PROCESS FOR THE PURIFICATION OF ACETYLENE POLYMERS

Abstract: A process for the purification of acetylene polymers comprising removing polymerization catalyst from the acety­ lene polymers by contacting the polymers with organic acids such as saturated fatty acids or acid anhydrides. This contacting with the organic acids enables the amount of the residual catalyst in the acetylene polymers in a short period of time to be greatly reduced. Hence the thus-purified acetylene polymers are suitable for use in the fabrication of, e.g., batteries or as photoconductive materials.

Description: PROCESS FOPs THE PURIFICATION OF ACETYLENE POLYMERS FIELD OF THE INVENTION The present invention relates to a process for the purification of acetylene polymers. More particularly, the present invention relates to a process for the purification of acetylene polymers wherein polymerization catalyst is removed from the acetylene polymers by contacting them with organic acids BACKGROUND OF THE INVENTION It is known that acetylene polymers containing a conjugated double bond chain, which are produced by polymerizing acetylene compounds in the presence of a Ziegler-Natta catalyst comprising a transition metal compound and an organoaluminum compound, are useful organic semiconductor r. terials for electric and electronic elements since electrical conductances of the polymers are within the semiconductor region. It is also known that the electrical conductance of acetylene polymers can be controlled appropri ately within a wide range of from 10 9 to 103 # #-1.cm-1 by chemically doping films of the acetylene polymers with electron-receiving compounds such as 12, CQ2, Br2, ICl, IBr, AsF5, SbF5 and PF5, or electron-donating compounds such as Na, K and Li (see J.C.S. Chem. Commu., 578 (1977), Phys. Rev. Lett., 39, 1098 (1977), J. Am. Chem. Soc., 100, 1013 (1978), and J. Chem. Phys., 69, 5098 (1978)). As a result, acetylene polymers are expected to be used not only as semiconductor materials, but also as antistatic agents for synthetic substances, materials for use in the fabrication of solar batteries, batteries (primary or secondary), and electric or magnetic switches, and in the conversion or fixation of beams, or as electric memory materials. Acetylene polymers containing a conjugated double bond chain are produced by polymerizing acetylene compounds in the presence of polymerization catalysts such as a Ziegler-Natta catalyst, a Luttinger catalyst and a Metathesis catalyst. These catalysts, however, are difficult to remove from the acetylene polymers since they contain transition metals such as Ti, V, Cr, Co, W and Mo, or metals such as At and Zn, and acetylene polymers are generally insoluble in solvents. Various methods have heretofore been used to remove the catalyst from acetylene polymers, including (1) washing repeatedly the polymers formed with polymerization solvents or inert solvents, and (2) washing the polymers formed with inorganic acids such as hydrochloric acid, nitric acid and phosphoric acid, or mixtures of the acids and organic solvents. Method (1), however, needs to be performed repeatedly and thus requires a lot of time for catalyst removal. Furthermore, the catalyst removal efficiency of this method is not satisfactory. For example, toluene can be used in the removal of a polymerization catalyst from the acetylene polymers. Toluene, however, is not a satisfactory solvent for use in the removal of polymerization catalyst since only a very limited amount of catalyst can be removed even if the process of removal is performed using a large amount of toluene and further if the process of removal is conducted over a long period of time. In Method (2), a reaction (doping) occurs between the inorganic acids and the acetylene polymers, and furthermore the catalyst removal efficiency of this method is not sufficiently satisfactory. This method, e.g., as described in Japanese Patent Application (OPI) No. 164109/82 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application"), however, is not suitable for practical use since an extensive amount of time is required and it is not suitable for use where the acetylene polymer is in the form of a film. Moreover, doping of the polyacetylene by the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid occurs, causing changes in the structure of polyacetylene and making the polyacetylene unsuitable for use as electrically conductive material. The residual catalyst seriously influences the stability of acetylene polymers and thus a significant subject for one engaged in this field has been to reduce the amount of the residual catalyst. Insufficient catalyst removal produces disadvantages in that (1) the acetylene polymers are readily subject to oxidation and degradation, (2) the electric conductance is low, (3) the electric conductance after doping is also low, and (4) when the acetylene polymers are used as electrodes, the performance of the resulting final battery is low. SUM4ARY OF THE INVENTION As a result of extensive investigations to reduce the amount of the residual catalyst in acetylene polymers, it has now been found that the residual catalyst which is bonded to the acetylene polymer chain can be effectively removed by contacting with a compound having properties to react with the catalyst bonded to thereby render the catalyst more soluble and that an organic acid possesses such properties. This catalyst rem3val can be attained in a short time and further using very small airounts of organic acids. The present invention thus provides in a first embodiment a process for the purification of acetylene polymers, comprising removing polymerization catalyst from acetylene polymers by contacting the polymers with an organic acid In a second embodiment the invention prpvides a method for purifying acetylene polymers by contacting the polymers with an organic acid by pulverizing the acetylene polymers in admixture with an organic acid, and this can be attained in short time and further using small amounts of organic acid. The present invention thus provides in a third embodiment a process for the purification of acetylene polymers, comprising contacting the acetylene polymers with an organic acid by washing the acetylene polymers with an organic acid under reflux conditions while stirring the polymes therein. BRIEF DESCRIPTION OF THE DRAWING The Figure is a schematic cross sectional view of a battery cell for the measurement of the characteristics of a button type battery, as described hereinafter wherein: 1 is a container, 2 is a negative electrode, 3 is a membrane, 4 is a felt, 5 is a positive electrode, b is a porous Teflon sheet, 7 is a Teflon container, 8 is a Teflon ring, and 9 is an Ni lead wire. DETAILED DESCRIPTION OF THE INVENTION The present invention has been achieved by the ,indings that organic acids react with the residual catalyst bonded to the acetylene polymer chain to render the catalystbonded acetylene polymer more soluble so that the residual catalyst can be effectively removed. For example, the organic acid (RCOOH) reacts with polyacetylene produced using tetrabutyl titanate as a polymerization catalyst as follows: Polyacetylene-Ti(OBu)3 + EMI6.1 <tb> RCOOK <SEP> --Polyacetylene-Ti <SEP> (OBu)2 <SEP> + <SEP> BuOH <tb> <SEP> , <SEP> %t <tb> <SEP> OCOR <tb> When the organic acid is acetic acid, 4 wt% of the reaction product, [Polyacteylene-Ti(OBu)2(OCOCH3)], is dissolved in acetic acid. On the other hand, organic compounds conven tionally used in the catalyst removal from polyolefins and acetylene poly mers such as toluene and alcohols, however, do not react with the catalyst-bonded polyacetylene to render it soluble. For example, toluene does not react with the catalyst-bonded polyacetylene , lPolyacetylene-Ti(OBu)31, and dissolves only 0.07 wt% of the catalyst-bonded polyacetylene Thus, by contacting acetylene polymers with an organic acid the amount of the residual catalyst in the acetylene polymers can be greatly reduced. This decrease in the amount of the residual catalyst leads to a reduction in the decomposition or degradation of acetylene polymers. Furthermore, the decrease results in an increase in the mechanical strength of the acetylene polymer, and it is expected that the change in electrical conductivity with time due to decomposition or degradation of the polymer can be greatly reduced. The thus-purified acetylene polymers are quite advantageous when used in the fabrication of solar batteries, primary batteries, and secondary batteries, or as photoconductive materials. For example, when used in the fabrication of primary batteries, advantages occur in that (1) the discharge capacity is great, (2) the voltage constancy is good, and (3) self discharge is low . On the other hand, when used in the fabrication of secondary batteries, advantages occur in that (1) the energy density is high, (2) the voltage constancy Qs good, (3) self discharge is low , and (4) cycle life for repeated use is long. When, however, acetylene polymers purified with inorganic acids are used in the fabrication of primary and secondary batteries, the advantages as described above cannot be obtained since doping by the inorganic acids occurs. In particular, the advantage (4), long cycle life for repeated use, as obtained in the fabrication of secondary batteries cannot be obtained. The manner in which contact of the organic acids and acetylene polymers is achieved is not critical in the invention; i.e., any suitable manner for contact can be used. When, however, acids which are solid at the temperatures at which the contacting occurs, i.e., temperatures at which they are contacted with the acetylene polymers, are used, Solvent (I) as described below must be used in combination with the acid. In the case of other acids, Solvent (I) may be used in combination with the acid, if desired. After the removal of the polymerization catalyst, the acetylene polymers are preferably washed with Solvent (II) as described below to remove the acids. Solvents (I) and (11) may be the same or different. The term "acetylene polymer(s)" as used herein includes both polymers having the recurring unit -repre- sented by the Formula (A) as described below, and copolymers of two or more monomers, containing the recurring unit represented by the Formula (A). EMI8.1 wherein R is a hydrogen atom, a halogen atom, an alkyl group containing 6 or less carbon atoms, or an aryl group containing from 6 to 10 carbon atoms. Typical examples of acetylene polymers to which the present invention is applicable include polymers derived from acetylene, phenylacetylene, methylacetylene, hexylacetylene, butylacetylene, naphthylacetylene, chloroacetylene and bromoacetylene. The effect of the invention can be obtained efficiently particularly when polyacetylene is used. The acetylene polymers are preferably in a powder form or in a lump form (including a short fibrous form having a fiber length of 1 mm or less). Of these, highly crystalline acetylene polymers having a fibrous fine crystalline structure are particularly preferred. If the acetylene polymers are in a film form, the catalyst present in the interior of the film is difficult to remove and a long period of time is required for the removal of the catalyst. This form is not suitable for practival use. The acetylene polymer as used herein is differ ent from the film-formed acetylene polymers as described in Japanese Patent Publication No. 32581/73, and the polymers which can be used mean a polymer purified in accordance with this invention and converted to a powdered or powdery, gelatinated or gelatinous, or swollen form as described in, for example, Japanese Patent Application (OPI) Nos. 129404/80, 128419/80, 142030/80, 145710/80, 145711/80, 10428/81, 133133/81, 115305/81, Japanese Patent Application Nos. 147717/82, 84145/83, Trans. Frady Soc., 64, 823 (1968), Makromol. Chem., Rapid. Corm., 1, 621 (1980), J. Chem. Phys., 69, (1), 106 (1978), Japanese Patent Application (OPI) Nos. 53509/82, 61008/82, 174340/82, 174351/82, 72421/83 and 74706/83. The above-described gelatinated or swollen acetylene polymer is in the state that acetylene polymer fibrilis insoluble in an organic solvent are intertwined with each other and swollen in an organic solvent and thus the polymer is substantially different from the usual crosslinked polymer gel. The powdery acetylene polymer is included in the gelatinized or swollen acetylene polymer and can be produced by drying the gelatinized or swollen acetylene polymer. The acetylene polymer which has been purified according to the process of the present invention is preferably a purified powdery acetylene polymer contain ing an organic solvent or an acetylene polymer swollen with an organic solvent. The advantages in use of this polymer in producing secondary batteries cannot be obtained sufficiently if the acetylene polymer is dried prior to the purification with the organic acid. The process of the invention can be applied very effectively to the acetylene polymers produced by the use of the Ziegler-Natta catalyst, Luttinger catalyst, and Metathesis catalyst, particularly to those polymers produced by the use of the Ziegler-Natta catalyst. These catalysts comprise a transition metal compound and an organometallic compound. The transition metal compounds contain at least one transition metal of Groups IVa, Va, VIa and VIII of the periodic table, including compounds of titanium, vanadium, chromium, iron, cobalt, tungsten and molybdenum which have a halogen atom or an alkyl group, alkenyl group, aryl group, aralkyl group, alkoxide group, phenoxide group or carboxylic acid residue each having at most 20 carbonatoms, a cyclopentadiethyl group, an acetylacetone residue or carbon monoxide (carbonyl group), and complexes of these compounds with electron donor compounds such as pyridine, triphenylphosphine and dipyridyl. Among the transition metal compounds, titanium, vanadium, iron, chromium and cobalt compounds are preferred, and the titanium compounds are especially preferred. Transition metal compounds represented by the following general formulae may be cited as typical examples of the preferred transition metal compounds: Ti (OR)4 M(acac)3 MO (acac) 2 wherein R represents an alkyl or aryl group having at most 20 carbon atims, (acac) represents an acetylacetonate group, and M represents a transition metal, titanium, vanadium, chromium or cobalt. Typical examples of the transition metal compounds include tetramethoxy titanium, tetraethoxy titanium, tetran-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetraoctadecyloxy titanium, tetraphenoxy titanium, triacetylacetonatotitanium, trisacetylacetonatovanadium, trisacetylacetonatoiron, trisacetylacetonatochromium, trisacetylacetonatocobalt, titanium oxyacetylacetonate and vanadium oxyacetylacetonate. The organometallic compounds have at least one metal selected from-metals of Groups IIa, IIb, IIIb and IVb of the periodic table. Some of such compounds are represented by the following formula MR n wherein M represents a metal of Group IIa, IIb, IIIb or IVb of the periodic table, R represents a hydrogen atom, a halogen atom, or an organic group selected from the group consisting of alkyl group , alkenyl group , aryl group, aralkyl group , alkoxide group , a phenoxy group and a cyclopentadieneyl group having up to 20 carbon atoms, two or more R's may be identical or different but at least one of them is a hydrogen atom or the organic group, and n is a positive integer equal to or smaller than the maximum atomic valence of the metal. Examples of the other organometallic compounds are compelxes of the above organometallic compounds with an equimolar proportion of pyridine, triphenylphosphine or diethylether, the reaction products formed between 1 mole of the above organometallic compounds and ata most 2.0 moles of water, and double salts of two of the above organometallic compounds. Examples of the organometallic compounds include organometallic compounds having magnesium, calcium, zinc, boron, aluminum, potassium, silicon and tin. The organometallic compounds of magnesium, zinc, aluminum and tin are preferred, and the organoaluminum compounds are especially preferred. Typical examples of the organoaluminum compounds are triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diethyl aluminum chloride, di-n-butyl aluminum chloride, ethyl aluminum sesquichloride, diethyl aluminum butoxide and the reaction product of triethyl aluminum and water (in a mole ratio of 1:0.5). Aluminum-siloxalene compounds, aluminum-amide compounds, dialumoxalene compounds and double salts containing the aforesaid organoaluminum compounds can also be used. Acetylene polymers which can preferably be used in the present invention can be obtained by polymerizing acetylene monomers in the presence of the catalysts with stirring wherein the concentration of transition metal compound is from 0.0001 to 0.1 mol per liter of polymerization solvent and the molar ratio of aluminum to transition metal is from 1/1 to 75/1. Acids which can be used in the embodiments of the invention include acids and acid anhydrides such as mono- or multivalent carboxylic acid anhydrides such as acetic anhydride, phthalic anhydride, maleic anhydride and succinic anhydride, mono- or multivalent unsaturated acids such as maleic acid, acrylic acid, crotonic acid, and oleic acid, mono- or multivalent aromatic acids such as benzoic acid, naphthoic acid, phthalic acid and salicylic acid, mono- or multivalent saturated fatty acids such as acetic acid, propionic acid, butyric acid, lactic acid, succinic acid, formic acid, and benzylic acid, sulfonic acid compounds such as benzenesulfonic acid, and oxalic acid compounds such as oxalic acid and monoethyl oxalate. These acids can be used alone or in combination with each other. Preferred examples are mono- and multivalent saturated fatty acids or acid anhydrides. Particularly preferred are acetic acid, acetic anhydride and hydroxycarboxylic acids (oxy acids). Typical examples of the oxy acids are -oxy acids such as glycolic acid, lactic acid, tartaric acid, malic acid, glyceric acid and aldonic acid. Solvents (I) and (II) as used in the ribodiments of this invention are not limited; any solvents can be used in the process of the invention as long as the solvents do not dissolve the acetylene polymers. Usually water and organic solvents are used. Suitable organic solvents which can be used include aromatic compounds such as benzene, toluene, xylene, decalin and tetralin; halogenated compounds such as chlorobenzene, dichlorobenzene, chloroform, carbon tetrachloride and trichlene; alcohol compounds such as methyl alcohol, ethyl alcohol and isobutyl alcohol; ketone compounds such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone; aliphatic compounds such as hexane and heptane; alicyclic compounds such as cyclohexane and methylcyclohexane; sulfolane compounds such as sulfolane, 3-methyl sulfolane and 3-ethyl sulfolane; nitro compounds such as nitrobenzene; ether compounds such as tetrahydrofuran, 2,5dimethyltetrahydrofuran, and diethyl ether; cyano compounds such as acetonitrile; aromatic ethers such as anisole and phenetole; esters such as ethyl acetate and ethyl benzoate; Cellosolves; monoglyme and diglyme; and ethylene carbonates or propylene carbonates. These organic solvents can be used alone or in combination with each other. The ratio of the organic acid to the acetylene polymers is not critical in the invnetion and can be varied depending on the form of the acetylene polymers, the type and amount of the catalyst residual, the type of the organic acid, the contacting time, i.e., the time during which the acid is contacted with the acetylene polymers, and so forth. The optimum ratio can be easily determined by routine experimentation. In general, the organic acid is used in an amount of from 0.1 to 1,000 parts by weight, preferably from 0.1 to 500 parts by weight, per part by weight of the polymer. If solid acids are used, solvents capable of dissolving the solid acids must be used. With other acids, such solvents do not always have to be used. In many cases, however, the use of such solvents is preferred to facilitate the subsequent acid removal or from an economic standpoint. The contacting time of the organic acid with the acetylene polymers varies with the form of the acetylene polymers, the type and amount of the residual catalyst, or with the amount of the organic acid used. In general, however, a suitable contacting time can range from about 1 minute to about 10 hours. The contacting temperature is not specially limited as long as it is below the decomposition temperatures (about 4000C) of the acetylene polymers. In accordance with the second embodiment of this invention, a mixture of the acetylene polymers and organic acids is pulverized. This pulverization is generally sufficient to be performed by the use of machines such as a ball mill, an oscillating ball mill, an impact pulverizer, and a colloid mill. In the case of polymers (e.g., polyacetylene ) which are degraded when treated in the air, it is necessary for the pulverization to be performed in an atmosphere of an inert gas (e.g., nitrogen and argon). In this pulverization process, the use of Solvent (I) as described above is not essential, but in many cases it is preferred since the acetylene polymers can be uniformly contacted with the organic acids. The pulverization temperature is not critical and is usually within the range of from 0 to 500C. The pulverization time cannot be determined unconditionally since it varies with the type of the pulverizing machine, the type and amount of the acetylene polymer, and the type and amount of each of the acid and solvent. However, in general, a suitable pulverization time ranges from about 1 minute to about 48 hours. In the third embodiment of the process of this invention, the reflux can be carried out under atmospheric pressure or reduced pressure with stirring, and can be performed in any suitable manner conventional in the art. The purified acetylene polymer can be subsequently washed with one of the solvents listed above, if desired, to remove any organic acid remaining. The acetylene polymers purified by the embodi- ments of the process of this invention are particularly useful in producing acetylene polrmer moldings for a secondary battery, e.g., for a positive electrode and/or a negative electrode thereof. The secondary battery produced using acetylene polymer purified by the process of this invention has advantages over conventional secondary batteries in that the number of cycles is great and self-discharge is low. Although the exact reason why a battery with an electrode made of an acetylene polymer purified with an organic acid as in this invention exhibits high performance is not known at present, it is assumed that (1) the purification decreases the amount of the residual catalyst, (2) the purification removes low molecular weight acetylene polymers, and (3) the organic acid is adsorbed onto the surface of acetylene polymers to prevent the degradation of the polymer. The acetylene polymer is molded under pressure in the presence or absence of an organic solvent, e.g., one or more of the solvents described above. This mold is used as an electrode for batteries. Press molding in the presence of an organic solvent produces a mold having an increased mechanical strength, which is more preferred for use as an electrode for batteries. In the secondary battery, the mold of the acetylene polymer purified with the organic acid is used in the following manners: (1) Type (1): a positive electrode alone is made of the acetylene polymer; (2) Type (2): a negative electrode alone is made of the acetylene polymer; and (3) Type (3): both positive and negative electrodes are made of the acetylene polymer. In Type (1) above, the negative electrode may be made of light metals such as lithium, sodium and aluminum; interlaminar compounds such as graphite, carbon fiber and TiS2; or conjugated polymeric compounds other than the acetylene polymer. In I Ty6e (2) above, the positive electrode may be made of conjugated polymeric compounds other than the acetylene polymer. Suitable conjugated polymeric compounds include poly(p-phenylene), poly(m-phenylene), polypyrrole, poly (2,5-thienylene), poly(3-methyl-2,5-thienylene), polyphenylene sulfide, polyphenyl acetylene, polyarylene quinones, polyazophenylene, poly(Schiff base), polvamino quinones, polybenzimidazoles, polyacequinones, electrically active polymers as described in Japanese Patent Application (OPI) No. 195731/82 and EP-67,444, and thermal decomposition products of polyimides, polyacrylonitrile and poly(a-cyano acryl). Typical examples of polyarylene quinones, polyazophenylene, poly(Schiff base), polyamino quinones, and poiybenzimidazoles among the above-described conjugated polymeric compounds are described in J.E. Katon ed. (translated by H. Tsuchida), Kobunshi Yuki Handotai, Shokodo Co. (1972), pages 87-112. Of the above-described conjugated polymeric compounds, poly(p-phenylene), poly(2,5-thienylene), poly (3-methyl-2,5-thienylene) and polypyrrole are preferred. These conjugated polymeric compounds can be used in any suitable form, such as in the form of film, powder or short fiber. In the production of the battery electrode, suitable electrically conductive materials such as graphite, carbon black, acetylene black, metal powders, and carbon fiber may be added to the acetylene polymer and conjugated polymeric compounds. Also, a metal net, for example, may be incorporated in the electrode as a current-collecting material. In addition, thermoplastic resins such as polyethylene, modified polyethylene and polytetrachloroethylene may be added as a reinforcing material. In the production of the electrode, positive or negative electrode of the senSky battery of the invention, as well as the acetylene polymer and the conjugated polymeric compounds, electrically conductive acetylene polymers and other conjugated polymeric compounds produced by doping with a dopant can be used. Either chemical doping and electrochemical doping can be employed in the doping of the acetylene polymer and other conjugated polymeric compounds. As dopants for use in chemical doping, various electron-accepting and electron-donating compounds which are known, such as (I) halogens such as iodine, bromine and bromoiodide, (II) metal halides such as arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus penta fluoride, aluminum chloride, aluminum bromide and aluminum fluoride; (III) proton acids such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid; (IV) oxidants such as sulfur trioxide, nitrogen dioxide and difluorosulfonyl peroxide; (V) AgCQO4; and (VI) tetracyanoethylene, tetracyanoquinodimethane, chloranil, 2,3dichloro-5,6-dicyano-p-benzoquinone and 2,3-dibromo-5,6dicyano-p-benzoquinone, can be used. Dopants which can be used in electrochemical doping include (i) anion dopants such as anions of halides of Group Va metals, such as Prs , SbF6 , AsP6 and SbCl26-; anions of halides of Group IIIa, such as BF ; halogen anions such as I-(I3-), Br and C±; and perchloric acid anions such as CGQ4 (which are effective as dopants to produce p-type electrically conductive acetylene and other conjugated polymers), and (ii) cation dopants such as alkali metal ions, such as Li+, Na+ and K+; and quaternary ammonium ions such as R4N (wherein R is a hydrocarbon group containing from 1 to 20 carbon atoms) (which are effective as dopants to produce n-type electrically conductive acetylene and other conjugated polymers). Typical compounds which produce the abovedescribed cation and anion dopants are shown below for exemplification: LiPF6, LiSbF6, LiAsF6, LiCQO4, NaI, NaPF6, NaSbF6, NaSsF6, NaClO4 KI, KPF6, KSbF6, KAsF6, KClO4, (n-Bu)4N+.(ASF6)-, (n-Bu)4N+.(PF6)-, (n-Bu)4N+.ClO4-, LiAlCl4, LiBF4, NO2.BF4, NO.BF4, NO2-AsF6, NO.AsF, NO2.ClO4, and NO.ClO4. These dopants can be used singly or as a mixture comprising two or more thereof. In addition to the above-described anion dopants, HF2 can be used. As cation dopants, other than the abovedescribed cation dopants, the following can be used. Pyrylium or pyridinium cations represented by the formula (I): EMI23.1 wherein X1 is an oxygen atom or a nitrogen atom, RÚ is a hydrogen atom, an alkyl group containing from 1 to 15 carbon atoms, or an aryl group containing from 6 to 15 carbon atoms, R2 is a halogen atom, an alkyl group containing from 1 to 10 carbon atoms, or an aryl group containing from 6 to 15 carbon atoms, m is 0 when X1 is an oxygen atom, or 1 when X1 is a nitrogen atom, and n is 0 or an integer of from 1 to 5. Carbonl cations represented bv the formula (II) or (III): EMI24.1 wherein R , R4 and R5 are each a hydrogen atom (provided that R3, R4 and R5 are not hydrogen atoms at the same time), an alkyl group containing from 1 to 15 carbon atoms, an aryl group containing from 6 to 15 carbon atoms, or a group of the formula -OR7 (wherein R7 is an alkyl group containing frori 1 to 10 carbon atoms or an 6 aryl group containing from 6 to 15 carbon atoms), and R is a hydrogen atom, an alkyl group containing from 1 to 15 carbon atoms, or an aryl group containing from 6 to 15 carbon atoms. The HF2 anion is usually prepared by dissolving the compound (a hydrogen fluoride salt) represented by the formula (IV), (V) or (VI) as described below, as a supporting electrolyte, in a suitable organic solvent. R84N.HF2 (IV) MHF2 (V) EMI25.1 wherein R8 and R9 are each a hydrogen atom, an alkyl group containing from 1 to 15 carbon atoms, or an aryl 10 group containing from 6 to 15 carbon atoms, R is an alkyl group containing from 1 to 10 carbon atoms, or an aryl group containing from 6 to 15 carbon atoms, X2 is an oxygen atom or a nitrogen atom, n is O or a positive integer of 1 to 5, and M is an alkali metal atom. Typical examples of compounds represented by the formulae (IV), (V) and (VI) are as follows: EMI25.2 <tb> H <SEP> H4N <SEP> N <SEP> HF2, <SEP> buzzBudNHF,, <SEP> NaHF21 <tb> The <SEP> pyrylium <SEP> or <SEP> pyridinium <tb> Li.HF2, and cation represented by the formula (I) is prepared by dissolving a salt of a cation represented by the formula (I) and an anion, such as ClO4-, BF4-, AlCl4-, FeCl4, FeCl4-, SnCl5-, PF6-, PCl6-, SbF6-, AsF6-, CF3SO3-, and HF2-, as a supporting electrolyte, in a suitable organic solvent. Typical examples of such salts are shown below: EMI26.1 EMI27.1 Typical examples of the carbonium cations represented by the formulae (II) and (III) are as follows: EMI27.2 These carbonyl cations are prepared by dissolving the salts of the cations and anions (carbonium salts), as supporting electrolytes, in a suitable organic solvent. Typical examples of such anions include BF, r AlCl4-, AlBr3Cl-, FeCl4-, SnCl3-, PF6-, PCl6-, SbCl6-, SbF6-, C4 , and CF3SO3 . Typical examples of the carbonium cations are as follows: (C6H5)3C.BF4, (CH3)3C.BF4, HCO.AlCl4, HCO.BF4, and C6H5CO.SnCl5. The electrolyte for use in electrochemical doping may be either an aqueous solution or a non-aqueous solution. Preferably the electrolyte is prepared by dissolving the above-described dopant in a non-aqueous organic solvent. This non-aqueous organic solvent is preferably aprotic and is of high dielectric constant. Examples are ethers, ketones, nitriles, amines, amides, sulfur compounds, phosphates, phosphites, borates, chlorinated hydrocarbons, esters, carbonates, and nitro compounds. Of these compounds, ethers, ketones, nitriles, phosphates, phosphites, borates, chlorinated hydrocarbons and carbonates are preferred. Typical examples of such preferred compounds include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, monoglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2-dichloroethane, y- butyrolactone, valerolactone, tolunitrile, dimethoxyethane, methyl formate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethylsulfoxide, dimethylthioformamide, methyl phosphate1 methyl phosphate, ethyl tosphite, methyl phosphite, sulfolane and 3-methyl sulfolane. These organic solvents can be used alone or as a mixture comprising two or more thereof. Depending on the type of the battery or the type of the electrode, oxygen, water, a protic solvent, and so forth in the organic solvents may reduce the characteristics of the battery. Thus, it is preferred for the organic solvents to be purified using conventional methods. The amount of the dopant doped onto the acetylene polymer and other conjugated polymeric compounds is from about 2 to about 40 mol%, preferably from 4 to 30 mol%, and most preferably from 5 to 20 mol%, per mol of the recurring unit of the acetylene polymer and other conjugated polymeric compounds. If the amount of the dopant is less than 2 mol% or greater than 40 mol%, a battery having a sufficiently high discharge capacity cannot be obtained. The amount of the dopant can be controlled appropriately by measuring the amount of electricity passed during electrolysis. The doping may be performed either at a constant current, or at a constant voltage, or under the conditions that both the current and voltage change. The current value, the voltage value, the doping time, and so forth in conducting the doping operation cannot be determined unconditionally since they vary with the bulk density of the acetylene polymer and other conjugated polymeric compounds, the area, the type of the dopant, and the type of the electrolyte. In the secondary battery which can be produced using the acetylene polymer purified by the process of this invention, as well as the above-described electrolytes, high ion conductivity organic solid electrolytes comprising polyethylene oxide and NaI, NaSCN or the like, and paste-like mixtures of electrolytes (dopants) and organic solvents can be used. Moreover, since the concentration of the electrolyte as used in this secondary battery varies with the type of positive or negative electrode, charge-discfiarge conditions, operation temperature, the type of electrolyte, the type of organic solvent, and so forth, the concentration cannot be set forth specifically. The electrolyte may be either a homogeneous system or a heterogeneous system, and the electrolyte concentration is usually within the range of from 0.001 to 10 mol/±. The acetylene polymer or the electrically conductive acetylene polymer prepared by doping a dopant onto the purified acetylene polymer produced with this invention can bemused in the production of a secondary battery in various manners: (1) only a positve electode is made of the polymer, (2) only a negative electrodeis made of the polymer, and (3) both the positive and negative electode are made of the polymer. In a preferred arrangement, both the positive and negative electrodes are made of the polymer. Typical examples of secondary batteries are shown below. Type (1): Negative Positive electrode Electrolyte electrode (CH)x LiClO4 Li [(CH)+0.06(ClO4)-0.06]x LiClO4 Li (CH)x LiBF4 (C6H4)x Type (2): Negative Positive electrode Electrolyte electrode (C6H4)x LiBF4 (CH)x Type (3): Positive Electrode Electrolyte Negative Electrode (CH)x Et4N.BF4 (CH)x [(CH)+0.024(ClO4)-0.024]x (n-Bu4N)+.(ClO4)- [(n-Bu4N)+0.024(CH)-0.024]x [(CH)+0.06(PF6)-0.06]x (n-Bu4N)+.(PF6)- [(n-Bu4N)+0.06(CH)-0.06]x [(CH)+0.050(ClO4)-0.050]x (n-Bu4N)+.(ClO4)- [(CH)+0.020(ClO4)-0.020]x [(n-Bu4N)+0.02(CH)-0.02]x (n-Bu4N)+.(ClO4)- [(n-Bu4N)+0.07(CH)-0.07]x [(CH)+0.010(I3)-0.010]x NaI [(CH)-0-010(Na)+0.010]x The symbols"(CH) ;and "(CH4)x represent an acetylene polymer and poly(p-phenylene), respectively. Other examples are shorn below: (CH)x/graphite, (CH)x/(C4H2S)x, (CH)x/graphite, (CH)x/carbon fiber, and (CH)x/TiS2. In the secondary battery, if necessary, a glass plate, a porous film made of a synthetic resin such as polyethylene or polypropylene, and a sheet of natural fiber paper can be used as a membrane. Some of the acetylene and other conjugated polymers as used herein are sometimes gradually oxidized by oxygen, decreasing the performance of the battery. Thus, it is preferred for the battery to be sealed and kept in a substantially oxygen-free state. The secondary battery produced using the acetylene polymer purified by the process of this inven tion has various advantages; for example, the cycle life is long, the energy density is high, and the self discharge rate, the voltage stability and the charge discharae efficiency are good. Furthermore, the secondary battery is light, small-sized, and has a high energy density. Hence, it is suitable for use in portable devices, electric cars, gasoline cars, and as a battery for te storage of electric power. The present invention is described in greater detail by reference to the following Examples and Comparative Examples. The amount of the residual catalyst was measured using a fluorescent X-ray method. The pulverizer used was a desk ball mill (manufactured by Irie Shokai Co., Ltd.), and stainless steel balls of a diameter of 10 mm were used. The results are shown in Tables 1, 2, 3 and 4 below. EXAMPLE 1 A l-liter glassclave was charged with 500 mQ of xylene, 1 g (8.7 mmol) of triisobutyl aluminum, and 1.5 g (4.4 mmol) of tetrapropyl titanate, and acetylene gas was blown through the above-prepared mixture at 600C for 2 hours while stirring the mixture. After the polymerization reaction was completed, a powder portion separated. Then, 10 g of the powder was added to a solution of 15 g of benzoic acid dissolved in 100 mQ of chlorobenzene and the mixture was stirred at room temperature (about 20-300C) for 2 hours. After the separation of the liquid portion, the resulting powder was fully washed with chlorobenzene and dried. EXAMPLE 2 A powdery polyacetylene was produced in the same manner as described in Example 1 except that 3 g of a powder prepared by grinding 50 g of diethoxymagnesium and 10 g of tetraethyl titanate in an oscillating ball mill (magnetic balls of a diameter of 10 mm constituted about 50% of the internal volume of I liter) was used in place of the tetrapropyl titanate. To 10 g of the thus-obtained powder were added 100 mQ of acetonitrile and 20 g of maleic acid, and the resulting mixture was then stirred at 600C for 6 hours. The powder was separated, fully washed with acetonitrile, and dried. EXAMPLE 3 The procedure of Example 1 was repeated and 2.0 g of phenylacetylene was introduced prior to the introduction of acetylene gas, whereby 12 g of a powder was formed. The content of phenylacetylene units of the powder was 10% by weight. To this powder was added 50 mQ of acetic anhydride, and the resulting mixture was stirred at room temperature for 2 hours. After the separation of the liquid portion, the residue was fully washed with toluene to remove the acetic anhydride and then dried. EXAMPLE 4 A powder material was produced in the same manner as in Example 1 except that ethyl alcohol was used in place of xylene, 10 g (0.26 mol) of sodium borohydride was in place of the triisobutyl aluminum, and 8 g (0.024 mol) of cobalt nitrate was used in place of the tetrapropyl titanate. To 0.5 g of the powder material was added a mixture of 50 mt of acetone and 20 mt of butyric acid, and the resulting mixture was then stirred at room temperature for 6 hours. Then, the powder material was fully washed with ethyl alcohol and dried. EXAMPLE 5 To 10 g of a powder material produced in the same manner as in Example 1 were added 100 mQ of tetrahydrofuran and 50 mQ of formic acid, and the resulting mixture was stirred at 400C for 5 hours. Then, the powder material was fully washed with tetrahydrofuran and dried. EXAMPLE 6 To 10 g of an polyacetylene powder produced in the same manner as in Example 1 were added 100 mQ of methyl alcohol and 40 mt of acetic acid, and the resulting mixture was stirred at room temperature for 2 hours. The powder was separated, and then fully washed with methyl alcohol and dried. COMPARATIVE EXAMPLE 1 A mixture of 30 mQ of toluene, 4 g (11.7 mmol) of tetrabutyl titanate, and 4 g (35 mmol) of triethyl aluminum was placed in a Shlenk's flask, which was then connected to a vacuum line system. Acetylene gas was blown through the mixture at -780C while at the same time the flask was agitated to form a film on the inner surface of the flask. After 2 hours, the polymerization reaction was stopped to obtain 2 g of the film. Then, 1 g of the film was immersed in 50 m± of acetic acid and allowed to stand at OOC for 48 hours. At the end of the time, the film was removed from the acetic acid, fully washed with toluene to remove the acetic acid, and dried. COMPARATIVE EXAMPLE 2 A film (1 g) produced in the same manner as in Comparative Example 1 was placed in 100 mQ of toluene and allowed to stand for 24 hours. At the end of the time, the film was removed and dried. COMPARATIVE EXAMPLE 3 The same procedure of purification as in Comparative Example 2 was repeated five times using 100 m± portions of toluene (total amount: 500 mQ) for 120 hours, and the film was then dried. COMPARATIVE EXAMPLE 4 To 10 g of a polymer powder produced in the same manner as in Example 1 was added 100 mt of toluene, and the resulting mixture was stirred at room temperature for 24 hours. The polymer was separated, and then fully washed with toluene and dried. COMPARATIVE EXAMPLE 5 The procedure of Example 6 was repeated but acetic acid was not added. COMPARATIVE EXAMPLE 6 The procedure of Example 2 was repeated but the amount of maleic acid was changed to 0.1 g. COMPARATIVE EXAMPLE 7 To 10 g of a powder material produced in the same manner as in Example 1 was added 100 mi of sulfuric acid, and the resulting mixture was stirred at room temperature for 24 hours. The powder material was separated, and then washed with toluene many times, but the sulfuric acid doping could not be removed. Thus, the powder material with sulfuric acid doped therein (about 5 mol%) was dried as such. COMPARATIVE EXAMPLE 8 The procedure of Comparative Example 7 was repeated wherein hydrochloric acid was used in place of sulfuric acid. The hydrochloric acid doping could not be removed and remained in an amount of about 4 mol%. EXAMPLE 7 A Shlenk's flask was charged with 30 mZ of toluene, 4 g (11.7 mmol) of tetrabutyl titanate, and 4 g (35 mmol) of triethylaluminum and then connected to a vacuum line system. After the mixture was cooled to -78 C, the flask was rotated to uniformly coat the catalyst solution on the inner surface thereof. Then, acetylene gas was passed thereinto to form a film of polyacetylene on the inner surface of the flask. After 2 hours, the polymerization was stopped, and 2 g of the film was obtained. Then, 1 g of the film was mixed with 10 mZ of acetic anhydride, and the resulting mixture was pulverized for 4 hours and subsequently washed with toluene. The pulverized product was removed and the amount of the residual catalyst was measured. EXAMPLE 8 A l-liter glassclave was charged with 500 m± of xylene, 1 g (8.7 mmol) of triisobutylaluminum, 1.5 g (4.4 mmol) of tetrapropyl titanate, and 0.5 g of phenylacetylene. Then, acetylene gas was passed through the mixture at 600C for 2 hours while stirring the mixture. After the completion of polymerization, a powder portion was separated. Infrated spectrum analysis showed that the copolymer thus-produced contained 8 mol% of phenylacetylene. To 10 g of the powder was added a solution of 15 g of benzoic acid dissolved in 100 mt of chlorobenzene, and the resulting mixture was pulverized at room temperature for 2 hours and washed with toluene. After this washing procedure, the amount of the residual catalyst was measured. EXAMPLE 9 A l-liter glass autoclave equipped with an impeller blade type mechanical stirrer was charged with 200 mQ of toluene, 2 mQ (5.9 mmol) of tetrabutoxy titanium, and 2 mt (14.6 mmol) of triethylaluminum in an atmosphere of nitrogen, and acetylene gas was introduced therein and polymerized at a polymerization temperature of -780C under an acetylene partial pressure of 2 0.9 kg/cm for 2 hours. Simultaneously with the intro- duction of the acetylene gas, polyacetylene in the form of short fibers of a length about 1 mm began to form. After the polymerization was completed, the short fiber-shaped polyacetylene was placed on a glass filter and fully washed with about 1 liter of toluene to remove the catalyst. The short fiber-shaped polyacetylene after the removal of the catalyst contained 52% by weight of toluene. Then, 1 g of the toluene-containing short fiber-shaped polyacetylene, 10 g of acetic acid, and 100 g of toluene were mixed, and pulverized for 4 hours. After washing with toluene, the amount of the residual catalyst was measured. EXAMPLE 10 A liter glass autoclave equipped with an impeller blade type mechanical stirrer was charged with 500 mi of toluene, 0.2 mi (0.59 mmol) of tetrabutoxy titanium and 2 mt (14.6 mmol) of triethylaluninum, and acetylene gas was introduced therein and polymerized at a polymerization temperature of 30 C under an acetylene partial pressure of 1.6 kg/cmê for 1 hour while stirring the mixture. Simultaneously with the introduction of the acetylene gas, a black polyacetylene powder with a grain size of about 0.1 mm was formed. To 1 g of the polyacetylene were added 50 g of xylene and 5 g of acetic acid, and the resulting mixture was pulverized for 6 hours and washed with toluene. Then, the amount of the residual catalyst was measured. EXAMPLE 11 The procedure of Example 8 was repeated wherein in place of tetrapropyl titanate was used 3 g of a powder prepared by pulverizing 50 g of diethoxy magnesium and 10 g of tetraethyl titanate in an oscillating ball mill (magnetic balls having a diameter of 10 mm occupied about 50% by volume of the inner volume of 1 liter). To 10 g of the above-produced acetylene polymer powder were added 100 mQ of acetonitrile and 20 g of maleic acid, and the resulting mixture was wet pulverized for 5 hours and washed with acetonitrile. The amount of the residual catalyst was measured. EXAMPLE 12 The procedure of Example 8 was repeated wherein ethyl alcohol was used in place of xylene, 10 g (0.26 mmol) of sodium borohydride was used in place of triisobutylaluminum, and 8 g (0.024 mmol) of cobalt nitrate was used in place of tetrapropyl titanium. To 0.5 g of the above-produced acetylene polymer powder were added 50 mQ of acetone and 20 mi of butyric acid, and the resulting mixture was wet pulverized at room temperature for 6 hours and then washed with ethyl alcohol. Then, the amount of the residual catalyst was measured. EXAMPLE 13 To 10 g of the powder produced in Example 10 were added 100 mQ of tetrahydrofuran and 50 mQ of formic acid, and the resulting mixture was wet pulverized for 5 hours. After the pulverization process, the mixture was washed with tetrahydrofuran, and then the amount of the residual catalyst was measured. EXAMPLE 14 To 10 g of the powder produced in Example 10 were added 100 m± of methyl alcohol and 40 mt of acetic acid, and the resulting mixture was wet pulverized at room temperature for 2 hours. After separation, the powder was washed with methyl alcohol, and then the amount of the residual catalyst was measured. COMPARATIVE EXAMPLE 9 The procedures of Example 10 were repeated but acetic acid was not used. COMPARATIVE EXAMPLE 10 The procedures of Example 10 were repeated and the mixture was immersed in a mixed solvent of acetic acid and xylene (weight ratio 1:10) for 6 hours without application of pulverization. EXAMPLE 15 A l-liter glass autoclave was charged with 500 mt of xylene, 3.4 g (14.6 mmol) of triethylaluminum, and 2.0 g (5.8 mmol) of tetrabutyl titanate, and acetylene gas was introduced therein and polymerized while stirring the mixture at room temperature under a partial pressure of 0.9 kg/cmê for 4 hours to form polyacetylene in the form of a powder. Then, S g of the powder was placed in a cylindrical filter paper, which was then placed in a Soxlet extractor filled with 300 mQ of lactic acid. A shaft for stirring was inserted from the top portion of the condensor of the Soxlet extractor in the inside thereof until it reached the filter paper. An extraction procedure was performed under reflux for 6 hours while stirring the polyacetylene. The thus-treated polymer was dried. EXAMPLE 16 A copolymer powder was produced in the same manner as described in Example 15 except that prior to the introduction of the acetylene gas, 2 mQ (about 9.8 mmol) of phenylacetylene Was introduced. Infrared spectral analysis showed that the acetylene copolymer powder contained 10 mol% of phenylacetylene units. This powder was extracted under reflux in the same manner as described in Example 15 and then dried. EXAMPLE 17 Polyacetylene was produced in the same manner as described in Example 15. This polyacetylene was extracted and dried in the same manner as described in Example 15 except that the type of organic solvent was changed to acetic acid and the extraction procedure was performed under atmospheric pressure. COMPARATIVE EXAMPLE 11 The procedures of Example 15 were repeated but the extraction using lactic acid was not performed, but rather a procedure of adding 100 mQ of toluene, stirring the mixture for 24 hours, and then filtering the mixture was repeated five times. COMPARATIVE EXAMPLE 12 The procedures of Example 15 were repeated but toluene was used in place of the lactic acid. COMPARATIVE ExAMPLE 13 The procedures of Example 15 were repeated but the polyacetylene was not stirred. TABLE 1 Run No. Amount of Residual Catalyst (wt ppm) Example 1 Al 350 Ti 400 2 Al 180 Ti 120 " 3 Al 100 Ti 110 4 4 Na 290 Co 300 5 Al 160 Ti 190 6 6 Al 70 Ti 70 TABLE 2 Run No. Amount of Residual Catalyst (wt ppm) Comparative Al 900 Ti 1,000 Example 1 " 2 Al 3,000 Ti 4,500 " 3 Al 1,500 Ti 2,000 " 4 Al 1,800 Ti 2,000 5 5 Al 2,000 Ti 2,300 6 6 Al 2,800 Ti 2,900 " 7 Al 300 Ti 400 " 8 Al 380 Ti 410 TABLE 3 Run No. Amount of Residual Catalyst (wt ppm) Example 7 Al 43 Ti 50 n 8 Al 70 Ti 95 9 9 AQ 39 Ti 83 " 10 AZ 49 Ti 77 " 11 Al 75 Ti 89 " 12 Na 63 Co 69 " 13 AZ 21 Ti 43 " 14 At 38 Ti 71 Comparative AZ 1,200 Ti 4,200 Example 9 " 10 Al 150 Ti 160 TABLE 4 Run No. Extraction Solvent Amount of Residual Catalyst (wt ppm Example 15 Lactic Acid A± 35 Ti 23 16 " Al 30 Ti 14 17 Acetic Acid AL 65 Ti 70 Comparative Toluene Example 11 (room temperature) Al 1m300 11 2,100 12 Toluene AL 1,020 Ti 1,300 " 13 Lactic Acid (without stirring) AL 680 Ti 630 REFERENCE EXAMPLE 1 Purified polyacetylene as produced in Example 1 was press molded under a presume of 1 ton/cm2 to form a sheet. Two pieces of a width of 0.5 cm and a length of 2.0 cm were cut from the sheet, fitted mechanically to platinum wires, and used as a negative electrode and an positive electrode. A sulfolane solution (concentration of LiBF4: 1.0 mol/Q) was used as an electrolyte. Charging was performed for 2 hours with a given amount of current 2 (1.0 mA/cm ) (the amount of electricity was equivalent to a doping level of 7 mol%). Immediately after the completion of charging, discharging was performed with a given amount of current (1.0 mA/cm2). When the voltage reached 0.5 V, charging was performed under the same conditions as above. This procedure of chargingdischarging could be repeated 488 times. The theoretical energy density per kilogram of the active substance used as determined after the first charging-discharging procedure was 136 Whr/kg, and the charging-discharging efficiency was 97%. The ratio of the amount of electricity discharged until the voltage dropped to 1.5 V in relation to the total amount of electricity discharged was 93%. REFERENCE EXAMPLES 2 TO 6 The procedures of Reference Example 1 were repeated wherein the acetylene polymers shown in Table 3 were used in place of the polyacetylene used in Reference Example 1. The results obtained are shown in Table 5 below. TABLE 5 Acetylene Number of Theoretical Polymer Procedures Energy Run. No Used Repeated Density (W.hr/kg) Reference Polymer of 367 132 Example 2 Example 2 3 3 Polymer of 405 128 Example 3 4 4 Polymer of 371 129 Example 4 5 Polymer of 316 133 Example 5 6 6 Polymer of 389 130 Example 6 REFERENCE PLE 7 The procedures of Reference Example 1 were repeated wherein the film-shaped acetylene polymer as produced in Comparative Example 1 was used in place of the polyacetylene used in Reference Example 1, and the same charging-discharging repeating test was carried out. After the test had been repeated only 15 times, the charging became impossible. After the test, the composite material was removed and examined. This examination showed that the mold was broken. Elemental analysis and infrared spectral analysis of part of the composite material demonstrated that the material was oxidized and degraded. The theoretical energy density per kilogram of the active substance used determined after the first charging-discharging test was 114 W.hr/kg, and the charging-discharging efficiency was 81%. The ratio of the amount of electricity discharged until the voltage dropped to 1.5 V with respect to the total amount of electricity discharged was 83%. REFERENCE EXAMPLES 3 TO 14 The procedures of Reference Example 7 were repeated wherein the acetylene polymers shown in Table 6 below were used in place of the acetylene polymer used in Reference Example 7. The results obtained are shown in Table 6 below. TABLE 6 Acetylene Number of Theoretical Polymer Procedures Energy Run No Used Repeated Density (W.hr/kg) Reference Polymer of Example 8 Comparative 128 115 Example 2 Polymer of " 9 Comparative 146 120 Example 3 Polymer of 10 Comparative 166 121 Example 4 Polymer of 11 Comparative 170 119 Example 5 Polymer of 12 Comparative 216 122 Example 6 Polymer of 13 Comparative 187 106 Example 7 Polymer of 14 " 14 Comparative 174 104 Example 8 In reference Examples 7 to 12, the amount of the residual catalyst was large, and in Reference Examples 13 and 14, the inorganic acids were doped although the amount of the residual catalyst was small. Thus, the number of procedures repeated and the theoretical energy density were low in all of Reference Examples 7 to 14. REFERENCE EXAMPLE 15 Battery Test The purified polyacetylene as produced in Example 15 was press molded under a pressure of 1 ton/cm2 to form a sheet. Two pieces of a width of 0.5 cm and a length of 2.0 cm were cut out of the sheet, fitted mechanically to platinum wires, and used as a cathode and an anode. A sulfolane solution (concentration of LiBF4: 1.0 mol/Q) was used as an electrolyte. Charging was performed for 2 hours with a given amount of current (1.0 mA/cm2) (the amount of electricity was equivalent to a doping level of 6 mol%). Immediately after the completion of charging, discharging a s performed with a given amount of current (1.0 mA/cm2). When the voltage reached 0.5 V, charging was performed under the same conditions as above. This procedure of chargingdischarging could be repeated 560 times. The theoretical energy density per kilogram of the active substance as determined after the first charging-discharging procedure was 118 W.hr/kg, and the. charging-discharging efficiency was 97%. The ratio of the amount of electricity discharged until the voltage dropped to 1.5 V to the total amount of electricity discharged was 95%. REFERENCE EXAMPLES 16 AND 17 The battery test was performed in the same manner as in Reference Example 15 except that the acetylene polymers shown in Table 4 were used in place of the polyacetylene used in Reference Example 15. The results are shown in Table 7 below. TABLE 7 Acetylene Number of Theoretical Polymer Procedures Energy Run No. Used Repeated Density (W.hr/kg) Reference Polymer of 508 117 Example 16 Example 16 17 Polymer of 410 114 Example 17 REFERENCE EXAMPLE 18 The battery test was performed in the same manner as in Reference Example 15 except that the polyacetylene produced in Comparative Example 12 was used in place of that used in Reference Example 15. When the charging-discharging procedure was repeated 190 times, charging became impossible. After the test, the composite material was removed and examined. This examination showed that the mold was broken. Elemental analysis and infrared spectral analysis of part of the mold demonstrated that the material was oxidized and degraded. The theoretical energy density per kilogram of the active substance used as determined after the first charging-discharging test was 114 W.hr/kg, and the charging-discharging efficiency was 90%. The ratio of the amount of electricity discharged until the voltage dropped to 1.5 V to the total amount of electricity discharged was 86%. Production of secondary batteries in which the purified acetylene polymer is particularly useful is described in greater detail below with reference to the following Production Examples and Comparative Production Examples. PRODUCTION EXAMPLE 1 Preparation of Electrode A l-liter glass autoclave equipped with an impeller blade type mechanical stirrer was charged with 200 mg of toluene, 2 mg (5.9 mmol) of tetrabutoxy titanium, and 2 mg (14.6 mmol) of triethyl aluminum in an atmosphere of nitrogen, and acetylene was introduced therein and polymerized at a polymerization temperature of -200C under an acetylene partial pressure of 0.9 kg/cm2 for 2 hours while stirring the mixture. Simultaneously with the introduction of the acetylene gas, a red-purple polyacetylene in the form of short fibers of lengths of about 1 mm started to form. After the completion of the polymerization, the short fiber-formed polyacetylene containing toluene was placed on a glass filter and purified with an organic acid by fully washing the polyacetylene with about 1 liter of a 1:1 (by volume) mixture of acetic acid and methanol to remove the catalyst. Subsequently, the polyacetylene - was washed with about 1 liter of toluene. The amount of the residual catalyst in the polyacetylene before or after the purification as follows: AZ Atom Ti Atom (ppm) (ppm) Before Purification 3,500 1,400 After Purification 78 50 The short fiber-formed polyacetylene after the removal of the catalyst contained 52% by weight of toluene. Then, 20.8 g of the polyacetylene and 0.45 g of carbon black powder (electrical conductance: 21 n lcm 1) were mixed in a ball mill. The resulting mixture was placed on a metal net, pressed at room temperature under a pressure of 300 kg/cmê, and then deaerated in vacuum, whereby a 150 pm thick composite material of the polyacetylene , metal net, and carbon black was obtained. This composite material had a structure that the metal net was sandwiched between the polyacetylene -carbon black mixture layers, and its surface had a metallic lustre. The amount of the metal net in the composite material was 50 parts by weight per 100 parts by weight of the polyacetylene The yield of the polyacetylene - was 13 g; the cis content was 76%; and the electrical conductance at room temperature (as determined by a D.C. two-terminal method) was 5.1X10 6Q l cm 1. Scanning electron microscope analysis showed that the polyacetylene was composed of fibrils having a diameter of from 200 to 400 A. Battery Test Two pieces of predetermined dimensions were cut from the composite material as prepared above and used as electrodes, cathode and anode, to fabricate a battery. The Figure is a schematic cross-sectional view of a battery cell for the measurement of the characteristics of a button type battery, an example of a secondary battery. This battery cell comprised an Ni-plated brass container 1, a circular negative electrode 2 (diameter: 20mm), a circular porous polypropylene membrane 3 (diameter: 26 mm), a circular carbon fiber felt 4 (diameter: 26 mm), a positive elecrode 5, a Teflon (Teflopore FP-200, produced by Sumitomo Electric Co., Ltd.) sheet 6 with holes (average daimeter: 2 pm) bored therein, a Teflon container 7 having a circular cross section, a Teflon ring 8 for the fixation of the positive electrode 5, and an Ni lead wire 9. Tlle positive electrode S was placed in a concave portion of the lower portion of the container 1, and the circular porous Teflon sheet 6 was superposed on tne positive elecrode 5. They were then fixed therein by clamping with the Teflon ring 8. The felt 4 was placed in a concave portion of the upper portion of the container 1, superposed on the positive electrode 5, and impregnated with an electrolyte. Tile negative electrode 2 was placed thereon through the membrane 3. They were then clamped with the container 7 to fabricate a battery. The electrolyte was a 1.5 mol/Z solution of Bu4NBF4 in distilled and dried acetonitrile. Charging was performed at a constant current (3.0 mA/cm2) for a predetermined period of time (the amount of electricity was equivalent to 5 mol% of the doping level ). After the completion of charging, discharge was immediately performed at a constant current 2 (5.0 mA/cm ) until the voltage dropped to 1.0 V. This charge-discharge cycle was repeated. It was found that the charging could be performed until the number of cycles reached 623. After the tenth charging, the battery was allowed to stand for 48 hours. At the end of the time, the self discharge rate was measured and found to be 7%. COMPARATIVE PRODUCTION EXAMPLE 1 The procedures used in the Preparation of Electrode section of Production Example 1 were repeated wherein toluene was used in place of the acetic acid/ methanol (1:1 by volume) mixture. The amount of the residual catalyst after the purification with toluene was as follows: At Atom Ti Atom (ppm) (ppm) 1,250 730 The thus-fabricated battery was subjected to the same battery test as in Production Example 1. The charge-discharge procedure could be repeated until the number of cycles reached 383, and the self discharge rate was 19%. PRODUCTION EXAMPLES 2 TO 6 AND COMPARATIVE PRODUCTION EXAMPLES 2 TO 5 The procedures as described in the Preparation of Electrode section of Production Example 1 were repeated wherein the solvents shown in Table 8 below were each used in place of the acetic acid/methanol (1:1 by volume) mixture. The thus-fabricated batteries were each subjected to the same battery test as in Production Example 1. The results obtained are shown in Table 8 below. TABLE 8 Number of Residual Charge- Self Catalyst Discharge Discharge Run No. Solvent AZ Ti Cycles Rate (volume ratio) (Z) Prod. Ex. 2 Acetic Acid 110 60 617 8 " 3 Glycolic Acid/ 60 60 583 9 Methanol (1:1) Lactic Acid/ 150 120 529 10 Methanol (1:1) Acetic Acid/ 90 80 532 11 Toluene (1:1) 6 Benzoic Acidl 150 140 489 10 Methanol (1:1) Comp. Prod. Hydrochloric 450 390 219 18 Example 2 Acid (HCQ) 3 3 Methanol 460 410 208 20 (1:1) " 4 Nitric Acid 770 590 227 19 " 5 Sulfuric Acid 840 460 244 21 COMPARATIVE PRODUCTION EXAMPLE 6 Preparation of Electrode Titanium tetrabutoxide (1.7 mZ) was placed in a 500-mQ glass reactor in a nitrogen atmosphere and dissolved in 30 ml of toluene, and 2.7 ml of triethyl aluminum was added thereto while stirring the mixture to prepare a catalyst solution. The reactor was cooled with liquid nitrogen, and the nitrogen gas in the system was evacuated by means of a vacuum pump. Then, the reactor was cooled to -780C, and the catalyst solution was shaken for attachment on the walls of the reactor. Subsequently, purified acetylene gas was passed therethrough at a pressure of 1 atmosphere. Immediately polymerization of acetylene occurred on the wall surface to which the catalyst solution had adhered, resulting in the formation of a film-form polyacetylene . Forty nine minutes after the introduction of acetylene, the acetylene gas was evacuated to stop the polymerization. The catalyst solution was removed under a nitrogen atmosphere by means of a syringe. The polyacetylene was washed five times with 100 mZ of purified toluene while maintaining it at -780C. The amount of the residual catalyst before or after the washing process was as follows: AZ Atom Ti Atom (ppm) (ppm) Before Washing 5,200 3,800 After Washing 1,700 1,200 The thus-produced polyacetylene was a uniform film-form product in which fibrils were densely intertwined. This film-form product was vacuum dried to obtain a red-purple film-form polyacetylene having a metallic lustre, in which the thickness was 85 pm and the cis-content was 98%. Battery Test Two pieces of predetermined dimensions were cut from the above-prepared film-form polyacetylene and used as electrodes, cathode and anode. Using these electrodes, a battery was fabricated in the same manner as in Production Example 1. The charge-discharge test was performed in the same manner as in Production Example 1. This chargedischarge cycle could be repeated until the number of cycles reached 394. The self-discharge rate was 17%. COMPARATIVE PRODUCTION EXAMPLES 7 TO 11 The procedures as in the Preparation of Electrode section and in the Battery Test section of Comparative Production Example 6 were repeated wherein in washing the film form polyacetylene after the completion of the polymerization, the solvents as shown in Table 9 were each used in place of toluene. The results are shown in Table 9 below. TABLE 9 Number of Residual Charge- Self Catalyst Discharge Discharge Run No. Solvent Al Ti Cycles Rate (volume ratio) (ppm) (ppm) (%) Comp.Prod. Hydrochloric 1,170 680 241 23 Example 7 Acid (HCl) 8 HCl/Methanol 970 550 235 21 9 9 Nitric Acid 1,340 720 127 25 " 10 Sulfuric Acid 1,510 790 153 20 ,, 11 Acetic Acid I 25 Methanol (1:1) 1,420 870 254 While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims: WHAT IS CLAIMED IS: 1. A process for the purification of an acetylene polymer, comprising removing a polymerization catalyst from the polymer by contacting the acetylene polymer with an organic acid. 2. The process of Claim 1, wherein the contacting of acetylene polymer with the organic acid is by pulverizing the acetylene polymer with the organic acid. 3. The process of Claim 1, wherein the contacting of the organic acid and the acetylene polymer comprises washing the acetylene polymer with the organic acid under reflux while stirring the acetylene polymer. 4. The process of Claim 1 or 2, wherein, after contacting the polymer with the organic acid, the process includes treating the acetylene polymer with a solvent. 5. The process of Claim 1, 2 or 3, wherein the organic acid is (a) a mono- or multivalent organic carboxylic acid, (b) an acid anhydride of said organic carboxylic acid, (c) a hydroxycarboxylic acid or (d) a mixture thereof. 6. The process of Claim 1, 2 or 3, wherein the acetylene polymer contains repeating units of the formula EMI63.1 wherein R is a hydrogen atom, a halogen atom, an alkyl group containing 6 or less carbon atoms or an aryl group containing from 6 to 10 carbon atoms. 7. The process of Claim 5, wherein the organic acid is a mono- or multivalent carboxylic acid anhydride, a mono- or multivalent unsaturated acid, a mono- or multivalent aromatic acid, a mono- or multivalent saturated fatty acid, an aromatic sulfonic acid or oxalic acid or co-derivative thereof. 8. The process of Claim 4, wherein the solvent is an aromatic solvent, a halogenated compound solvent, an alcohol, a ketone, an aliphatic solvent, an alicyclic solvent, a sulfolane, a nitro compound, an ether compound, a cyano compound, an aromatic ether, an ester, a Cellosolve or an ethylene or propylene carbonate. 9. The process of Claim 1, wherein the contacting is for 10 hours or less. 10. The process of Claim 6, wherein the acetylene polymer is polyacetylene.

Inventors: KAWAKAMI, SOICHIRO, KIRA, MASAAKI, KOBAYASHI, YUKIO, NAITO, KAZUMI
Applicants: SHOWA DENKO K.K.
Application year: 1984
Main classification: C08F6
IPC codes: C08F6