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WO2006004161A1 - Nouveaux dérivés du polyphénylacétylène - Google Patents

Nouveaux dérivés du polyphénylacétylène Download PDF

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Publication number
WO2006004161A1
WO2006004161A1 PCT/JP2005/012508 JP2005012508W WO2006004161A1 WO 2006004161 A1 WO2006004161 A1 WO 2006004161A1 JP 2005012508 W JP2005012508 W JP 2005012508W WO 2006004161 A1 WO2006004161 A1 WO 2006004161A1
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Prior art keywords
derivative
group
chemical
polyphenylacetylene
polyacetylene
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English (en)
Japanese (ja)
Inventor
Toshio Masuda
Masashi Shiotsuki
Toshiki Kono
Yuichi Shida
Saeed Irfan
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Kyoto University NUC
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Kyoto University NUC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
    • C08F38/02—Acetylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/125—Intrinsically conductive polymers comprising aliphatic main chains, e.g. polyactylenes

Definitions

  • the present invention relates to a novel polyacetylene derivative, and more particularly to a polyacetylene derivative having a hydroxyl group, an amino group, two esters, two carboxylic acids or imides on a phenyl group. .
  • Substituted acetylene can be polymerized with a suitable transition metal catalyst to give a high molecular weight polymer.
  • the resulting polymer has a conjugated double bond in the main chain, and various properties such as deep coloration, photoconductivity, nonlinear optical properties, and material permeability based on conjugation of the main chain are normal bull polymers. Can not be expected.
  • substituted polyacetylene is a conjugated polymer having alternating double bonds in the main chain
  • the properties based on the conjugation of the main chain greatly depend not only on the substituents on the side chain but also on the degree of conjugation of the main chain.
  • the polymer having the widest conjugation is polyacetylene having no substituent, and exhibits high conductivity equivalent to that of metal by appropriate doping.
  • polyacetylene is insoluble and infusible, has poor moldability and is unstable in air, making it very difficult to apply as a functional material.
  • substituted polyacetylene having an appropriate substituent exhibits high solubility and stability, and provides a strong self-supporting film. Therefore, the potential application as a functional material is very large.
  • membrane separation is a resource-saving and energy-saving eco-friendly eco-technology and is expected to be used in many fields.
  • Membrane separation mainly used for water purification such as MF, UF, and RO, has advanced considerably in technology, and seawater desalination is actually widely used.
  • gas separation and pervaporation separation are currently put to practical use only in limited fields. Therefore, it is necessary to develop a high-performance separation membrane that satisfies these conditions.
  • Substituted polyacetylene is characterized by having high material permeability, and the above-mentioned high performance It may be used for separation membranes.
  • polyacetylene having a polar group examples include polyacetylene monoester having an ester at the para position of phenylacetylene (see Non-Patent Documents 1 to 4), and polyphenyl having an amide at the para position of phenylacetylene.
  • -Ruacetylene monoamide see Non-Patent Documents 5 and 6) has been reported.
  • Non-Patent Document 1 Y. Kishimoto, M. Ito, T. Miyatake, T. Ikariya, and R. Noyori, Macromolecules, 28, 6662 (1995)
  • Non-Patent Document 2 B. Z. Tang, X. Kong, X. Wan, and X. D. Feng, Macromolecules, 3
  • Non-Patent Document 3 X. Kong, J. W. Y. Lam, and B. Z. Tang, Macromolecules, 32, 172 2 (1999)
  • Non-Patent Document 6 E. Yashima, S. Hung, T. Matsushima, and Y. Okamoto, Macromole cules, 28, 4184 (1995)
  • Non-Patent Document 7 Tabata, M., Lindgren, M., Lee, H., Yokota, K., Yang, W. Polymer, 32 (8), 1531-1534, 1991.
  • Non-Patent Document 8 Yashima, E., Maeda, Y., Matsushima, T., Okamoto, Y. Chirality, 9, 593-600, 1997.
  • polyacetylene derivatives having monoesters or monoamides on the phenyl group have already been reported.
  • Polyethylene derivatives having diesters, dicarboxylic acids or imides on the phenyl group have been reported in the past. Reported to,,,.
  • polyacetylene derivatives having a hydroxyl group have been reported in the past.
  • the present invention has been made in view of the above-mentioned problems, and the object thereof is a hydroxyl group, an amino group, two esters, and two carbos on a phenol group that has not been reported or confirmed so far.
  • the object is to provide a polyphenylacetylene derivative having an acid or an imide.
  • the present inventors synthesized a phenylacetylene compound having a diester, dicarboxylic acid or imide on a phenol group, and superposed these monomers. Polyphenylacetylene derivatives having diesters, dicarboxylic acids or imides were successfully synthesized. Furthermore, the present inventors polymerized a phenylacetylene monomer having a structure in which a hydroxyl group or an amino group is protected by a substituent, and deprotected the resulting polymer to obtain a polyphenol having a hydroxyl group or an amino group. Ruacetylene induction The body was successfully synthesized and the present invention was completed.
  • polyacetylacetylene derivative according to the present invention is characterized by having a structure represented by the following general formula (I), ( ⁇ ) or ( ⁇ )! /
  • R 1 is hydrogen or an alkyl group
  • R 2 is an alkyl group
  • R 3 is a hydroxyl group or an amino group
  • n is an integer of 10 or more.
  • R 1 in the above formula (I) is preferably a linear alkyl group having 10 or less carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group or an n-hexyl group.
  • R 2 is preferably a linear alkyl group having 15 or less carbon atoms, more preferably an n-dodecyl group.
  • R 3 is preferably in the para position or the meta position.
  • polyacetylene derivative according to the present invention is characterized by having a structure represented by the following general formula (IV).
  • n is an integer of 10 or more.
  • R 4 is preferably in the para position or the meta position.
  • the polyphenylacetylene derivative according to the present invention preferably has a weight average molecular weight of 10,000 or more.
  • the conductive resin composition according to the present invention contains the polyacetylene derivative according to the present invention, and further includes a compound serving as an electron donor or acceptor as a dopant. It is characterized by that.
  • the phenylacetylene compound according to the present invention is such that one hydrogen atom of acetylene is benzene.
  • Each of the above-mentioned phenylacetylene compounds is a novel substance that has not been reported so far, and the above-mentioned polyacetylene derivative according to the present invention can be obtained by polymerizing these compounds as raw materials.
  • the method for producing a polyphenylacetylene derivative according to the present invention comprises deprotecting a polyphenylacetylene derivative having a structure in which a hydroxyl group or an amino group bonded to a phenyl group is protected with a substituent, and the following general formula: (III)
  • the method for producing a polyacetylene derivative according to the present invention includes the following general formula (IV):
  • n is an integer of 10 or more.
  • R 3 is a hydroxyl group or an amino group, and n is an integer of 10 or more.
  • It may include a step of producing a polyacetylene derivative represented by
  • the method for producing a polyacetylene derivative according to the present invention preferably includes a step of producing a polyacetylacetylene derivative having a structure represented by the above general formula (IV).
  • the method includes a step of forming a film of a polyacetylacetylene derivative having a structure represented by (IV).
  • a rhodium catalyst may be used when producing a polyacetylacetylene derivative having a structure represented by the general formula (II).
  • [Rh (nbd) Cl] as the main catalyst
  • K as the cocatalyst
  • N (SiMe) is preferably used.
  • the polyphenylacetylene derivative according to the present invention has a structure represented by the above formula (I), and R 1 may be hydrogen or an alkyl group.
  • R 1 alkyl group is especially Although not limited, a linear alkyl group having 10 or less carbon atoms is preferable. More preferably, it is a linear alkyl group having 1 to 6 carbon atoms.
  • a linear alkyl group having 10 or less carbon atoms imparts sufficient solubility to the polymer, and its raw materials are readily available. Examples of the linear alkyl group having 10 or less carbon atoms include a methyl group, an ethyl group, an n-butyl group, and an n-hexyl group.
  • the polyacetylene derivative according to the present invention has a structure represented by the above formula (R), and R 2 may be an alkyl group.
  • the alkyl group for R 2 is not particularly limited, but a linear alkyl group having 15 or less carbon atoms is preferable. More preferably, it is a linear alkyl group having 1 to 12 carbon atoms. A linear alkyl group having 15 or less carbon atoms imparts sufficient solubility to the polymer, and its raw materials are readily available. Examples of the linear alkyl group having 15 or less carbon atoms include n-dodecyl group.
  • the polyphenylacetylene derivative according to the present invention may have a polymerization degree n of 10 or more.
  • it is selected within the range of 100 to 10 7 .
  • the molecular weight of the polyacetylene derivative according to the present invention is not particularly limited, but the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. It is particularly preferred to be over 100,000. V, most preferably over 500,000. If the weight average molecular weight is less than 10,000, sufficient mechanical strength can be secured!
  • the polyacetylacetylene derivative having the structure represented by the above formula (I) or (II) can be produced, for example, as follows. That is, it can be produced by polymerizing a phenylacetylene compound (raw material monomer) which is a repeating unit in a dry inert gas atmosphere in an appropriate solvent in the presence of a catalyst.
  • the concentration of the raw material monomer in the solution is 0.1 M to 2 M, preferably 0.5 M to 1 M.
  • the reaction temperature is 0 ° C ⁇ 80. C, preferably in the range of 30 ° C to 60 ° C, and in the range of 60 minutes to 48 hours reaction time.
  • Examples of the inert gas include nitrogen and argon.
  • the solvent various solvents can be used depending on the type of the monomer and the catalyst.
  • hydrocarbon aliphatic hydrocarbon, aromatic hydrocarbon, etc.
  • halogenated hydrocarbon Alcohols, nitrogen compounds, ethers, ketones, fatty acids, esters and the like can be mentioned.
  • THF tetrahydrofuran
  • toluene toluene
  • chloroform etc.
  • the solvent may be a mixed solvent in which two or more types are mixed.
  • a transition metal catalyst is preferred.
  • the phenylacetylene compound as the raw material monomer may have any structure represented by the following general formula (VII) or (VIII). Further, the compound is not limited to a novel compound, and may be a known compound.
  • R 1 is hydrogen or an alkyl group, and R 2 is an alkyl group.
  • the polyacetylacetylene derivative having the structure represented by the above formula (I) or formula (II) can be suitably used for a gas separation membrane or a liquid separation membrane.
  • a gas separation membrane is an oxygen-enriched membrane.
  • liquid separation membranes include ethanol separation membranes synthesized using biomass.
  • diester diester Since it has a carboxylic acid or an imide, it can be expected to be used in a wider range than conventional substituted polyacetylene, which has a very high polarity.
  • the polyacetylene derivative according to the present invention is a conductive resin compound containing the polyphenylacetylene derivative and further containing a compound serving as an electron donor or acceptor as a dopant.
  • a conductive resin compound containing the polyphenylacetylene derivative and further containing a compound serving as an electron donor or acceptor as a dopant.
  • the conductive resin compound is not limited as long as it contains at least the primer phenylacetylene derivative according to the present invention and the above-mentioned dopant, for example, other polymers such as V are included. Okay, that's ugly.
  • Examples of the dopant include proton acids such as HC1, HBr, HI, perchloric acid and sulfuric acid, halogens such as chlorine, bromine and iodine, antimony pentafluoride, phosphorus pentafluoride, arsenic pentafluoride, Examples thereof include Lewis acids such as boron fluoride and ferric chloride, and electron acceptors such as tetracyanethylene.
  • the phenylacetylene compound according to the present invention has a structure represented by the above formulas (V) and (VI). It is what you have. These phenylacetylene compounds shown in (V) and (VI) are novel compounds that have not been reported so far.
  • (V) is di-n-butyl 4-ethynylphthalate, which is polymerized to produce poly (4-n-butyl phthalate) (in formula (I) above, R 1 is a polyacetylene derivative which is an n-butyl group). Further, (VI) is N-dodecyl-4-ethynyl-phthalimide, and by polymerizing this, poly (N-dodecyl-4-ethur-phthalimide) according to the present invention (in the above formula ( ⁇ ), R 2 Is a n-dodecyl group).
  • the di-n-butyl 4-ethyl phthalate of (V) above can be produced, for example, by mixing commercially available 4-ethyl phthalic anhydride and n-butanol, adding sulfuric acid and stirring with heating. .
  • N-dodecyl-4-ethyl-phthalimide of (VI) above is prepared by, for example, dissolving commercially available 4-ethyl phthalic anhydride and n-dodecylamine in toluene, and using a Dean-Stark trap. It can be produced by heating to reflux.
  • the polyphenylacetylene derivative according to the present invention has a structure represented by the above formula (III), and R 3 may be a hydroxyl group or an amino group. R 3 is preferably in the para or meta position.
  • the following formula (IX) is a polyacetylacetylene derivative having a hydroxyl group at the para position
  • the following formula (X) is a polyphenylacetylene derivative having a hydroxyl group at the meta position
  • the following formula (XI) is a para position
  • the following formula (XII) is a polyphenylene acetylene derivative having an amino group at the meta position.
  • the polyacetylene derivative according to the present invention has a structure represented by the above formula (IV), and R 4 is
  • OSiMe t-Bu (Hereafter referred to as “OSiMe t-Bu”.)
  • R 4 is preferably in the para or meta position.
  • the following formula ( ⁇ ) is a polyacetylene derivative having OSiMe t-Bu in the para position
  • the following formula (XIV) is a polyacetylene derivative having OSiMe-t-Bu in the force meta position.
  • the polyphenylacetylene derivative according to the present invention may have a polymerization degree n of 10 or more. Preferably, it is selected within the range of 100 to 10 7 .
  • the molecular weight of the polyacetylene derivative according to the present invention is not particularly limited, but the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. It is particularly preferred to be over 100,000. V, most preferably over 500,000. If the weight average molecular weight is less than 10,000, sufficient mechanical strength can be secured!
  • Polyphenylacetylene derivatives having the structure represented by the above formula (III) can be suitably used for high-performance separation membranes such as gas separation membranes and liquid separation membranes.
  • An example of the gas separation membrane is an oxygen-enriched membrane.
  • the oxygen-enriched film can be applied to, for example, an air conditioner having an oxygen-enriching function.
  • Examples of liquid separation membranes include ethanol separation membranes synthesized using biomass.
  • the method for producing polyphenylacetylene according to the present invention comprises a polyphenyl having a structure in which a hydroxyl group or amino group bonded to a phenyl group is protected by a substituent. Any method may be used as long as it includes a step of producing the polyacetylacetylene derivative represented by the above general formula (III) by deprotecting the acetylene derivative.
  • the substituent for protecting the hydroxyl group or amino group (hereinafter, also referred to as "protecting group”) is not particularly limited. However, the substituent is bulky and sufficiently protects the polar group. Don't react! Substituents with / ⁇ and ⁇ ⁇ characteristics are preferred ⁇ . Specific examples include t-butyldimethylsilyl group, t-butoxycarbonyl group, and trityl group.
  • the polyacetylene derivative having a structure in which the hydroxyl group or amino group bonded to the phenyl group is protected with a substituent is not particularly limited, and the polyacetylene derivative derivative having the protecting group shown in the above example is not particularly limited. If so! More specifically, a polyacetylene derivative having a structure represented by the above formulas (XIII) to (XVI) can be mentioned.
  • the method for deprotecting the substituent protecting the hydroxyl group or amino group is not particularly limited, and a known method may be appropriately selected and used.
  • a t-butyldimethylsilyl group for example, the above formulas (XIII) and (XIV)
  • a t-butoxycarbonyl group for example, the above formulas (XV) and (XVI)
  • a polyacetylene derivative having a structure represented by the above general formula (IV) for example, the above formula (XIII) to It is preferable to include a step of producing a polyacetylene derivative having a structure represented by (XVI).
  • the polyacetylene derivative having the structure represented by the general formula (IV) is obtained by polymerizing a phenylacetylene compound (monomer) having the structure represented by the following general formula (XVII). It can be manufactured from Tsujiko.
  • the production method of the monomer represented by the general formula (XVII) is not particularly limited, and a known method may be appropriately selected and produced. For example, it can be produced by the method described in Examples described later.
  • the method for polymerizing the monomer is not particularly limited, and may be produced by appropriately selecting a known polymerization method. For example, it can be produced as follows.
  • the monomer can be produced by polymerizing the monomer in a suitable solvent in the presence of a catalyst in a dry inert gas atmosphere.
  • concentration of the monomer in the solution is adjusted to be in the range of 0.1 ⁇ 2 ⁇ , preferably 0.5M ⁇ l ⁇ .
  • the reaction temperature is selected in the range of 0 ° C to 80 ° C, preferably 30 ° C to 60 ° C, and the reaction time is selected in the range of 60 minutes to 48 hours.
  • Examples of the inert gas include nitrogen and argon.
  • solvents can be used as the solvent depending on the kind of the monomer and the catalyst.
  • hydrocarbons aliphatic hydrocarbons, aromatic hydrocarbons, etc.
  • halogenated hydrocarbons alcohols, nitrogen compounds, ethers. , Ketones, fatty acids, esters and the like.
  • THF tetrahydrofuran
  • toluene toluene
  • chloroform etc.
  • the solvent may be a mixed solvent in which two or more types are mixed.
  • a rhodium catalyst is particularly preferable among transition metal catalysts.
  • rhodium catalysts examples include [Rh (nbd) Cl], Rh + (nbd) [h 6 -CHB "(CH)] and the like.
  • the present invention is not limited to this.
  • a polyacetylene derivative having a structure represented by the above general formula (IV) (for example, the above formula
  • the method includes a step of forming a film of a polyacetylene derivative having a structure represented by (XIII) to (XVI).
  • the method of film formation is not particularly limited, and a known method may be appropriately selected and used.
  • a casting method using a polymer solution can be suitably used.
  • the mixture was heated and stirred at ° C for 20 hours (see the following scheme (4)). After completion of the reaction, the solvent was distilled off under reduced pressure and extracted with ethyl acetate. The mixture was washed with an aqueous sodium hydrogen carbonate solution and water, and anhydrous sodium sulfate was added to the solvent of the organic layer and left for half a day for dehydration. Anhydrous sodium sulfate was removed by filtration, and the solvent of the organic layer was distilled off under reduced pressure to obtain a crude product as a yellow liquid.
  • Table 1 shows the yield, weight average molecular weight (Mw), and weight average content of each polymer (poly (l) to poly (5)) obtained by polymerization of each monomer (phenylacetylene compound, compounds 1 to 5). The ratio of molecular weight to number average molecular weight (MwZMn) is shown. The molecular weight of the polymer was measured by GPC (PSt conversion).
  • poly (l) As a typical example of the polymerization reaction, a polymerization method of poly (4-ethyl phthalate) (poly (l)) will be described.
  • Poly (4-ethyl phthalate di n-butyl) (poly (3)) was identified by 1 H-NMR and 13 C-NMR. The results are shown below.
  • Poly (4-n-hexylphthalate) (poly (4)) was identified by 1 H-NMR and 13 C-NMR. The results are shown below.
  • Poly (N-dodecyl-4-ethyl-phthalimide) (poly (5)) was identified by 1 H-NMR and 13 C-N MR. The results are shown below.
  • Monoma ⁇ is a paper by Yashima et al. (Yashima, E.; Huang, S.; Matsusita, T.; Okamoto, Y Macromolecules 1995, 28, 4184.) In the above paper, only the method for synthesizing para-monomers is described.
  • [Cocat] / [Cat] 10. That is, a polymerization method in which a toluene solution of a monomer is mixed with a toluene solution of a catalyst and a cocatalyst. [0100] When Rh + (nbd) [h 6 -CHB "(CH)] is used as the main catalyst, the cocatalyst is not used.
  • the polymerization solvent used was purified by distillation.
  • the polymer was dropped into a large amount of methanol, and the methanol-insoluble part was recovered with a glass filter.
  • Table 3 shows the results of the meta form. Similar to the result of the para-body, the molecular weight was greatly increased in the combination of the main catalyst [Rh (nbd) C1] of run5 and the cocatalyst KN (SiMe).
  • a free-standing membrane was prepared by casting a toluene solution of the polymer on a petri dish.
  • the obtained meta polymer film (a polymer synthesized under the conditions of run 2 in Table 3) was a transparent and uniform film.
  • the desilylation reaction was performed by immersing the polymer film in a mixed solution of trifluoroacetic acid and water or an organic solvent for 24 hours.
  • Monomers were synthesized by refluxing 3-ethulurin (meta) or 4-etulurin (para) and tert-butyl pyrocarbonate in tetrahydrofuran (THF).
  • IR (KBr, cm '' 1 ): 3340, 3310, 2952, 1698, 1605, 1530, 1479, 1454, 1367, 1242, 1154, 888, 870, 787, 685, 658.
  • IR (KBr, cm '' 1 ): 3390, 3295, 2957, 1705, 1609, 1584, 1559, 1512, 1408, 1316, 1231, 1156, 1056, 902, 837, 774, 761.
  • the rhodium catalyst was used alone without using a cocatalyst.
  • Table 5 shows the results of the meta form.
  • Table 6 shows the results of the para body. A high molecular weight polymer was obtained in a high yield (80% to 95%) when any rhodium catalyst was used. Among them, in the combination of the main catalyst [Rh (nbd) Cl] of run5 in Table 5 and the cocatalyst KN (SiMe),
  • a very high molecular weight (310,000) polymer was obtained. Both the meta polymer and para polymer were yellow, soluble in organic solvents such as black mouth form, THF, acetone, and methanol, and immediately insoluble in hexane and toluene.
  • IR (KBr, cm '' 1 ): 3370, 2980, 1685, 1559, 1540, 1457, 1368, 1313, 1231, 1160, 1052, 836, 768.
  • a free-standing membrane was prepared by casting a THF solution of the polymer synthesized under the conditions of run 5 in Table 5 onto a petri dish.
  • Deprotection was performed by immersing the polymer membrane in a mixed solution of trifluoroacetic acid and an organic solvent such as hexane for 24 hours.
  • the polyacetylacetylene derivative according to the present invention has a hydroxyl group, an amino group, a diester, a dicarboxylic acid, or an imide in its repeating unit, and is therefore a very high molecular weight molecule. Therefore, if a membrane is formed using the polyacetylene derivative, a high-performance separation membrane having an unprecedented function can be realized, and the usable range is wide.
  • the polyacetylacetylene derivative according to the present invention can be used as a gas separation membrane such as an oxygen-enriched membrane or a liquid separation membrane such as a water purification membrane.
  • the oxygen-enriched film can be applied to air conditioners with an oxygen-enriching function. Application to batteries is also expected.

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Abstract

Dérivés du polyphénylacétylène dans lesquels chaque groupe phényle comporte un groupe hydroxy, amine, diester, acide dicarboxylique ou imide. Les dérivés de polyphénylacétylène ont une structure représentée par les formules (I), (II) ou (III) suivantes. (Dans les formules, R1 représente un atome d’hydrogène ou un groupe alkyle ; R2 représente un groupe alkyle ; R3 représente un groupe hydroxy ou amine ; et n représente un entier égal ou supérieur à 10.)
PCT/JP2005/012508 2004-07-06 2005-07-06 Nouveaux dérivés du polyphénylacétylène Ceased WO2006004161A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
JP2010238663A (ja) * 2009-03-09 2010-10-21 Sumitomo Chemical Co Ltd 空気電池

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JPH03103441A (ja) * 1989-07-31 1991-04-30 General Electric Co <Ge> アセチレンビス‐フタル酸化合物およびそれから形成されたポリイミド
JPH04246405A (ja) * 1991-01-31 1992-09-02 Asahi Chem Ind Co Ltd エステル置換ジアセチレン重合体
JPH07292037A (ja) * 1994-04-21 1995-11-07 Daicel Chem Ind Ltd 新規な光学活性ポリアセチレン誘導体及びその製造方法
JPH09143129A (ja) * 1995-11-16 1997-06-03 Fuji Photo Film Co Ltd ４−アミノフェニルアセチレン化合物の製造方法
JPH09176243A (ja) * 1995-10-25 1997-07-08 Daicel Chem Ind Ltd 新規なアセチレン誘導体の重合体
JP2002540231A (ja) * 1999-03-22 2002-11-26 アメルシャム・バイオサイエンシーズ・アクチボラグ アミノ基含有担体マトリックス、その使用および製造

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