oligomeric　Polyaniline'', M, Jozefowi cz% L-T., Yu, G., Be Iorgey and R. Buyet, J. Po. tym, Sci, Part C, 16, 2943 (1967);”Produc ts of the Catalytic Oxidation of Ar omatic Am1nes”, R, De 5urville, M, Jozef owicz and R. Buyet, Ann, Chem, (Paris), 2,149 (1967): Conductivity and Chemical Com p.

5ition of Macromolecular Sem1conduct ors”, Rev, Gen, Electr, 75.1 ([4 (1966); ”Re1ation Between the Chemical and E electrochemical Properties of Macromo regular Sem1 conductors”, M, Jozefowicz and L-T, Yu, Rec, Gen, Electr, 75.1008 ( 1966);”　Preparation, Chemical　Propert ies.

and Electrical Conductivity of Poly- N-Alkyl Anilines in the 5olid 5tate” , D. Muller and M. Jozefowicz%Bu11. Soc, Ch. em, Eng, Fr, 4087 (1972).

U.S. Patent Nos. 3.963,498 and 4.025.463 include aniline Oligomeric polyanilines and substituted polyanilines with 8 or fewer repeating units are described. are soluble in certain organic solvents and have a volume conductivity of approximately 7X. IO-” Semiconductor with S/am and surface resistivity of 4xlO’ohm/5square It is described as useful in forming compositions. European Patent No. 0017717 No. 3,963,498 and No. 4,025,463 Polyaniline is a clear improvement on polyaniline. By using an acetone solution of the oligomer and a suitable binder polymer, It states that it can be formed into a Tex composite material.

U.S. Pat. No. 4,855,361 discloses that a polyamide-like group is a nitrogen source in a basic polymer. Salts containing polyamides and carbon-nitrogen bonds, such as polyaniline, covalently bonded to molecules. Conductive polymer formulations have been described that include admixtures with base polymers. this Conductive polymer formulations are first made from basic types containing carbon-nitrogen bonds, such as polyaniline. 3. a non-conductive polymer; 4. 3’, 4’-benzophenone tetracarbo By reacting with carbonyl anhydride such as phosphoric acid dianhydride, the polyimide-like group is converted into basic form. Covalently bonded to the nitrogen atoms of the polymer to form a conductive polymer, such conductive polymerization The body is mixed with a non-conductive polyamide in a suitable solvent, the solvent is removed, and the polyamide formed by forming a conductive continuous phase blend of conductive polymers and conductive polymers. Ru.

U.S. Pat. No. 4,798,685 describes carbon-nitrogen bonds such as polyaniline. Non-conductive polymers containing base groups and R in which R is an organic group such as methyl iodide ゛The donor compound is reacted with the donor compound, and the R group is covalently bonded to the nitrogen atom of the polymer. Base-type conductivity, especially from conductive polyaniline systems, by forming conductive polymers. There is a description of the production of electrically conductive polymers.

U.S. Pat. No. 4,806.271 describes carbon-nitrogen bonds such as polyaniline. base-type non-conductive polymer containing RxSO4, R'SO, CI or R"xsi Cations such as c[(R, R' and R' are alkyl or aryl) react with a donor compound, such as dimethyl sulfate or tosyl chloride, and R2 504(7) R group, R'5(hC1(7)R'SO2 group or t=ciR's S　C1(7)R'　sS　Electroconductivity in which the i group is covalently bonded to the nitrogen atom of the polymer Base-type conductivity, especially from conductive polyaniline systems, by forming polymers There is a description of the production of polymers.

U.S. Pat. No. 4,822,638 describes non-conductive polymerization, particularly from polyaniline systems. A method for fabricating electronic devices onto a body substrate is described, which includes covalent doping agents, For example, an R+ donor compound in which R is an organic group, such as methyl iodide, is combined with a carbon-nitrogen applied to a preselected portion of the base-type nonconductive polymer substrate containing the bond, and by covalently bonding the R group of the donor compound to the nitrogen atom of the nonconductive polymer substrate. Therefore, converting such preselected portions of the polymer substrate into conductive polymer portions This is a method that includes By the method of this invention, stable and conductive parts can be diffused. Resistors, capacitors, inductors, signs in the form of non-metallic lightweight polymers Electronic devices such as printed circuits etc. are obtained.

U.S. Pat. No. 4,851,487 describes carbon-nitrogen bonds such as polyaniline. A base type non-conductive polymer containing R-3Oz　0-SOx　R'　, RCo　0 -Co-R' or R-Co-0-5O2R or mixtures thereof Anhydrides (R and R' are alkyl or aryl), such as tosyl anhydride or or benzophenone tetracarboxylic dianhydride, and S ChR and the COR group is covalently bonded to the nitrogen atom of the conductive polymer and the COR group is covalently bonded to the nitrogen atom of the conductive polymer. Forming a conductive polymer in which the ions are RS　Os- or R'　CO2- groups on the production of basic-type conductive polymers, especially from conductive polyaniline systems, by There is a description of

U.S. Pat. No. 4,798,685 describes carbon-nitrogen bonds such as polyaniline. base-type non-conductive polymers, and R+ donors where R is an organic group such as methyl iodide. conductivity by reacting with a donor compound and the R group covalently bonding to the nitrogen atom of the polymer Base-type conductivity, especially from conductive polyaniline systems, by forming polymers There is a description of the production of polymers.

PCT WO39101694 includes doped with specific sulfonated dopants. A variety of conductive polyanilines have been described. These substances are thermally stable. and can be melt compounded to form blends with other types of polymers. It has been posted.

Summary of the invention One embodiment of the present invention includes one or more substituted or unsubstituted polyanilines: one or more Lewis base/dopant complex (this Lewis base has a pK of , and the dopant has a larger pK, and the dopant is the complex of the dopant. Upon release from the polyaniline, the polyaniline is doped to form a conductive polyaniline. ): and the above complex and the above polyaniline can be dissolved to some extent. or one or more types capable of plasticizing the above polyaniline. for non-conductive solutions or plasticizing compositions containing solvents or combinations thereof. do. As used herein, "solution" refers to a true solution or an average particle size of approximately 100 nanometers. The “plasticizing composition” used herein is a liquid or low melting point solids generally in an amount of greater than about 1% by weight and no droplets of about 20% by weight. A polymer or polymer blend that is softened by used here "Polyamines" are synthesized by, for example, single-layer bonding of substituted or unsubstituted anilines. and depending on the oxidation state, the phenyl ring and the amine bond [-NH- or - NR- (R is a substituent other than hydrogen)] with various amounts of quinoid rings and It is a polymer having amine (-N=) bonds. “Undoped polyurethane” used here 'min' is characterized by an uncharged backbone, and 'polyaniline base' is characterized by at least A specific form of undoped polyaniline containing one quinoid cyamine bond in the backbone. Ru.

Another aspect of the invention is to prepare a conductive article or polymer coating from a solution or plasticized composition. Regarding the method of forming a substrate, the method includes the following steps: (a) One or more substituted or unsubstituted polyanilines: one or more Lewis-bases/dopane complex (this Lewis base has a pK larger than that of the above polyaniline) and said dopant is added to said polyester upon release of said dopant from said complex. Aniline can be doped to form conductive polyaniline): and on The complex and the polyaniline can be dissolved to some extent or one or more solvents or a combination thereof capable of plasticizing the polyaniline; forming a non-conductive solution or plasticized composition comprising: (b) said non-conductive placing all or part of the solution or plasticizing composition on a substrate or in the form of an article; Shi: And (c) all of the above solvent and the above Lewis base from the above solution or plasticizing composition; or by removing a part of the above article or the base coated with the above conductive polyaniline. Solidified doped conductive polyaniline in the form of a plate is formed.

Yet another aspect of the invention is the formation of solutions and methods of the invention. relating to goods that have been

Yet another aspect of the invention is a substituted polyaniline doped with a dopant or dissolves unsubstituted polyaniline or a combination of these to give it conductivity. The method relates to a method for determining the relative pK of the polyaniline.

liquid or molten liquid whose basicity, as measured by Lewis base (This Lewis base is complexed with the dopant in the above polymer to form a Lewis base. - Capable of forming base/dopant complexes and undoped polyaniline ) and the above composite and mixed in the solvent for undoped polyaniline. forming a solution of the complex and the undoped polyaniline in the solvent; and/or polyaniline containing the above complex plasticized by the above solvent. including the step of forming. The polymer of the present invention can be prepared using conventional solution or plasticized polymer methods. Useful derivatives from Lianiline in all forms such as fibers, coatings, films etc. Electrical articles can be conveniently processed.

Detailed description of the invention A more detailed understanding of the invention may be obtained from the following detailed description of the invention and the accompanying drawings. , further advantages of the invention will become apparent.

Figure 1 shows triethylamine, tripropylamine and tributylamine in methanol. UV-visible-near infrared spectrum of sulfonated polyaniline complexed with polyamine FIG.

Figure 2 shows tri-n-propylamine in methanol and ethanol, and of sulfonated polyaniline complexed with tri-n-butylamine in ethanol. It is a figure showing an ultraviolet-visible-near-infrared spectrum.

Figure 3 shows the sulfonated polyamide complexed with tri-n-propylamine in methanol. Aniline, tetrafluoroethylene/chlorotrifluoroethylene copolymer film It is a figure showing an ultraviolet-visible-near-infrared spectrum as a film.

Figure 4 shows the Hansen solubility parameters of solvents and cosolvents for polyaniline base. This is a graph showing the data.

Figure 5 shows the Hansen solubility parameters of solvents and nonsolvents for polyaniline base. This is a graph showing the data.

one of which is doped with a suitable dopant to at least about 10-10OS' (c.

-1inear conductivity (measured by four-probe method) Substituted or unsubstituted polyaniline.

Any form of substituted and unsubstituted polyaniline may be conveniently used in the practice of this invention. Can be used. Examples of useful shapes are Green, A, G, and Woodhe. ad, A, E,, CXVII Aniine-black and A11ie d Compounds, Part I', J, Chem, Sac, 101 , ppH17 (1912) and Kobayashi et al., “Electrochemica l　Reactions,,,,,of　Polyaniline　Film -Coated Electrodes”, J, Electroanal, Ch em2.1ヱ7Spp, 281-91 (1984) and 5hacklet e.

L, W, etc., “5structure and Properties of Po1yaniline as Modeled, by Single-Cr ystal Oligomers”, J, Chem, Phys, 88.39 55 (1988), and these are cited as reference. For example, Characterized by different proportions of nyleneamine and quinoneamine main chain segments. Useful forms of unsubstituted or substituted polyanilines include leucoemeraldine, protoemeraldine, Includes lalgin, emeralgin, nigraniline and vernigraniline.

In a preferred embodiment of the invention, the polyaniline used in the invention has the following formula: Homopolymers and copolymers of the type derived from the polymerization of unsubstituted and substituted anilines of ■ It is a combination: [In the formula, n is an integer from 0 to 5; m is an integer from 0 to 5, provided that the sum of n and m is 5; R2 is the same are the same or different, R3 substituent or hydrogen; and R1 are the same or different, and include boric acid, phosphinic acid, phosphoric acid, and Rufinates, amides, carboxylic acids, hydroxyaminophosphonic acids, halo, hydro Roxy, cyano, sulfinic acid, carboxylate, borate, phosphate, sulfonate , phosphinates, phosphonates, sulfonic acids, nitro, amino, cyano, jute -thylium or substituted or unsubstituted arylsulfinyl, alkoxycarboxylic Nyl, arylsulfonyl, alkyl, alkenyl, alkoxy, cycloalkyl cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkyl ruthioalkyl, alkylaryl, arylalkyl, alkylamino, dia Lucylamino, alkylarylamino, arylamino, diarylamino, Aryl, alkynyl, alkylsulfinyl, allyloxyalkyl, alkyl Kylsulfinylalkyl, alkoxyalkyl, alkoxyaryl, alkyl rusulfonyl, arylthio, alkylsulfonylalkyl or alkylsila selected from the group consisting of or any R1 group together with any R2 group may be substituted or unsubstituted. forming alkylene, alkynylene or alkenylene chains 3.4.5.6.7. 8.Completing a 9- or 10-membered aromatic, heteroaromatic, heteroalicyclic or ring ring and these rings optionally contain one or more divalent nitrogen, sulfur, sulfinyl, ester permissible substituents include carbonyl, carbonyl, sulfonyl or oxygen atoms. one or more amino, alkylamino, dialkylamino, arylamino, sulfur Phinic acid, diarylamino, alkylaryl amino, phosphonic acid, sulfone Acids, Phosphoric Acid, Boric Acid, Carboxylate, Borate, Sulfonate, Phosphinate, Phosphate phonate, hydroxylamino, quaternary ammonium, phosphate, sulfinate, Phosphinic acid, sulfate, carboxylic acid, halo, nitro, cyano or epoxy radicals or R3 is the same or different substituted or unsubstituted aniline moiety; or R3 is a divalent organic moiety bonded to the formula: %formula% (In the formula, q is a positive integer) is an aliphatic moiety having repeating units].

An example of a polyaniline useful in practicing the invention is a polyaniline of the formula -v. .

■ ■ ■ (In the formula, R2 and R8 are as above: n and m are the same or different, and are integers from 0 to 4, provided that and the sum of n and m is 4: and y and X are the same or different, respectively. is an integer greater than or equal to 0, provided that the sum of Y and X is greater than O, and is preferred. or X is an integer greater than or equal to about 1 and/or the ratio of X to y is greater than or equal to about 0.5. and 2 is an integer greater than or equal to 1).

The substituted and unsubstituted anilines listed below are polymers useful in the practice of this invention. and are examples of those that can be used in the production of copolymers.

2-cyclohexylaniline 2-acetylaniline o-toluidine 2.3- Dimethylaniline 4-propanoylaniline N-pentylaniline 2-( methylamine)aniline 4-benzylaniline 2-(dimethylamino)aniline Phosphorus 4-aminoaniline 2-methyl-4-methoxy-2-methylthiomethyl Aniline Carbonylaniline 4-(2,4-dimethylphenyl) N-dithi Luaniline Aniline 4-carboxyaniline 2-ethylthioaniline N -Methylaniline N-methyl 2,4-dimethylaniline N-propyl m -Toluidine N-hexylaniline N-methyl-cyanoaniline m- Toluidine 2,5-dibutylaniline 0-ethylaniline 2,5-dimeth xyaniline m-ethylaniline tetrahydronaphthylamine 0-ethoxy Cyaniline 0-cyanoaniline m-butylaniline 2-methylthioaniline m-hexylaniline 2,5-dichloroaniline m-octylaniline 3-(n-butanesulfonic acid) 4-bromoaniline 2-bromoaniline 3- Propoxymethylaniline 3-bromoaniline 2,4-dimethoxyaniline 3-acetamidoaniline 4-mercaptoaniline 4-acetamidoaniline Phosphorus 4-ethylthioaniline 5-chloro-2-methoxy-aniline 3-ph Phenoxyaniline 5-chloro-2-ethoxy-aniline 4-phenoxyaniline Phosphorus N-hexyl-m-toluidine N-octyl m-toluidine 4-ph phenylthioaniline 4-trimethylsilylaniline 3-amino-9-methyl Carbazole 3-aminocarbazole 2-aminocarbazole 4-aminocarbazole Rubazole N-(p-aminophenyl)aniline 3-butoxyaniline 2 -Butoxyaniline 2.5-dibutoxyaniline.

Examples of useful R2 groups are hydrogen, methyl, ethyl, isopropyl, butyl, isobutyl. These include hexyl, octyl, benzyl, etc.

Examples of useful R3 groups are hydrogen, alkyl such as methyl, ethyl, octyl, noni Al, t-butyl, neopentyl, isopropyl, S-butyl, dodecyl, etc. Kenyl, such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl Alkoxy, such as propoxy, butenyl, 1-hebutenyl, 1-octenyl, etc. Oxy, methoxy, isopropoxy, pentoxy, tunoxy, ethoxy, octoxy cycloalkenyl, such as cyclohexenyl, cyclopentenyl, etc. Kanoyl, such as butanoyl, pentanoyl, octanoyl, ethanoyl, pro- panoyl, alkylsulfinyl, alkylsulfonyl, alkylthio, ali lsulfonyl, arylsulfonyl, etc., such as butylthio, neopentylthio , methylsulfinyl, benzylsulfinyl, phenylsulfinyl, propylene ruthio, octylthio, nonylsulfonyl, octylsulfonyl, methylthio, Isopropylthio, phenylsulfonyl, methylsulfonyl, nonylthio, phenylsulfonyl Nylthio, ethylthio, benzylthio, 7enethylthio, S-butylthio, naphthio Toylthio, etc.: alkoxylic groups such as methoxycarbonyl, ethoxyl, etc. cycloalkyl, ethoxycarbonyl, butoxycarbonyl, etc.; cycloalkyl, e.g. Chlorhexyl, cyclopentyl, cyclooctyl, cycloheptyl, etc.: alkoxy sialkyl, such as methoxymethyl, ethoxymethyl, butoxymethyl, propoxymethyl, xyethyl, pentoxybutyl, etc.; aryloxyalkyl and aryloxy Sialyl, such as phenoxyphenyl, phenoxymethyl, etc.; and various substitutions Alkyl and aryl groups, such as 1-hydroxybutyl, 1-aminobutyl, 1-hydroxypropyl, 1-hydroxypentyl, 1-hydroxyoctyl, 1-hydroxyethyl, 2-nitroethyl, trifluoromethyl, 3,4-epo xybutyl, cyanmethyl, 3-chloropropyl, 4-nitrophenyl, 3-cyanmethyl Acid groups such as anophenyl, sulfonic acid, carboxylic acid, etc.: Acid groups and their Organic radicals substituted with salts, e.g. phosphonic acids, phosphinic acids, sulfinates various acid groups such as ethyl, sulfonic acid, sulfinic acid, phosphoric acid, boric acid, or ethyl sulfuric acid. Phonic acid, propyl sulfonic acid, butyl sulfonic acid, phenyl sulfonic acid and phase corresponding phosphoric acid, boric acid, sulfonic acid, carboxylic acid, sulfinate, sulfinic acid, alkoxy substituted with carboxylic acid groups such as phosphonic and phosphinic acids, alkoxyalkyl, alkylamino, arylamino, alkyl or ary group; and amino, alkylamino, dialkylamino, arylamino, di- Arylamino or alkylaryl amino groups, e.g. amino, methylamino , ethylmethylamino, ethylamino, dimethylamino, phenylamino, diphenyl phenylamino, methylphenylamino, etc.

Examples of useful R3 groups include any two R3 groups or any R3 group and any R2 group. A divalent group component derived from a group, e.g. formula: %formula%) (wherein a is an integer from about 3 to about 7, b is an integer from 1 to 2, and R5 is , each the same or different, hydrogen or alkyl, e.g. (CH2 )4, (CH2)! -1(CH=CH-CH=CH)-1[-CH2-CH(C Hri-CH2]- and -(CH2)S, and these group constituent moieties are optionally acidic. nitrogen, ester, sulfonyl, carbonyl, sulfinyl and/or sulfur Contains a yellow complex atom, for example -CH2SCH2-1CHz N HCH2-15 CH2NHCH2-1OCHz S CH2-1-CH2S (O□) CH2- 1-0 (CH2) 20-1- CH2S (0) CHz-1-QC (0) CH 2CH2-1-CHzC(0)CH2- and -CHz OCH2-) moieties and heterocyclic amino compounds, such as tetrahydronaphthylamine, Drobenzopyrroleamine, benzofuranamine, dihydrobenzobilanamine , dihydrobenzofuranamine, dihydrobenzo I, laoxazinamine, dihydrobenzo Drobenzoparadiazinamine, dihydrobenzotriazolamine, dihydro Benzothiazinamine, benzothiopyranamine, dihydrobenzoxazole Forming Min et al. Examples of useful R1 groups include divalent aryl groups containing from 1 to about 3 unsaturated bonds. alkylene chains, such as divalent 1,3-butadiene, which are also moieties with 1 More than one divalent oxygen, nitrogen, sulfinyl, sulfonyl, carbonyl, ester and/or may contain sulfur groups, such as benzodiazineamine, benzodiazineamine, zoleamine, pencitriazepineamine, benzimidazoleamine, benzo isoxazoleamine, benzoxazoleamine, benzotriazineamine, Benzoxazine amines, naphthalene amines, benzopyran amines, benzothia diamine, anthraceneamine, aminobenzothiobilane, aminobenzodia gin, penzethiovironamine, aminocoumarin, benzothiopheneamine, compounds such as nzothiodiazole amines and the like.

The polyaniline preferably used in carrying out the present invention is such that n is an integer from 0 to about 2. Yes.

m is an integer of 2-4, provided that the sum of n and m is 4, and R2 is the same, respectively. are the same or different, and R1 substituent or hydrogen: R3 is aryl, alkyl or alkoxy having 1 to about 30 carbon atoms, cyano -, halo, sulfonic acid, carboxylic acid, boric acid, borate, phosphoric acid, phosphate, phosphonic acid , phosphonate, phosphinic acid, phosphinate, sulfinic acid, sulfinic acid salts, carboxylates, sulfonates, aminoalkylamino, dialkylamino, Arylamino, hydroxy, diarylamino, alkylaryl amino, or phosphonic acid, phosphate, phosphoric acid, borate, sulfonate, amino, alkyl amide No, dialkylamino, arylamino, diarylamino, alkylaryl Amiotacarboxylate, hydroxy, alkoxy, phosphonate, boric acid, alkyl , phosphinic acid, phosphonate, phosphinate, carboxylic acid or sulfonic acid Alkyl, aryl or alkoxy substituted with a substituent: X is 1 or more is an integer.

y is greater than or equal to 0, provided that the ratio of X to y is greater than about 1, and 2 is greater than or equal to about 5; is an integer It is a polyaniline of the above formula (■-■).

Particularly preferred polyanilines for use in carrying out the invention are polyanilines in which n is an integer of 0-1. It is a number.

m is an integer of 3-4, provided that the sum of n and m is 4, and R2 is the same, respectively. are the same or different, and are R8 substituents or hydrogen: R3 is aryl, alkyl or alkoxy, sulfur having 1 to about 20 carbon atoms; Phonic acid, halo, carboxylic acid, amino, carboxylate, alkylamino, phosphonic acid Acid acid, dialkylamino arylamino acid, posonic acid, boric acid, phosphate, phosphoric acid, boron acid salts, diarylamino, alkylaryl amino, or carboxylic acids, phosphoric acids, Boric acid, phosphate, phosphonic acid, borate, sulfonate, amino, alkylaminocarbon Alkinogemi Arylamino, Sialinogemi Alkinogeri - Luami Cal Alkyl substituted with a bonate, halo, phosphonate or sulfonic acid substituent Or is aryl: X is an integer greater than or equal to 2: y is greater than or equal to 0, provided that the ratio of X to y is greater than about 2, and 2 is greater than or equal to about 5; is an integer It is polyaniline of the above formula.

Among the particularly preferred embodiments, the most preferred polymers for use in practicing the invention are: Aniline is n is an integer from 0-1: m is an integer of 3-4, provided that the sum of n and m is 4: R2 is hydrogen: R5 is aryl, alkyl or alkoxy having 1 to about 15 carbon atoms, amino alkylamino, dialkylamino, arylamino, diarylaminoalkylamino Kylarylamino, halo, sulfonic acid, sulfonate, carboxylic acid, carvone acid salts, or one or more sulfonic acid, carboxylic acid salts, amino, alkylamino, dialkylamino, arylamino, diarylamino, halo, alkylary Alkyl substituted with sulfonate, sulfonic acid or carboxylic acid substituents may also be used. or aryl; X is an integer greater than or equal to 2: y is greater than or equal to 1, provided that the ratio of X to y is greater than about 2; and 2 is greater than or equal to about 5; is an integer, It is polyaniline of the above formula (1) or (V).

In the most preferred embodiment of the invention, the polyaniline is unsubstituted aniline, alkoxy , alkyl- or sulfonic acid-substituted anilines or copolymers thereof is induced from

Generally, the number of aniline repeat units is not limited and can vary over a wide range. Anili As the number of repeating units increases, the viscosity and molecular weight of polyaniline increase. Ru. If polyaniline with lower molecular weight and viscosity is required, such materials can be polyaniline with higher molecular weight and viscosity is required. Any substance can be used. The number of aniline repeat units is at least about 10. It is preferable to The upper limit can vary widely depending on the desired viscosity and molecular weight. Ru. In a further preferred embodiment of the invention the number of repeating units of aniline is at least about 20, and in particularly preferred embodiments the number of repeating units is at least about 30. . Among particularly preferred embodiments, most preferred are those in which the number of repeating units is at least about 4. This is a specific example of 0.

Useful polyanilines can be produced using chemical and electrochemical synthesis methods . For example, aniline is mixed with ammonium persulfate (NH 4) Producing one form of polyaniline by treatment with zszos I can do that. This powdered polyaniline is blue-green in color. Wash with methanol. The conductivity of this material after air drying is IO8/cm. This conductive port When lianiline is treated with ammonium hydroxide in ethanol, it becomes non-conductive. of polyaniline, its color is dark blue, and its conductivity is about 1O- It is 10S/cm or more. Other chemical methods for producing polyaniline in various chemical forms is described in detail in the above-mentioned document by Green et al.

Useful forms of polyaniline can also be produced electrochemically. for example, A useful form of polyaniline is to prepare aniline in an aqueous fluoroboric acid electrolyte with a platinum foil anode. can be produced by electrochemical oxidation on

Alternative chemical and electrochemical syntheses and transformations of conductive forms of polyaniline are being explored. Therefore, one might expect these to be useful. In addition, polyaniline Other forms or types of may become apparent in the future. Therefore, here The compositions, transformations, or structures derived or assumed are not limited beyond the scope of the claims. It is.

The second essential component of the solution or plasticizing composition of the present invention is a Lewis base/dopant complex. It is a combination. The purpose of the dopant component of the complex is to release the dopant from the complex. from a solution or composition of time and/or solvent and/or Lewis base. Upon removal, doping the polyaniline and making it conductive It is. We don't want to be tied to a theory, but when we add polyaniline , such that the dopant solute comes out of the compound and forms a dopant solute component. ionizes the polymer through oxidative electron transfer or protonation to form a polyamine. It is thought that it forms a charge transfer complex with Nilin. The conductivity of this composite is approximately 1 0-'ohm-'am-' or more, preferably about 10-'ohm-'cm-' ' or more, more preferably 1010-2oh'cm-' or more, most preferably is 10-'ohm-'Cm-' or more.

Dopants preferred for use in practicing the invention may vary within a wide range. conjugated backbone polymers can be doped to form conductive or semiconductive polymers. It may be any conventionally known substance used for. Such substances are referenced here, for example. No. 4,442,187 and 4,321,114, cited as It is as described in detail. An example of a useful dopant component is an oxidized dopant. It's a punt. Oxidized dopants are well known in the conductive polymer art; Any such known oxidizing dopant can be used. useful oxidation Examples of dopants are AsF5, MOOC14, MoCl5, PCIs, POCIs , PCIl, AlCl5. No” and No2+ salts (e.g., N0BF4, N0 PF6, NO8bFg, NOAsF, , N0CHxCOz, N028F, , No 2PF6, N02AsFe, N0zStlFs and N0zCFsSOz), HClO4, HN Os, R2S O,, benzoyl peroxide, SOx, Br2, (FSOs)2, ZnCl2, FSO, H Oyohi Fe(III) salts (e.g. F e (BF4) s, FeBr5, Fe (CH3SOri s, Fe (C104 )! , FeC1x, Fe(OTs)s and Fe(CHsSOs)s) Yes, these are NO3-1CH3SOx\AlCl4-1B F, -1ZnC1 <-1PC1, -1PFg-1AsFg-1SbF6-1CF3SOs-1CI O, -1OTs-1SOS\Ce Hs CO2-1CHsSOs-1FSO3 - and resulting in doped polymers containing dopant solutes such as FeCl<- . Other useful oxidized dopants include LiC101, LiBF, LiAsF, NaPF,, Bu < NCl0 <, Bu 4 N OT s.

There are Bu, NCF3SO3, LiCFsSOs, Ag0Ts, etc. carrying out the invention Oxidizing dopants preferably used in this case are Mo0CI<, MoCl5 and and Fe(I[[) salts, such as Fe(ClO2)s, FeCl,, FeBr5 and and Fe (CF3SO3)! An oxidized dopant selected from the group consisting of A particularly preferred oxidizing dopant for use in practicing the invention is MOOC14 , MOCIs and FeCl3.

Among these particularly preferred embodiments, the most preferred oxidizing dopant is FeCl3 It is.

Yet another example of a dopant is a protic acid dopant. Such a do Punt contains inorganic acids such as hydrofluoric acid, hydroiodic acid, hydrochloric acid, phosphoric acid, nitric acid, and boric acid. , sulfuric acid, etc.

Yet another example of useful dopants are protic acids and their derivatives. , for example the formula: %formula%( contains the anionic moiety of and Mll　m can be; S is a positive integer of 1 or more, preferably from 1 to about 8; M has a positive charge between it and S; and r are each the same or different, and 01 or more than one positive nylamino, phenanthryl, etc., or substituted or unsubstituted Substituted heteroaromatics or poly(4-phenylstyrene), poly(a-vinylnaphtha) In poly(vinylben), R1 is substituted or unsubstituted phenyl or naphthyl. be. The properties of the M’S group are similar to metal cations such as Co”, Api, Fe”, etc. good.

Preferably, organic acid dopants are used in carrying out the present invention, and more preferably, organic acid dopants are used. Preferably the formula: %formula%)( (wherein R1 and r are as above) It is in a formalized form.

More preferably used in carrying out the present invention are acids of the following formulas or are acid derivatives of: R8(BO2Mri-(PChMz), (SO3M), (CO2M)-M is metal or hydrogen or other nonmetallic cation: C is 0.1.2.3 or 4; the law of nature: d is 0.1 or 2: e is Oll or 2: f is 0.1 or 2: g is 0.1 or 2, provided that at least one of c, d, f and g is 0 or more outside: and R6 is nitro, phosphonate, phosphonic acid, sulfinate, sulfinic acid, sulfate Acid acid, quaternary ammonium, cyano, hydroxy, halo, amine, alkyl amine dialkylamino, arylamino, diarylamino, alkylarylamide octaalkoxy or substituted or unsubstituted aryl having 1 to about 30 carbon atoms; is alkyl, and permissible substituents include behaloalkyl, phenyl , alkoxy, halo, cyano, amino, phosphate, alkylamino, dialkyl mino, arylamino, diarylamino, borate, alkylarylamino, Haloalkyl, hydroxy, sulfonic acid, sulfonate, phosphoric acid, boric acid, sulfuric acid phosphate, sulfinic acid, carboxylic acid, nitro, carboxylic acid, etc. R8 together form an alkylene or alkenylene chain, with the chain optionally one or more oxygen, nitrogen, ester, sulfur, carbonyl or combinations thereof halo, sulfate, hydroxy, amino, alkyl containing and/or one or more chains Ruamino, dialkylamino, alkyl, arylamino, diarylamino, Alkylaryl amino, boric acid, nitro, cyano, sulfinate, phosphoric acid, sulphate Phinic acids, alkoxy, phosphates, carboxylates, phosphonic acids, phosphonates, Substituted or substituted with sulfonate, borate, sulfonic acid or carboxylic acid groups completes an unsubstituted aromatic, heteroaromatic, ring ring or heteroalicyclic ring system or the expression: %formula% (where q is a positive integer from 1 to about 10).

In a further preferred embodiment of the invention, useful dopants are acids of the formula: is an acid derivative: R6(BO□M2)-(PO3Mz), (SO3M)-(CO2M)-[in the formula , M are each the same or different and are metals or hydrogen or other non-metals. It is a metal cation.

C is 0, 1.2, or 3; d is O or 1;

e is O or 1; f is O or 1; g is 0 or 1, however, if c, d, f, and g are small (one is other than 0) can be.

R6 is halo, amino, alkylamino, dialkylamino, arylamino, di Arylamino, alkylaryl amino, hydroxy, phenyl, haloalkyl haloalkyl, cyano, nitro, alkoxy, phosphonate, phosphonate acid, sulfinic acid or sulfinate substituted or unsubstituted phenyl or alkyl (Permissible substituents include alkyl, halo, amino, alkylamino, dial Kylamino, arylamino, diarylamino, alkylarylamino, droxy, phenyl, haloalkyl, behaloalkyl, cyano, nitro, al Koxy, boric acid, borate, phosphonate, phosphonic acid, carboxylate, sulfonic acid salts, phosphates, sulfonic acids, carboxylic acids, phosphoric acids, sulfinic acids or sulfinates ), or R6 is an unsubstituted or substituted alkylene group. naphthalene, anthracene or penanthyl by forming an alkenylene chain or an alkenylene chain. helical fused ring systems (permissible substituents include one or more halo, amino, alkylamino) No, sialkylamino, arylamino, alkyl, diarylamino, alkyl Ruaryl, Amino, Hydroxy, Phenyl, Haloalkyl, Berhaloalkyl , cyano, nitro, alkoxy, boric acid, borate, hydroxy, phosphonate, phosphonate Sulfonic acid, carboxylate, sulfonate, alkoxy, phosphate, sulfonic acid, carbonate Rubonic acid, phosphoric acid, sulfinic acid or sulfinate with substituted or unsubstituted phenyl ), and M is a cation, such as No”, NO2”, Fe (I[I), H”, Pb (■), Ce (IV), AI (I [I), 5r (rV), Cr (VI) , Mn (■), Co (III), Au (IF), Os (■), Na (1) , Li (i), K (I) or Bu4 (I).

In the most preferred embodiment of the invention, useful dopants are acids of the formula: are their acid derivatives.

R6(SO3M) e(CO2M)- (SOsM)c (R11).

(CChM).

[In the formula, C is 1.2 or 3; d and e are the same or different and are 0 or 1: R6 is a alkyl, phenyl, biphenyl, fluoro, amine, alkyl amine phosphate, phosphorus acid, borate, boric acid, dialkylaminoarylamino, diarylamino, alkaline kylaryl amino, one or more fluoro, sulfonic acid, phosphate, phosphoric acid, boric acid, Borate, sulfonate, alkoxy, carboxylate, hydroxy, nitro, sia No, amino, alkylamino, dialkylamino, arylamino, diaryl Alkyl substituted with amino, alkylarylamino or carboxylic acid groups, or or one or more alkyl, fluoro, alkoxy, fluoroalkyl, perfluor Oroalkyl, sulfonic acid, sulfonate, amino, alkylamino, dialkyl Ruamino, arylamino, diarylamino, alkylarylamino, cal Bonate, phosphate, phosphoric acid, borate, boric acid, hydroxy, nitro, cyanide or carbonate phenyl or biphenyl substituted with a rubonic acid group, or R6 is forming unsubstituted or substituted alkylene or alkenylene chains to form naphthalene, anhydride The thracene or phenanthracene fused ring system contains one or more alkyl, alkyl, xy, fluoro, fluoroalkyl, phosphate, phosphoric acid, borate, boric acid, sulfonic acid , perfluoroalkyl, sulponate, carboxylic acid, carboxylate, hydroxy optionally substituted with cy, nitro or cyano groups), and then M is a cation].

Useful in practicing the most preferred embodiments of the invention for forming dopant solutes: Useful dopants are listed below.

1-anthracene sulfonic acid, 9-anthracene sulfonic acid, 2-phenanthracenesulfonic acid, 3-7 enanthracene sulfonic acid, 9-7 enanthracene sulfonic acid, N0zCFsSOx-1 CH3SO3H.

perfluorooctyl sulfonic acid, perfluorooctylcarboxylic acid, octylsulfonic acid, dodecyl sulfonic acid, cetyl sulfonic acid, toluenesulfonic acid (TsOH), Fe　(OTs)s, Fe　(CH3SO3)s, Me3SiOTs.

dodecylbenzenesulfonic acid, naphthalenesulfonic acid, benzenedisulfonic acid, benzenesulfonic acid, 1.3-penzenedisulfonic acid, 2.5-dihydroxy-1,4-penzenedisulfonic acid, camphor sulfinic acid, naphthalene trisulfonic acid, dodecylbenzenesulfonic acid, ethanesulfonic acid, 1.5-naphthalenedisulfonic acid, Nickel phthalocyanine tetrasulfonic acid, phenylphosphonic acid, Poly(vinyl sulfonic acid), 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfamic acid, 5-sulfosalicylic acid, Trilon (4,5-dihydroxy-1,3-benzenedisulfonic acid), Vinyls sulfonic acid, sulfanilic acid, 4-sulfophthalic acid, sulfoacetic acid, methyl orange, sulfonated polystyrene, Sulfonated poly(a-vinylnaphthalene), naphthol yellow, naphthol blue black, 1.2-naphthoquinone-4-sulfonic acid, naphthylacexin 51 1-octane sulfone, t-butylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, 1.2-benzenedisulfonic acid, 4-octylbenzenesulfonic acid, 2-mesitylenesulfonic acid, 2.6-naphthalenedisulfonic acid, 2-naphthalenesulfonic acid, 1, 3. 6-naphthalene trisulfonic acid, 1, 3. 7- Naphthalenetri Sulfonic acid, sulfonazo acid, biphenyldisulfonic acid, biphenylsulfonic acid, 1,8-dihydroxynaphthalene-3,6-disulfonic acid, 3,6-dihydroxy Sinapthalene-2,7-disulfonic acid, 4,5-dihydroxynaphthalene-2, 7-disulfonic acid, 6.7-cyhydroxy-2-naphthalenesulfonic acid, 1-Na phthalene phosphate, 1-naphthalenesulfonic acid, 1-naphthalene-5,7-sinitro-8-hydroxysulfonic acid, 1-naphthalene 4-hydroxysulfonic acid, 4-bromobenzenesulfonic acid, 4-Hydroxy-5-isopropyl-2-methylbenzenesulfonic acid, 3.4- Diaminobenzenesulfonic acid, benzenephosphoric acid, 1, 3. 5-pencentrisulfonic acid, 2-methyl-5-isopropylben Zenesulfonic acid, 3,4-dinitrobenzenesulfonic acid, 2-methoxybenzene Sulfonic acid, 1-naphthalene-5-hydroxysulfonic acid, 1-naphthalene-7-hydroxy Sulfonic acid, 1-naphthalene-3-hydroxysulfonic acid, 2-naphthalene-1 -Hydroxysulfonic acid, 4-phenylaminobenzenesulfonic acid, 1.6-Na Phthalenedisulfonic acid, 1.5-naphthalenedisulfonic acid, 1.3-naphthalene-7-hydroxydisulfonic acid, and MesS i105 OzCF.

The amount of dopant is not limited and can vary within a wide range. Generally, dopa from the complex release of compounds and removal of Lewis bases and/or solvents from compositions or solutions. Sometimes polyaniline is doped to a conductivity of at least about 10 = 'ohm-'cm-'. Sufficient dopant is included in the complex so that it is doped. The upper level of conductivity is It is not specified and usually varies depending on the type of aniline polymer used. In general, the highest level The conductivity of the bell can be obtained without significantly affecting the environmental stability of the polymer. Ru.

In preferred embodiments of the invention, the amount of dopant used is at least about 1 (I' .

in an amount sufficient to obtain a conductivity of hm-'cm-', and in particularly preferred embodiments. , sufficient to obtain a conductivity of about 10-'ohm-'cm-'. these Among the particularly preferred examples, the most preferred is to use unsubstituted polyaniline. at least about 1010 oh'cm-' or more with sufficient dopants This is a specific example of obtaining a conductivity of about 10'ohm-'c m-'. About 10'ohm -’cm-’ to about 10”.

An amount sufficient to obtain a conductivity of hm-'cm-' is usually selected.

The second component of the Lewis base/dopant complex is a Lewis base. Lewis base is have some essential characteristics. The base is the p of the polyaniline in the solution or composition. K has a large pK, and is complexed with a dopant for conductive polyaniline. to form a dopant/Lewis base complex that is soluble to some extent in the solvent. I can do it. The pK of a Lewis base is the pK of polyaniline in its neutral (undoped) form.

bigger. In formula (■), n-4, m=0. Neutral with x=2, y=t and z>L The pK of the conjugate acid of polyaniline of the form is estimated to be in the range of 5.4 ± 0.4. Ru. At this time, the pK of the conjugate acid of the Lewis base component of the solution is preferably about 5.4. more preferably greater than about 6, most preferably greater than about 9.

The Lewis base can be either solid or liquid, but it releases the dopant and drives the polyaniline. and preferably in a solution or composition. It can be removed from Lewis bases can be used in many ways, such as chemical reactions, extraction, evaporation, etc. It can also be removed from the complex by any suitable method.

Lewis base conductive polyaniline articles formed from solutions or plasticized compositions Preferably, it is relatively volatile to enhance the quality of the product. “Volatile” used here ” means that a Lewis base evaporates from a composition or solution when heat is applied. and under the conditions of use, preferably at atmospheric pressure or autogenous pressure, below about 300°C. It means having a volatilization temperature such as boiling point, sublimation point, etc. The base is under the conditions of use. There is no lower limit to the volatilization temperature as long as it can be easily handled. lewis salt The volatilization temperature of the group may vary, preferably less than about 250°C, more preferably about 3 0 to about 150°C, most preferably about 35 to about 100°C.

In a preferred embodiment of the invention, the Lewis base is liquid under the conditions of use. this is, When a composition or solution is used to form an article or coating, a Lewis base from a composition or solution.

Examples of suitable Lewis bases include primary, secondary and tertiary aromatic and aliphatic amines, Sphine compounds, amides, phosphoramides and amine or phosphine functional groups such as morpholine, 4-aminomorpholine, 2-picoline, methyl Ruamine, pyridine, piperidine, ethylamino 4-picoline, pyrrolidone, 2-oxazolidone, 2-imidazolitone, triphenylamine, benzylamine diethylmethylamine, allylmethylamine, aniline, dibutylamine, Triethylamine, dibenzylethylamine, piperazine, diethylamide Soprobylamine, diphenylmethylamine, dipropylamine, triisobutylene triamine, tripropylamine, cyclohexylamine, 2-(ethylamino) Ethanol, ethanolamine, 2-(aminomethyl)pyridine, 1-aminopyridine Peridine, 2,3-cyclohexenopyridine, 1-(3-aminopropyl)- 2-picoline, 1,1-dimethylhydrazine, propylamine, amylamine, Butylamine, ethylenecyamine, N, N-dimethylethylenediamine, N, N'-dimethyl-ethylenecyamine, tetrahydrofurfurylamine, 1. 2 ．． 3.4-tetrahydroisoquinoline, trimethylphosphine, triethylphosphine Sphin et al.

In preferred embodiments of the invention, Lewis bases include amines, amides and phosphoamides. Choose from the following groups. More preferred Lewis bases are primary, secondary and tertiary aliphatic bases. amines, diamines, pyridines and amides. amides, diamines, amines and Liquid Lewis bases such as pyridine and pyridine are strong enough to complex with dopants. Because they are bases: and they are liquid at room temperature and relatively volatile (boiling point about 3 0'' to about 200'), by casting the solution or composition in a preferred form. Easy and complete removal when forming the desired solid conductive article or coated substrate. This is preferable because it allows for Most preferred amines, diamines, pyri Examples of gins and amides include piperidine, pyrrolidine, 2-picoline, pencylamide. 2,3-cyclohexenopyridine, 2-(methylamine)pyridine, 3-pyridine Choline, N, N'-dimethylethylenecyamine, N, N-dimethylethylene Diamine, ethylenediamine, morpholine, 2-pyrrolidone, 2-oxazolide ion, tetrahydrofurfurylamine, trimethylamine, triethylamine, Lipropylamine, tributylamine, dimethylamine, diethylamine, dipropylamine Lopylamine, dibutylamine, methylamine, ethylamine, propylamine , butylamine, amylamine, pyridine, isopropylamine, cyclohexy Ruamine, phenylethylamine Examples include ethanol, isobutylamine, t-butylamine, and the like.

The amount of Lewis base can vary widely, but usually at least The amount is sufficient to complex all or a portion of the dopant in Nilin. use The amount of Lewis base used can be varied over a wide range, depending on the dopant and polyamine. It varies greatly depending on the amount of Nilin. Generally, the amount of dopant and polyaniline The more The amount of Lewis base required to form the desired degree of base complex is greater; , the lower the amount of dopant and polyaniline, the more complex the dopant is. The amount of Lewis base required is reduced. Generally, the amount of Lewis base is At least about 25 mole percent, based on the total moles of repeat units. Preferences of the present invention In specific embodiments, the amount of Lewis base may be less than and in more preferred embodiments of the invention, the amount of Lewis base is greater than 100 mole percent, based on the total moles of polymer repeat units. Lewis There is no upper limit to the amount of base, but excess Lewis base may be used as a Lewis base/dopant. Excess salt acts in part as a solvent or plasticizer for the complex and polyaniline The solubility parameter of the group is also considered in conjunction with the solubility parameter of the additional solvent. must be considered.

The third component of the solution of the invention is a neutral polyaniline and a Lewis base/acid dopant. A polar organic or inorganic compound capable of dissolving the ant complex to form the solution of the present invention. It is a solvent. As used herein, "polar organic or inorganic solvents" have a relative dielectric constant of about 5 or more. The upper and dipole moments are approximately 3. The solvent is 5×10-”cm or more . Preferred solvents have a dielectric constant of about 6 or more and a dipole moment of about 5X10-" cm or more of these solvents.

Harsh solvents have relatively strong hydrogen bonding forces. The degree of hydrogen bond strength varies It can be investigated by law. Find a solvent that seems to be the most suitable for this invention. One method is described by Craver, J. Appl Polym. Sci. ,1 The solvent has a hydrogen bond strength of greater than about 50, more preferably greater than about 60. Ru.

Another useful measure of a suitable solvent is the Hildebrand parameter (d), also called the Hildebrand parameter (d). is the solubility parameter of the liquid. Preferred solvents are from about 17 to about 29, more Hildebra preferably ranges from about 18 to about 26, most preferably from about 19 to about 25. has a set of parameters.

A further useful measure of a suitable solvent is the dispersion of the Hildebrand parameter of the liquid ( d4), polar interactions (d,) and hydrogen bond interactions (d,) It is based on dividing into separate contributions from This formula (which is Alla n　F. M. Barton's “Handbook of Solubility” Parameters and Other Cohesion Parameters ter” (CRC Press, 1983), pp. 141-162, 94- 110), the Hildebrand parameter is defined by the following relation d2 -da”+ds”+db” dispersion (d, L polar interaction (d,) and hydrogen bond (d.) (“Hanse For example, for ponianiline To determine solvent suitability, we determined that the amine to imine nitrogen bond ratio was approximately 5075. The solubility parameters of the neutral base form of polyaniline 0 are as follows: Experimentally measured: da=17.4MPa d-=8.5MPa d. -10.4MPa d=22.0MPa If we define the quantity (r) as follows: r − [4 (17. 4 − d =) 2+ (8. 5-d,) 2+ (10. 4-d=) 2] (where d4, d, and dk are the expected Hansen parameters of the solvent for the polyaniline base. ) Suitable solvents have an r of less than about 7, more preferably less than about 6, most preferably about 5M It is a solvent without Pa.

The solvents used in practicing this invention are volatile. “Volatile” solvent used here is a liquid with a boiling point of about 300°C or less under the conditions of use, preferably at atmospheric pressure or autogenous pressure. It is the body. The lower limit of the boiling point is not limited, provided that the solvent is in a liquid state under the conditions of use. be. In preferred embodiments of the invention, the boiling point of the solvent is less than about 250°C. especially Preferred solvents have boiling points below about 200°C. A more preferred solvent has a boiling point of about 15 The boiling point of the most preferred solvent is from about 40 to about 100C.

Examples of useful solvents include alkyl alkanesulfonates, such as methane sulfonate. Ethyl methanesulfonate, Butyl methanesulfonate, Proethyl ethanesulfonate pill; nitriles such as acetonitrile, propionitrile, petite nitrile, Penzonitrile etc.: Aromatic solvents such as nitrobenzene, benzene, toluene etc. ; carbonates such as propylene carbonate, dimethyl carbonate, ethyl nitroalkanes such as nitromethane, nitroethane, nitrocarbonate, etc.; Tropropane etc.; amides such as dimethylformamide, dimethylthioformamide Mido, diethylformamide, N,N-dimethylacetamide, N. N-dimethy Bionamide, N-methylpyrrolidone, pyrrolidone, 2-methyl-3-o xazolidone, 1,3-dimethyltetrahydride-2-pyrimidone, lactam, carbon Brolactam etc.: Organophosphorus compounds such as hexamethylphosphoramide, diethyl phosphoramide, etc. Sphate, triethyl phosphite, trimethyl phosphate, etc.: Glycol , such as tetraethylene glycol; organic sulfur compounds, such as sulfolane, methane, etc. Tylsulfolane, dimethylsulfone, dimethylsulfoxide, glycolsulf amines, such as virolidine, piveridine, tetraethylsulfamide, etc. , morpholine, ethylamine, penzylamine, butylamine, probylamine , ethylenediamine, propylenediamine, piperazine, pyridine, indoline and other organic nitrogen compounds, such as: , vicoline, toluidine, quinoline, aniline, etc. For example, dimethylhydrazine, tetramethylurea, 1,3-dimethyl-3-imida Zolidinone, 4,4-dimethyl-2-imidazoline, 3,5-dimethylisoazo -L, 1-(3-aminopropyl)-2-pipecoline, 2-(ethylamino ) ethanol, 2,3-cyclohexenopyridine, 2-(methylamine)pyridine and 6-methylindole. Ethers, such as tetrahydrofuran, 1 ．． 3-dioxane, dimethoxyethane and 1,3-dioxolane.

Mixtures of such organic solvents, such as N-methylpyrrolidinone and pyrrolidine Alternatively, a mixture of tetrahydrofuran and 2-(ethylamino)ethanol can also be used. Can be used. When using mixtures of organic solvents or superimposed Lewis bases, The average setting of the input parameters can be calculated using the matrix algebra method. Ru.

A suitable solvent mixture is such that the average value of d, Sd, and d, is less than about 7 MPa. Solvents that lead to r values are preferred.

Essential polyaniline, Lewis base/done complex and neutral polyaniline In addition to the liquid that dissolves or plasticizes the Lewis base/dopant complex, the The solution may contain other optional components that may or may not be soluble in the solution. Like that The characteristics of the optional ingredients can vary widely and can be determined by those skilled in the art to include the polymeric article. This known substance can be contained. For soluble components, solution or final contains substances that change the physical or mechanical properties of the article being cast from solution I can do it. Examples of such substances include salts such as LiCl, LiBr, LiCF 3SOs, LiCFxSOx, KCF! (CF.)2S03 etc., these may be included to provide a dopant counter ion for the polyaniline, or or increase the solubility of polyaniline or other added common polymers. . These other common polymers that may be present include, for example, polycarbonate. nate, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polysalt vinylidene chloride, polyvinyl alcohol, polyethylene oxide, polystyrene, Nylon, cellulose, poly(1,4-cyclohexylidene dimethylene tetraph) thalate), poly(phenylene sulfide), poly(ethylene terephthalate) ), poly(4-aminocarboxylic acid), poly(hexamethyleneadipamide), poly( p-phenylene terephthalamide), poly[methane bis(4-phenyl)ka] carbonate], snorephonated polystyrene, sulfonated polystyrene (2-methylstyrene), ), sulfonated poly(4-phenylstyrene), sulfonated poly(a-vinyl styrene) Luna 7 Talen), sulfonated poly(pencil methacrylate, poly(acetate) butyrate), polypropylene, polyethylene, cellulose acetate, etc. Non For a soluble fourth component, a substrate for the conductive polymer cast from solution. There may be a substance that fills or forms the These fourth components contain other conductive components. Polymers such as poly(phenylene sulfide), which become conductive when doped , conjugated backbone polymers such as polyacetylene, polyphenylene, polythiophene, etc. , graphite, carbon black, metal conductors, reinforcing fibers and inert fillers ( (e.g. clay and glass).

Substituted or unsubstituted polyaniline homopolymers or copolymers, Lewis bases/Dova Polymerization in a solution or plasticizing composition of the invention containing a compound complex and an organic solvent The proportions of body and solvent are not limited and can be varied within a wide range, and the composition It varies from liquid to plasticized composite material. However, the following guidelines It is believed to be important for obtaining solutions and plasticizing compositions that are particularly useful for . Generally, any amount as a liquid will be at least a viscous gel or liquid. Since the plasticizing composition is formed with the polymer, the amount of solvent as a proportion of the amount of solution is limited. It is considered that it is not determined. Specific examples of these viscous gels of the invention include Silk Scree For conductive circuits and when applying thick film coatings to substrates, Particularly useful. However, for other applications, sufficient liquid solvent can be used to The viscosity of a composition or solution can be reduced to the form of a container in a fairly short period of time, such as 30 minutes or less. It is preferable to reduce the flow to at least sufficient to form or Delicious. The solvent reduces the viscosity of the solution to less than about 10,000 centivoise, preferably about 1 - Preferably present in an amount sufficient to reduce the Delicious.

The method of forming the solutions or plasticized compositions of the present invention is not limited and can vary widely. be able to. For example, the present string compositions containing substituted or unsubstituted polyanilines or One preferred method of forming a solution is to add toluene sulfonic acid in a mixing vessel. a suitable dopant such as piperidine or pyrrolidine. The polyaniline doped with base is treated with a suitable solvent such as N-methylpyrrolidone. It is added to. All or part of the Lewis base is a conductive polyaniline acid. Complexed with dopants to form Lewis base/acid complexes and neutral undoped polyas Forms a niline base. The complex and neutral undoped polyaniline are then liquid The term "compound" used here refers to the Lewis base and the conductive polyaniline. form conjugate acid-base pair-like associations or ionic bonds with the dopant for It means to do. During use, the solution or plasticizing composition can be placed in the desired form. I can do that. As the liquid and Lewis base are removed, the complex decomposes and releases the dope. emits a punt, which is then doped with polyaniline to form a doped conductive Solid polyaniline is formed in the desired form.

Another preferred method involves dissolving the undoped polymer, dopant and Lewis base in a suitable solution. The reactions are carried out simultaneously in a medium flow. That is, for example, y≧1, X≧1 and and polyaniline as a solid powder, such as polyaniline of the formula ■ with 2≧1, or Polyaniline (Vernigraniline type) or and a mixture of polyanilines (leuco form) of formula pyramine, morpholine or pyrrolidine, as well as acid dopants as solids, For example toluenesulfonic acid, dodecylbenzenesulfonic acid or naphthalene sulfonic acid is introduced into a mixing vessel containing N-methylpyrrolidone as a solvent. Therefore, solutions of polyaniline and dopant/Lewis base complexes can be quickly formed. A conductive polymer is then cast.

Similarly, undoped polyaniline in the leuco form of formula a suitable solvent such as pyrrolidine or piperidine, and a suitable Lewis base such as pyrrolidine or piperidine. and a suitable oxidizing dopant such as NOSbF, FeC15, or an acid and a mixture of oxygen and an oxidizing agent, e.g. toluenesulfonic acid and oxygen. The solution or composition of the present invention is formed from a conductive polyaniline. can be cast. Mixing conditions are not limited, but sufficient dopant Dope the desired amount of polyaniline using Complex the punt to the desired degree and use enough solvent to bring up the viscosity of the solution. reduce it to a manageable level. The solution of the invention containing the doped polymer Another method of production is to first mix polyaniline, Lewis base and solvent, and then Afterwards, if the dopant is dissolved in the solvent, add the dopant to the solution or If the pant is insoluble, a two-phase system is formed. That is, for example, non-dose propolyaniline base in a soluble solvent such as N-methylpyrrolidone and propyl Toluene mixed with an amine, a Lewis base like morpholine or pyrrolidine Adding a suitable dopant such as sulfonic acid to this suspension results in Lewis base and Dopants are complexed. Even if the dopant is insoluble in the solvent, the complexed dopant If the agent and base are soluble in the solvent, this will still result in a solution.

Various methods are possible for using the solutions of the invention. What about Lewis bases and solvents? It can also be removed from solution using common solvent removal methods such as Removal by evaporation is preferred to form polyaniline. or, Lewis base solvents are much more effective than Lewis base and solvent doped polymers. It can be removed by extraction with an extractant that is soluble.

As is clear to those familiar with polymer processing, solvents can be removed from solution or plasticized compositions. The ability to form polymeric articles by removing Enables the manufacture of goods. That is, for example, the present solution or of any desired thickness by removing volatile components from the plasticized composition. Films can also be produced. Producing extremely thin films that are virtually transparent can be done. By extruding the solution or plasticizing composition through a die , fibers or films can be produced. Similarly, melts in molds of various shapes Shaping to a mold by removing volatile components from the liquid or plasticizing composition. A compact molded article can be produced. The solution in its final fluid state or It is clear that some shrinkage will occur between the plasticized composition and the final article. However, such shrinkage is generally considered when molding polymers from solution.

Once the solution or plasticized composition is formed, the solution or plasticized composition is or before placing in the mold, some or much of the solvent is removed, and the final removal of the solvent is It may occur on the surface or in the mold. Introducing additional soluble components into the solution If they are not volatile, they are unlikely to be present in the article formed. It will be done. If the added component is a non-volatile liquid, removing the volatile component creates a new liquid. Doped conductive polymers or undoped neutral polymers in body or plasticized form The body remains. If the additional components are volatile, a foamed or expanded cell morphology of the polymer will form. be done.

If a fourth or additional insoluble component is present (or suspended fs) in solution, the dosing Polymers formed around or surrounded by insoluble materials I can't stand it. For example, if the additional component is glass fiber, the fiber and doped polymer Depending on the relative amount of the solvent, the polymer embeds in the fibers when removed, or polymerizes. The extent of fibers coated or impregnated with fibers or polymers doped with fibers An intermediate complex is formed. The amount of insoluble components far exceeds that of doped polymers. systems, individual grains of insoluble components coated or impregnated with doped polymers. A child or shape is formed.

Examples of articles formed from insoluble components and the present polymer solution are Conductive polymer coated housing for f1 (microprocessor), infrared and magnetic Microwave absorption shield, flexible conductive connector, conductive bearing, bra and semiconducting photoconductor contacts, antistatic materials for electronic component packaging, computers carpet fibers, tiles or waxes, and plastics for room floors. anti-static spray finish for screens, CRT screens, aircraft, and automobiles. A thin, optically clear antistatic finish for windows.

A third use of the polymer solution is to dope it with other substances, especially electron acceptor dopants only. In the doping of other conjugated backbone polymers, which can also be doped.

Such doping involves a process of casting a polymer solution on a second polymer article. cast as part of a process, but necessarily cast a conductive polymer from solution (You can also get it.

The following specific examples are intended to illustrate the invention and are not intended to limit it.

Example 1 1770 ml H2O, 50 g aniline (0.54 mol) and 172 g p - Ammonium persulfate is added to a solution containing toluenesulfonic acid (0.90 mol). (153.4 g in 336.5 ml H2O) at 15 °C for 40 min. I added it dropwise. Thereafter, the reaction was carried out at 15°C with 0. It lasted for 5 hours.

The resulting solid precipitate was collected and added to 6 liters of an aqueous toluenesulfonic acid solution (10 %) and then with 3 liters of methanol. The resulting blue-black The solid was dried in air for 25 hours and under dynamic vacuum at 130'C for 3 hours. After drying, poly(anilinium tosylate) was obtained as a green powder. Is this substance? The electrical conductivity of the dried and pressed pellet formed from the same material is co-1inear f.

When measured by the ur-probe method, it was lScm-'. satiate water The conductivity of the combined pellet was 205 cm-1.

Yield was 78g. The intrinsic viscosity (in CHZSOs at 25°C) is 0.66 dl/ It was g. The elemental analysis results of the dry green powder were as follows: C: 64.3 7 (weight%) H: 4.86% N: 8.59% S: 8.40% 0:13-5 1% Moisture: Less than 0.8% by weight Example 2 Poly(anilinium tosylate) (13 g) obtained from Example 1 was added to 270 ml of Suspended in fuming sulfuric acid and stirred for 10 hours. Next, the obtained solution was added to 2700ml When added dropwise to methanol, sulfonated polyaniline precipitated. obtained The sulfonated polyaniline was collected by filtration and washed with 4 liters of methanol. , dried under dynamic vacuum for 15 hours. Yield was 11 g. formed from this substance The conductivity of the pellet was measured (co-inear four-pr obe method), 0.05-0. It was lScm-'. Elemental analysis results are below It was as follows: C: 52.81%, H: 4.13%, N: 10.07%, O: 17.50%, S +10.84% Example 3 A series of experiments were conducted to investigate the solubility of Lewis base/acid dopant complexes and polyaniline. The influence of Lewis bases on solubility was determined. In these experiments, the polyaniline of Example 2 A 3 mg sample of phosphorus sulfonate was added to 0.2 ml of amine and 0.8 ml of polar solid organic solvent and the solubility of the solid was evaluated. The results are shown in Table 1 below and Shown in 2. In the table, the abbreviations have the following meanings: a) rVsJ is highly soluble; It means something.

b) rsJ means soluble.

c) rssJ means slightly soluble.

d) rIJ means insoluble.

Pyridine vs ss Triethylamine vs vs ss Tripropylamine vs vs Tri(in-octyl)amine ss vs vs pyridine SS II Triethylamine SS I 1 Tripropylamine S SS I Tri(in-octyl)amine vs vs r dimethylformamide vs vs Dimethyl sulfoxide vs vs N-methylpyrrolidone vS S Acetonitrile SS Nitromethane S1 Methylene chloride SS SS Acetone SS S Tetrahydro 7ran IS Nitrobenzene ■ vs Chloroform ■S Cyclohexanone I SS petroleum ether i The solubility of the sulfonated polyaniline/amine complexes tested was It is strongly influenced by amines. By using selected amines, sulfone polyaniline is water, methanol, ethanol, 1-propanol, 1-butano ol, 1-octatool, dimethylformamide, dimethyl sulfoxide, N- Methylpyrrolidone, acetonitrile, nitromethane, ethylene chloride, acetone, Such as tetrahydrofuran, nitrobenzene, chloroform, cyclohexanone, etc. It can be solution processed in a wide range of solvent media.

Figure 1 shows a sulfonated polyaniline (tributyl amine) compounded with three different amines. ultraviolet-visible-near-infrared (UV-v (2) It is a figure showing a 5-NIR) spectrum. These three samples have different dissolution characteristics. UV-VIS in methanol (see Tables 1 and 2) - NIR absorption properties are not different. Figure 2 shows that the solvent also has little effect on the spectrum. FIG.

Example 4 The solution prepared in Example 3 was used to deposit sulfonated polyamide on a plastic film. Nilin coatings can be produced. The first coated film is initially blue. , non-conductive, and can be made conductive by evaporating the complexed amine. became. During the evaporation process, the color of the coated film gradually changes to green and four- The electrical conductivity measured using the in-1ine probe method gradually increased.

Although heat treatment is not necessary for the evaporation process, it helps shorten the process time.

If-V I S-N I R spectroscopic analysis was performed from the tripropylamine complex form. Analyzing the characteristics of sulfonated polyaniline coatings produced and evaporated at room temperature It turned out to be a very useful analytical method. The spectrum is recorded in Figure 3. Ru. Changes in the UV-VIS-NrR absorption pattern Showing the color change of the acid salt coating. Peaks between 800-1100 nm (combined a The appearance of new near-infrared absorption (depending on the degree of disappearance of It shows that something has been accomplished.

Example 5 The poly(anilinium tosylate) produced in Example 1 was dissolved in N-methylpyrrolidone. (NMP) as an insoluble green powder. Then an equivalent amount of tripropyl amine added as a complexing agent to the dopant (i.e., toluene sulfonic acid). Ta. As soon as the amine is added, the green solid turns blue and then becomes soluble. , a particle-free deep blue solution was obtained.

The intrinsic viscosity of polyaniline in solution is 0.53 dl/g, which is comparable to the intrinsic viscosity (0.55 dl/g) obtained when added to a concentrated sulfuric acid solution. . This result indicates that the above poly(anilinium tosylate) solution is a true solution. It shows.

Poly(anilinium tosylate) coatings were successfully prepared from the above solutions on various substrates. I was able to build it. The coating was initially blue and non-conductive, but After the combined amine evaporated, it turned green and became conductive.

Example 6 Poly(anilinium tosylate) (2 g) obtained in Example 1 was added to 2 ml of tripe. 150 ml of N-methylpyrrolidone (NM P). The resulting solution was filtered through a glass sintered filter to remove traces of insoluble matter. Sexual particles were removed. The filtered solution was then heated to 60-70°C under dynamic vacuum in a flat-bottomed dish. and gradually evaporated. A free-standing film with a thickness of 120 microns was obtained. Ta. This film was measured using the four-in-one probe method. The conductivity is 0.005-0.018 cm”, which is the same for undoped polyaniline. This value is at least five orders of magnitude greater than the conductivity of the thin film.

The conductivity of this film is increased by heating or redoping the composite amine. This can be further increased by promoting the removal of 20% by weight toluene The conductivity after redoping with sulfonic acid aqueous solution for 2 days was 0.568 cm”. there were. Conductivity number after redoping with IN HCI for 1 hour: 3Scm-' A series of experiments were conducted using the methods of Examples 5 and 6 in which N-methylpyrrolidone ( NMP) and in a mixture of NMP and tri-n-propylamine (NPr3). The solubility of various doped polyanilines was investigated. poly(anilinium) tosylate) was produced by the method of Example 1. Poly(anilinium di/1hydro) dinin phosphate) and poly(anilinium triple olomethane sulfone) phosphoric acid and trifluoromethanesulfone, respectively. It was produced by the method of Example 1 except that acid was used instead. Poly(anilinium methane J-ray) poly(aniliniumbenzene sulfonate), poly(aniliniumbenzene sulfonate), poly(anilinium polystyrene sulfonate) from poly(anilinium tosylate), Methanesulfonic acid, poly(styrenesulfonic acid) and benzenedisulfonic acid respectively It was prepared by anion exchange with a solution of fonic acid. Poly(anilinium chloride) Lorido) is A.

MacDiarmid et al., 5ynthetic Metals, Vol. 13, p.

193 (1986). Solubility of these polyanilines was evaluated in NMP and NPr5. The results are shown in Table 3 below.

In Table 3, abbreviations have the following meanings: (a) rIJ means insoluble .

(b) rSJ means soluble.

(c) “vsJ means very soluble.

Poly(anilinylmutosylate) I VS sulfate) Poly(anilinium-trifluoromethane IS sulfonate) Poly(anilinium methanesulfonate) I VS poly(anilinium ben zendisulfonate) I VS poly(anilinium polystyrene sulfonate) )IS poly(anilinylmuchloride) fs Example 8 The conductive polymer gel (poly(nilinium tosylate)) obtained in Example 1 was g of poly(anilinium tosylate) was added to 35 ml of N-methylpyrrolidone or and 3.3 ml of tripropylamine. It can be manufactured as follows. Next, the obtained blue solution was heated at 100 °C for 30 minutes. do. After cooling the solution to room temperature, a viscous gel was formed. Evaporating the amine By stretching this conductive polymer gel after removing it by An electrically conductive polymer fiber was obtained.

This conductive polymer gel can also be used in other applications such as conductive molded articles, compression molded sheets, etc. It is also useful in making electrically conductive polymer articles.

Example 9 Hilde et al. for suggesting suitable solvents for use with unsubstituted, undoped polyaniline. Additional contribution of the group to determine the individual components of the brand parameter (d) Calculations were made using In explaining Hansen, the following terminology is used: )Terminology (1) d is the Hildebrand parameter (11th place: MPa), and Hansen It is related to the parameters (d,, d,, d,) as follows: d"-cL" s=d*”+d, 2+dh2(2) d is the contribution from the dispersion interaction.

(3) d is the contribution from polar interactions.

(4) d is the contribution from hydrogen bond interactions.

These components of d are dispersive interactions (F, ), polar interactions (F, ), and aggregation Estimate from the tabulated group molar attraction contribution from the hydrogen bond energy (U,) be able to. This analysis shows that the solubility properties of the undoped (base) form of polyaniline are The estimated value of parameter is derived as follows: d, -18.5 MPa d, -4.1 MPa d==7.4MPa d − (d a2 + d e” + d b”) −2o, 3 M P a vaporization Hildebrand's estimate based on the group contribution to heat yields d-23.8 MPa. It was done. Solvents that dissolve or swell undoped polyaniline have their own solubility parameters. The solvent will be close to that of this polymer. Has relatively strong hydrogen bonds The solvent is generally a good solvent.

Example 10 A series of possible solvents with significant polarity and hydrogen bonding contributions were prepared as in Example 1. Sea urchin is synthesized and then undoped by treatment with an aqueous sodium carbonate solution. (neutralized) polyaniline. Dissolving undoped polyaniline The solvents that showed this are shown in Table 4 and FIG. 4 below.

Blue A Approved solvent liquid for unsubstituted undoped polyaniline base Melting point ('C) ■ L　L　4 Morpholine 129 200.0 7.3 5.0 22.1 Piperidine 10 6 89.0 5.8 4.0 19.3 Pyridine 115 80.0 12. 3 7.3 21.7 Pyrrolidine 88 - 5.3 - N-) +) L pioIJ di: / 204 - 32.0 - 23.7 dimethyls Sulfoxide 189 79.0 46.5 13.3 26.4 Dimethylform Amide 158 68.0 37.0 11.2 24.1 Dimethylhydrazine 63 - - - 19.8 Propylamine 48.5 - 5.3 4.7 19.7 Butylamine 78 - 5.3 4.7 18.6 Vicolin 12 9 - 9.8 6.3 20.9 Aniline 182 94.0 6.9 5. 0 22.6 Quinoline 114 - 9.0 7.6 22.02-Pyrrolidine 245 - - 7.7 28.4 Dimethylacetamide 165 87.0 38.0 12.7 22.7 Tetramethylurea 177 - 23.1 1 3.0 21.7 Ethylenecyamine 117 - 12.9 6.6 25.3 Hexamethylphosphoamide 235-30.0 17.6 23.2m-k Resol 203 - 11.8 - 22.7 Benzyl Alcohol 206 -13.0 5.5 23.5 Benzylamine 185---- "-" means that no data is available.

The parameters listed in Table 4 are as follows: "Melting point" is the melting point in °C; rgwJ is the relative sound velocity of the paper moistened with solvent (water - 100), and the hydrogen bonding force "e" is the permittivity relative to the permittivity of free space (eO-8, 854X10-12 F/m); rmJ is the dipole mode at 10-30 cm and rdJ is the Hildebrand (solubility) parameter in MPa. - is. Using the data, we used the method developed by Hansen to An experimental measure of solubility parameters characterizing the interaction of lianiline was determined.

Hansen parameter values for the solvents used are A and F.

“Handbook of 5olubility” by M. Barton parameters and other Cohesive Parameters ers” (CFCC Press, 1983). When significantly different Hansen parameter values are found for a given solvent, Then, we took the string with the value closest to the theoretically expected value.

B) Hansen's method for determining solubility parameters: (1) In this method, polymerization The body is a ``melting magic sphere'' in the three-dimensional space defined by za end, d2, d. It is characterized as having J. The center point of the melting magic sphere is (d'4, d' 2, d', ), and the radius of the sphere is R.

(2) The interaction distance of a given solvent is then defined as: r − [ 4 (da-d' a)"+ (d, -d' p) "+ (db-d' b) ”] (3) When r<H, the polymer should be soluble in the given solvent .

C) Hashisen method for polyaniline and various solvents (1) Series of Table 5 Hansen space for the solvent (i.e. range of expected values of d, d, and d) By sampling the following values of Hansen parameters (all MP unit of a) was determined for polyaniline.

(i i i) d’ h-10,4 (iv) R=6 (v)d-22,0 Table 5 below shows the solvents for unsubstituted and undoped polyaniline bases. This shows the Hansen parameters of various liquids.

Table 5 Hansen Parameters of Solvents for Unsubstituted and Undoped Polyaniline Base Liquids d, d, tun [ Morpholine 16.0 11.4 10.1 4.0 Piperidine 16.2 8 ．． 7 5.8 5.2 Pyridine 17.6 10.1? , 7 3.2 dimethyl Sulfoxide 18.4 16.4 10.2 8.2N-methylpyrrolidine 16.5 10.4 13.5 4.1 Dimethylformamide 17.4 13 ．． 7 11.3 5.3 Dimethylhydrazine 15.3 5.9 11.0 5 ．． 0 Propylamine 17.0 4.9 8.6 4.1 Butylamine 16. 2 4.9 8.0 4.9 Picoline 18.2 7.8 6.8 4.0 Ani Rin 19.4 5. L 10.0 5.3 Quinoline 19.4 7.0 7. 6 5.12-Pyrrolidine 19.4 17.4 11.3 9.8 Dimethyla Cetamide 16.8 11.5 10.2 3.2 Tetramethylurea 16. 8 8.2 11.1 1.4 Ethylenediamine 16.6 8.8 17.0 18 Hexamethylphosphoramide 18.3 8.6 11゜32.0m-cle Sol 18.7 4.8 13.5 5.5 Benzyl alcohol 18.5 4.9 13.9 5.5 The average values of parameters d4, d, and dk in Table 5 are Determine the approximate center of the dissolution sphere (d'4, d'1, d' h) and find the length of the r value. determines the approximate radius.

(2) Example: (i) N-methylpyrrolidone (NMP): d, = 16.5, d, = 10.4, d, = 13.5r - [4 (16,5-17,4) 2+ (10,4~8. 5)”+(13,5-10,4)2]=4.1 Since r<H, N-methylpyrrolidone is expected to be a solvent, and the solvent It turned out to be.

(ii) Methanol: d, = 11.60, d, = 13.0, d, = 24r - [4 (16-17, 4) 2+ (13-8,5) 2+ (24-10,4) 2] = 18. 4 Since r >> H, methanol must be a non-solvent, and this is observed to be the case. It was noticed.

d,=14.1,d,=9.3,d,=9.5r=[4(14,1-17,4 )”+ (9,3-8,5)”+ (9,5-10゜4) z co-6,7 Since r>H, methyl ethyl ketone cannot be a solvent. As expected, the mail Tyl ethyl ketone swells undoped polyaniline but does not appreciably dissolve it. I found out that there isn't.

(iv) Piperidine.

d,=16.2,d,-8,7,d,-9,5r　-[4(16,2-17,4 )”+(8,7-8,5)”+(5,8-10°4)”]-5,2 Since r<H, pyridine must be a solvent and was observed to be .

Example 11 Tested a number of potential solvents and found a non-solvent for undoped polyaniline . These non-solvents are shown in Table 6 below and the expected interaction distance (r) of the Hashisen method and copolymerization. Non-solvent of lianiline tosylate and polyaniline base non-solvent Non-solvent qw m s d cL Air acetonitrile -111,224,415,3 dipropylamine -16 ,314,0 Triethylamine 2.2 15.3 14.6 Tributylamine 2.3 15.9 15.1 Diisopropylamine - -15,213,8 Cyclohexanone 38.0 9.3 20.2 17.7 Methylene chloride 5. 0 20.2 13.4 Chloroform -6,218,711,0 Methyl ethyl Ketone 31.0 9.0 19.3 14.1 Tetrahydrofuran 32.0 5.4 18.5 13.31.4-dioxane 46.0 0.0 19. 8 1g, 31.3-dioxirane-23,214,8 diethyl ether 24.0 3.8 15J 14.4 Methanol 72.0 5.7 29. 7 11.6 Ethanol 38.0 5.6 26.1 12.6 Acetone 2 9.0 9.1 19.7 13.0 Water 100.0 6.1 47.9 12 ．． 3N-ditylaniline - -21,517,14-butylaniline - - 20,416,9 Toluene 27. OL, 2 18.2 To 17.9 Cow San 2 4.0 0.3 14.9 14.9 Nitrobenzene -14,122,517 ,6 Ethyl acetate 29.0 6.0 18.2 13.4 Table 6 (continued) Polyaniline tosylate nonsolvent and polyaniline base nonsolvent Nonsolvent d, Small E Acetonitrile 18.0 6.1 11.2 Dipropylamine 6.2 5. 8 8.5 Triethylamine 3.7 1.9 11.3 Tributylamine 2 ．． 8 4.0 9.7 Diisoprobylamine 6.2 2.0 11.3 Cyclo Hexanone 8.9 5.1 5.3 Meethylene chloride 11.7 9.6 8. 7 Chloroform 13.7 6.3 14.4 Methyl ethyl ketone 9.3 9 ．． 5 6.7 Tetrahydrofuran 11.0 6.7 9.31.4-Dioxa 1.37.48.01.3-dioxolane 11.3 13.9 6.9 di Ethyl ether 2.9 5.1 9.8 Methanol 13.0 24.0 1 8.4 Ethanol 11.2 20.0 13.8 Acetone 9.8 11.0 8.9 Water 31.3 34.2 34.5 N-ethylaniline 10.5 7.7 3.44-butylaniline 9.1 6.6 4.0 Toluene 1.1 2.1 11.2 Hexane 0. OO,014,3 Nitrobenzene 14.0 0.0 11.8 Ethyl acetate 8.6 8.9 8 ．． 1 "~" indicates that no data is available.

In FIG. 5, the Hansen parameters of these non-solvents are compared to those of the solvent of Example 10. Compare using parameters and graphs. Most of the nonsolvents in Table 6 are r >R (R-6 from Example 10), but there are some exceptions. Such an exception is Often seen and arises from inaccurately known Hansen parameters. Table 4 , the solvent for polyaniline has a hydrogen bonding parameter greater than 68 in known cases. -, gl. The non-solvents for g=>68 in Table 6 are methanol and These are all r　＞＞R, so they are not expected to be solvents. Not possible.

Example 12 Various amines were dissolved in the poly(anilinium tosylate) produced in Example 1. We evaluated their ability to The experiment consisted of 2 mg of poly(anilinium tosylate) This was done by mixing with 1 ml of amine. The results are shown in Table 7 below.

In Table 7, abbreviations are defined as follows: (a) ff5J is highly soluble; be.

(b) rsJ is soluble.

(c) rssJ is slightly soluble.

(d) rlJ is insoluble.

2.3-cyclopentenopyridine ■ 2.3-cyclohexenopyridine 5 2-(methylamihabilicin 5S 1-(3-aminopropyl)-2-pipecoline S tetrahydroisoquinoline S.S. Tetrahydroquinoline I N-methylaniline ■ Diethylamine ■ Diisopropylamine l N, N-dimethylethylenediamine SN, N’-dimethylethylenedia Min 52-(ethylamino)ethanol S Ethylenediamine S l,1-dimethylhydrazine 5S N-methyl-2-pyrrolidone ■ Hexamethylphosphoamide S l, 1. 3. 3-tetramethylurea IN-methylpiperidine ■ 1-Aminopiperidine SS Tetrahydrofurfurylamine S Butylamine SS Propylamine SS A doped polyaniline powder was prepared as in Example 1 and as in Example 12. Dissolved. Table 8 below shows the solvents found for polyaniline toshisheets. Physical parameters such as boiling point (B, P, ), hydrogen bond (gw), dielectric constant ( e), dipole moment (m), Hildebrand parameter (d) and pK , a single solvent for polyaniline tosylate between Solvent Milk L Criminal Tar 2nd 1 2 Morpholine 129 200.0 7. 3 5.0 22.1 8.3 Pyrrolidine 88 - - 5.3 - 11. 3 Piperidine 106 89.0 5.8 4.0 19.3 11.1 Propi Luamine 48.5 - 5.3 4.7 18.2 10.8 Butylamine 78 - 5.3 4.7 17.7 10.82-pyrrolidone 245 - - - 28.4 - Ethylenediamine 117 - 12.9 6.6 25 ．． 3 10.1 Hexamethylphosphoamide 235 - 30.0 17.6 23.2 - Pencylamine 185 -9.32- (methylamino) Pyridine 201----2-Picoline 129-9.8 6J 20. 9 -4-Picoline 145 - - 8.6 - 6.0 Imidazole 25 6 - - - -7.11.1-dimethylhydrazine 64 - - - 1 9.8 -Tetrahydrofurfurylamine 154----Tetrahydroiso Quinoline 233-----1-aminopiperidine 150-----2-(E thylamino)ethanol 170 ---- "-" indicates that no data is available. vinegar.

These solvents have a dipole moment, m2, of 4.0XIO-''cm or more. Both are characterized by relatively high basicity (pK, >6).

Example 14 Using the method of Example 3, some Lewis base mixtures are poly(anilinium) tosylate), but none of the mixture components could be dissolved by themselves. I couldn't. The results are shown in Table 9 below. In Table 9, the abbreviations are: It has a meaning like: (a) rsJ is soluble.

(b) ff5J is highly soluble.

(c) "SS" is slightly soluble.

Aodan Binary solvent amine mixture solubility for doped polyaniline Aniline/triethylamine S l, 1. 3. 3-tetramethylurea/tripropylamine ■S Quinoline/diethylamine S Pyridine/tripropylamine SS Procedural amendment □ February 3, 1994 1.Display of the incident PCT/US91109570 1992 Patent Application No. 503738 2. Name of the invention Processing method of conductive polyaniline in solvent mixture 3, person performing correction Relationship to the incident: Patent applicant address Name: Allied-Signal Incorporated 4, Agent Address: Shin-Otemachi Building, 206-ku, 2-2-1 Otemachi, Chiyoda-ku, Tokyo 5. Date of amendment order: January 25, 1994 (transmission date) 6. Subject of amendment (1) Drawing translation International investigation report ervzut 01/110% 7n Continuation of front page (51) Int, C1,5 identification code Internal reference number HOIB 1/12 G 7244-5G (72) Inventor Shacklett, Lawrence Doubleniere Alden Bre, Maplewood, New Chassis, USA 07040 Chair 11I (72) Inventor: Miller, Granville Gee, New Chassis, USA Western Avenue, Morristown, State 07960

Claims (9)

[Claims] 1. A solution or plasticizing composition comprising: (a) a substituted or unsubstituted polya; Niline; and (b) a Lewis base/dovant complex, where the Lewis base is has a pKa greater than that of aniline, and in the presence of the polyaniline, the doba and the dopant can be complexed with the complex of the dopant. doping the polyaniline to form conductive polyaniline upon release of the polyaniline. can; and (c) A solvent capable of dissolving or plasticizing the polyaniline. 2. The polyaniline is of the type derived by polymerization of aniline of the formula or The solution of claim 1, which is a homopolymer or copolymer comprising unsubstituted polyaniline: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n is an integer from 0 to 5; m is an integer from 0 to 5, provided that the sum of n and m is 5; R2 is the same are the same or different, R3 substituent or hydrogen; and R3 is phosphinic acid, phosphonic acid, sulfonic acid, boric acid, phosphoric acid, amino, sulfone Acid salts, borates, hydroxy, phosphonates, phosphinates, phosphates, sulfates acid, nitro, sulfinate, carboxylic acid, halo, carboxylate, cyano, di eutherium or substituted or unsubstituted alkyl, alkenyl, alkoxy, Chloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkynyl, dialkylamino, arylamino, diarylamino, alkylarylamide No, aryloxy, hydroxy, alkylthioalkyl, alkylaryl, arylalkyl, aryloxy, amino, alkylthioalkyl, alkyl Aryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkyl arylsulfonyl, aryl, arylthio, arylsulfinyl, alkoxy cycarbonyl, alkylsilane or arylsulfonyl and are permitted herein. Substituents include one or more amino, alkylamino, dialkylamino, aryl Amino, diarylamino, alkylaryl amino, phosphonic acid, sulfonic acid , boric acid, sulfinic acid, sulfinate, phosphoric acid, sulfonate, borate, carbo phosphate, phosphonate, phosphate, carboxylic acid, halo, nitro, hydroxy, sia or epoxy; or any two R3 substituents are together or any one R3 substituent and R2 substituent group together 3 by forming a substituted or unsubstituted alkylene, alkynylene or alkenylene chain. , 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroalicyclic, heteroaromatic or completes the alicyclic rings, and these rings are optionally filled with one or more divalent esters, Contains carbonyl, nitrogen, sulfur, sulfinyl, sulfonyl or oxygen and is permitted herein The substituents included can be one or more amino, alkylamino, dialkylamino, aryl Ruamino, diarylamino, alkylaryl amino, phosphonic acid, sulfone acid, boric acid, sulfinic acid, sulfinate, phosphoric acid, sulfonate, borate, calcium Bonates, phosphonates, phosphates, carboxylic acids, halo, nitro, hydroxy, silyl is an ano or epoxy group moiety; or R3 is of the formula: -(OCH2CH2 )qO-CH3, -(OCH2CH(CH3))qO-CH3-(CH2)qC F3, -(CF2)qCF3 or -(CH2)qCH3 (where q is a positive integer ) It is an aliphatic group component having a repeating unit of ]. 3. Claim 2, wherein the homopolymer or copolymer is a polymer of formula II-V: Solution of: II ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ III ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ IV ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ V ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, x is an integer greater than or equal to 1; y is an integer greater than or equal to 1, provided that the ratio of x to y is greater than about 0.5; z is an integer greater than or equal to about 1; is an integer above; n is an integer from 0 to 3; m is an integer from 1 to 4, provided that the sum of n and m is 4; R2 is the same are the same or different, R3 substituent or hydrogen; R3 are the same or different, and are alkyl, alkenyl, alkyl, xy, cycloalkyl, cycloalkenyl, alkanoyl, amino, alkyl Mino, dialkylamino, arylamino, diarylamino, alkylary Ruaminoalkylthio, aryloxy, alkylthioalkyl, alkylari alkyl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkyl rusulfonyl, aryl, arylthio, arylsulfinyl, alkoxyca Rubonyl, phosphinic acid, phosphonic acid, alkylsilyl, boric acid, aryl sulfonate Nil, carboxylic acid, halo, hydroxy, phosphate, sulfonate, phosphonate, Borate, phosphinate, carboxylate, nitro, cyano, sulfonic acid, phosphoric acid, or one or more sulfonic acids, carboxylic acids, sulfinates, phosphoric acids, boric acids, sulfonic acids, finic acid, halogen, nitro, cyano, epoxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphinate, carboxylate, phosphonate aryl, alkyl or alkoxy substituted with phosphoric acid or boric acid substituents; or any two R3 substituents together or any one R3 The substituents and the R2 substituent groups together represent a substituted or unsubstituted alkylene or alkyl group. 3, 4, 5, 6, 7, 8, 9 or 10 membered heteroaromatics forming a kenylene chain; completing a heteroalicyclic, aromatic or alicyclic ring, these chains optionally containing one or more divalent nitrogen, ester, carbonyl, sulfur, sulfinyl, sulfonyl or containing an oxygen group, where the permissible substituents include one or more of sulfonic acids, carboxylic acids, Sulfinate, phosphoric acid, boric acid, sulfinic acid, halogen, nitro, cyano, epo oxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphoric acid phinate, carboxylate, phosphonate or borate substituent]. 4. R2 is hydrogen; R3 is hydrogen or alkyl; m is 3 or 4; and n is 0 or 1, 3. The solution of claim 2. 5. The base has a pKa of about 5.4 or more and a volatilization temperature of 760 mmHg. 5. The solution of claim 4, wherein the temperature is about 150<0>C or less. 6. Where the base is primary, secondary and tertiary aromatic and aliphatic amines, phosphine and 6. The solution of claim 5, wherein the solution is selected from the group consisting of: 7. The base is pyrrolidine, 2-(ethylamino)ethanol, trimethylamine , triethylamine, tripropylamine and tributylamine, 2-pyrroli 7. The solution of claim 6, wherein the solution is Don, 2-oxazolidone or 2-imidazolidone. 8. The hydrogen bonding power (gw) of the solvent is greater than about 50, and the volatilization temperature is about 15 7. The solution of claim 6, wherein the temperature is below 0°C. 9. The solution of claim 8, wherein the dopant is a compound of the formula: ▲ mathematical formula, chemical formula There are tables, etc.▼ [In the formula, M is a metal cation or a non-metal cation; c is 1, 2, 3 or 4; ; e is 0, 1 or 2; f is 0, 1 or 2; g is 0, 1 or 2; d is 0, 1 or 2; and R7 is hydroxy, alkyl, halogen, cyano, phosphonic acid, phosphonate, phosphinic acid, phosphinate, alkoxy, hydroxy, sulfinic acid, sulfinic acid phinate, or substituted or unsubstituted aryl having 1 to about 30 carbon atoms, or alkyl, where the permissible substituents are perhaloalkyl, halogen, cyano No, phosphonate, borate, phosphonic acid, sulfonate, carboxylate, phosphate , haloalkyl, sulfonic acid, sulfinic acid, sulfinate, phosphoric acid, boric acid, carbon is a rubonoic acid, or any two R7 substituents together form an alkenylate completes a fused aromatic ring system, this chain may be unsubstituted or one or more halogen, hydroxy, phosphonate, borate, phosphonic acid, sulfonate phosphate, phosphate, nitro, boric acid, phosphoric acid, carboxylate, cyano, sulfonic acid or may be substituted with a carboxylic acid group, or R6 has the formula: -(OCH2CH 2) qOCH3 or -(OCH2CH(CH3))qOCH3 (where q is 1 or about 10) ].