WO2009084419A1 - Complexe de polyaniline, et composition et article moulé le comprenant the same - Google Patents

Complexe de polyaniline, et composition et article moulé le comprenant the same Download PDF

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WO2009084419A1
WO2009084419A1 PCT/JP2008/072803 JP2008072803W WO2009084419A1 WO 2009084419 A1 WO2009084419 A1 WO 2009084419A1 JP 2008072803 W JP2008072803 W JP 2008072803W WO 2009084419 A1 WO2009084419 A1 WO 2009084419A1
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group
acid
hydrocarbon group
organic
polyaniline
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PCT/JP2008/072803
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English (en)
Japanese (ja)
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Toru Bando
Yosuke Jibiki
Norihiro Kuroda
Ichiro Nasuno
Shinobu Yamao
Takeharu Tajima
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Idemitsu Kosan Co., Ltd.
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Priority to JP2009547986A priority Critical patent/JPWO2009084419A1/ja
Publication of WO2009084419A1 publication Critical patent/WO2009084419A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention relates to a novel polyaniline composite and a method for producing the same, and further relates to a conductive composition using the polyaniline composite and a molded product obtained therefrom.
  • Polyaniline is a well-known material as one of conductive polymers. In addition to its electrical properties, polyaniline has the advantage and property of being able to be synthesized relatively easily from inexpensive aniline and exhibiting excellent stability against air or the like in a state of conductivity.
  • a method for producing polyaniline As a method for producing polyaniline, a method of electrolytic oxidation polymerization or chemical oxidation polymerization of aniline or aniline derivatives is known. In electrolytic oxidation polymerization, a film having excellent electrical properties can be obtained. However, in general, the production cost is higher than chemical oxidation polymerization, and it is not suitable for mass production. Have difficulty.
  • a dopant is added to polyaniline obtained in a non-conductive base state (so-called emeraldine base state).
  • emeraldine base state a non-conductive base state
  • polyaniline in the non-conductive base state is not suitable for industrial production because it hardly dissolves in most organic solvents.
  • the conductive polyaniline (so-called emeraldine salt state) generated after the protonation is substantially insoluble and infusible, and it is difficult to easily manufacture a conductive composite material and a molded body thereof.
  • Patent Document 1 International Publication No. 2005/052058 Pamphlet
  • an object of the present invention is to provide a novel and excellent polyaniline complex, a method for producing the same, a composition and a molded body using the same.
  • the conductivity of the polyaniline composition depends on the organic acid and inorganic acid doping ratio of the polyaniline complex, and the ratio of the organic dopant to the inorganic dopant, the molecular weight, and the molecular weight distribution. Further, it has been found that according to the multistage polymerization method, the polyaniline complex having high conductivity can be obtained by controlling the doping rate, the ratio between the organic dopant and the inorganic dopant, the molecular weight, and the molecular weight distribution within a specific range. In a conductive polymer, the doping rate, doping species, molecular weight, and molecular weight distribution listed here are important structural factors that determine the performance. That is, the polyaniline complex disclosed in the present invention is a novel substance in that it has a characteristic structure factor. According to the present invention, the following polyaniline complex and its composition are provided.
  • An organic solvent, an organic acid, a substituted or unsubstituted polyaniline complex doped with an inorganic acid, and A conductive polyaniline composition comprising a compound having a phenolic hydroxyl group, The sum (a) of the organic acid and inorganic acid doping rates in the polyaniline composite is 0.4 ⁇ a ⁇ 0.6, Of the total doping rate (a), the proportion (b / a) of the doping rate (b) of the inorganic acid is 0.02 or more, A conductive polyaniline composition, wherein the polyaniline complex has a weight average molecular weight of 20,000 or more and a molecular weight distribution of 5.0 to 10.0. 2.
  • the organic acid is represented by the following formula (I) HXARn (I) ⁇ In the formula, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently —R 1 , —OR 1 , —COR 1 , —COOR 1 , —CO (COR 1 ), or —CO (COOR 1 ) [wherein R 1 is a hydrocarbon group, silyl group, — (R 2 O) x -R which may contain a substituent having 4 or more carbon atoms.
  • the organic protonic acid represented by the formula (I) is represented by the following formula (II) HXCR 4 (CR 5 2 COOR 6 ) COOR 7 (II) ⁇
  • X is an acidic group
  • R 4 and R 5 are each independently a hydrogen atom, a hydrocarbon group or an R 8 3 Si- group (wherein R 8 is a hydrocarbon group, Three R 8 may be the same or different)
  • R 6 and R 7 are each independently a hydrocarbon group or a — (R 9 O) q —R 10 group
  • R 9 is carbon A hydrogen group or a silylene group
  • R 10 is a hydrogen atom, a hydrocarbon group or R 11 3 Si— (R 11 is a hydrocarbon group, and three R 11 may be the same or different
  • q is an integer greater than or equal to 1] ⁇ 4.
  • the organic protonic acid represented by the formula (II) is represented by the following formula (III) HO 3 SCH (CH 2 COOR 12 ) COOR 13 (III) ⁇
  • R 12 and R 13 are each independently a hydrocarbon group or — (R 14 O) r —R 15 group [where R 14 is a hydrocarbon group or a silylene group, and R 15 is hydrogen An atom, a hydrocarbon group or an R 16 3 Si— group (wherein R 16 is a hydrocarbon group, and three R 16 may be the same or different), and r is an integer of 1 or more] Is ⁇ 5.
  • the conductive polyaniline composition according to 4 which is a sulfosuccinic acid derivative represented by the formula: 6). 6.
  • the organic solvent is a mixture of a water-immiscible organic solvent and a water-soluble organic solvent, and the mixing ratio (water-immiscible organic solvent: water-soluble organic solvent) is a mass ratio of 99-50: 1-50.
  • the water-immiscible organic solvent is selected from aromatic solvents, halogen-containing solvents, ester solvents, ketones having 4 or more carbon atoms, alcohols having 5 or more carbon atoms, and acrylic derivatives. 12.
  • the substituted or unsubstituted aniline is polymerized in the first step at a temperature of ⁇ 10 ° C. to 20 ° C. together with an organic acid or a salt thereof and an inorganic acid or a salt thereof.
  • the organic acid or a salt thereof is represented by the following general formula (I ′) M (XARn) m (I ′) ⁇ Wherein M is a hydrogen atom or an organic or inorganic free radical, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently- R 1 , —OR 1 , —COR 1 , —COOR 1 , —CO (COR 1 ), or —CO (COOR 1 ) [wherein R 1 is a hydrocarbon having 4 or more carbon atoms which may contain a substituent.
  • the organic protonic acid represented by the formula (I) or a salt thereof is represented by the following formula (II ′) M (XCR 4 (CR 5 2 COOR 6 ) COOR 7 ) p (II ′) ⁇
  • M is a hydrogen atom or an organic or inorganic free radical
  • X is an acidic group
  • R 4 and R 5 are each independently a hydrogen atom, a hydrocarbon group or an R 8 3 Si— group.
  • R 8 is a hydrocarbon group, and three R 8 may be the same or different
  • R 6 and R 7 are each independently a hydrocarbon group or — (R 9 O ) Q —R 10 group
  • R 9 is a hydrocarbon group or a silylene group
  • R 10 is a hydrogen atom, a hydrocarbon group, or R 11 3 Si— (R 11 is a hydrocarbon group, R 11 may be the same or different, and q is an integer of 1 or more]
  • p is an valence of M ⁇ , or an organic protonic acid or a salt thereof represented by 15 A method for producing a polyaniline complex. 17.
  • the organic protonic acid represented by the formula (II) or a salt thereof is represented by the following formula (III ′) M (O 3 SCH (CH 2 COOR 12 ) COOR 13 ) m (III ′) ⁇
  • M is a hydrogen atom or an organic or inorganic free radical
  • R 12 and R 13 are each independently a hydrocarbon group or a — (R 14 O) r —R 15 group
  • R 15 is a hydrogen atom, a hydrocarbon group or an R 16 3 Si— group (where R 16 is a hydrocarbon group, and three R 16 s may be the same or different)
  • r is an integer of 1 or more
  • m is a valence of M ⁇ .
  • a process for producing a conductive polyaniline composition comprising reacting a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid as described in 18 above with a compound having a phenolic hydroxyl group.
  • 20. 13 A conductive molded article obtained by molding the conductive polyaniline composition according to any one of 1 to 12 above. 21. 13.
  • the conductive polyaniline composition of the present invention comprises an organic solvent, a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid (hereinafter referred to as polyaniline complex), and a compound having a phenolic hydroxyl group (hereinafter referred to as “polyaniline complex”).
  • polyaniline complex a compound having a phenolic hydroxyl group
  • a phenolic compound A phenolic compound).
  • the polyaniline complex and the phenolic compound are dissolved in an organic solvent.
  • the sum (a) of the doping rates of the organic acid and the inorganic acid in the polyaniline complex is 0.4 ⁇ a ⁇ 0.6.
  • the sum (a) of the doping ratio of organic acid and inorganic acid in the polyaniline complex is 0.5, which means that one molecule of dopant is doped with respect to two molecules of nitrogen, and this value and the vicinity thereof. , The conductivity is the highest.
  • the ratio of the doping of the organic acid and the inorganic acid is such that the ratio (b / a) of the doping ratio (b) of the inorganic acid is 0.02 or more in the total doping ratio (a), preferably organic acid: inorganic
  • the acid is 0.98: 0.02 to 0.90: 0.1.
  • the doping rate of the inorganic acid plays a very important role, and a total doping rate of 0.02 or more is necessary.
  • the doping rate of the inorganic acid is 0.02 or more of the total doping rate, the effect of adding the phenolic compound, that is, the intermolecular interaction with the phenolic compound is manifested. As a result, the conductive composition having high conductivity Is given.
  • the polyaniline complex has a weight average molecular weight (hereinafter referred to as molecular weight) of 20,000 or more and a molecular weight distribution of 5.0 to 10. If the molecular weight is less than 20,000, the conductivity is lowered. Preferably the molecular weight is in the range of 50,000 to 200,000. On the other hand, the molecular weight distribution is preferably narrow from the viewpoint of electrical conductivity, but is preferably wide from the viewpoint of solubility in solvents and moldability. In some applications, moldability is often more important than electrical conductivity, and the molecular weight distribution is preferably in the range of 5.0 to 10.0 from the viewpoint of industrial usefulness.
  • molecular weight weight average molecular weight
  • the molecular weight distribution is preferably narrow from the viewpoint of electrical conductivity, but is preferably wide from the viewpoint of solubility in solvents and moldability. In some applications, moldability is often more important than electrical conductivity, and the molecular weight distribution is preferably in the range of 5.0 to 10.0 from the
  • the molecular weight distribution when the molecular weight distribution is less than 5.0, the strength and stretchability of the conductive article obtained from the composition tend to decrease. On the other hand, when the molecular weight distribution exceeds 10.0, in most cases, the ultra high molecular weight is obtained. It is a composition containing a component, and in such a composition, there exists a tendency for the solubility to a solvent to fall.
  • the molecular weight and molecular weight distribution are measured by gel permeation chromatography (GPC), and detailed measurement conditions will be described later in Examples.
  • the polyaniline complex and the polyaniline composition of the present invention can be produced by the method described below.
  • Examples of the substituent of the substituted polyaniline in the polyaniline complex include linear or branched hydrocarbon groups such as methyl group, ethyl group, hexyl group and octyl group, alkoxyl groups such as methoxy group and phenoxy group, aryloxy group, CF And halogen-containing hydrocarbon groups such as 3 groups.
  • organic acids to be doped into the polyaniline complex include the following formula (I) HXARn (I) And organic protonic acid (hereinafter referred to as organic protonic acid (I)).
  • X is an acidic group.
  • A is a hydrocarbon group which may contain a substituent, and examples thereof include a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, a substituent such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, menthyl and the like.
  • cycloalkyl groups including optionally substituted cycloalkyl groups, dicyclohexyl groups such as bicyclohexyl, norbornyl, adamantyl or the like or polycycloalkyl groups, phenyl, tosyl, thiophenyl, pyrrolinyl, pyridinyl, furanyl and the like
  • An aryl group containing an aromatic ring, naphthyl, anthracenyl, fluorenyl, 1,2,3,4-tetrahydronaphthyl, indanyl, quinolinyl, indonyl, etc. may be condensed diaryl group or polyaryl group, alkylaryl group, etc. Is mentioned.
  • R is each independently —R 1 , —OR 1 , —COR 1 , —COOR 1 , —CO (COR 1 ), or —CO (COOR 1 ).
  • R 1 may contain a substituent hydrocarbon group having 4 or more carbon atoms, silyl group, alkylsilyl group, — (R 2 O) x—R 3 group, — (OSiR 3 2 ) x—.
  • OR 3 (R 2 is an alkylene group, R 3 is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more).
  • R 1 is a hydrocarbon group
  • examples of when R 1 is a hydrocarbon group include linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosanyl, etc. Can be mentioned.
  • n is an integer of 2 or more.
  • dialkylbenzenesulfonic acid dialkylnaphthalenesulfonic acid
  • a compound represented by the following formula (II) can be preferably used.
  • X is an acidic group, for example, —SO 3 — group, —PO 3 2- group, —PO 4 (OH) 2 — group, —OPO 3 2- group, —OPO 2 ( OH) - group, -COO - group and the like, -SO 3 - group.
  • R 4 and R 5 are each independently a hydrogen atom, a hydrocarbon group or an R 8 3 Si— group (where R 8 is a hydrocarbon group, and three R 8 may be the same or different). ).
  • Examples of the hydrocarbon group when R 4 and R 5 are hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, aryl groups containing aromatic rings, and alkylaryl groups.
  • the hydrocarbon group when R 8 is a hydrocarbon group is the same as in the case of R 4 and R 5 .
  • R 6 and R 7 are each independently a hydrocarbon group or — (R 9 O) q —R 10 group [wherein R 9 is a hydrocarbon group or a silylene group, R 10 is a hydrogen atom, a hydrocarbon A group or R 11 3 Si— (R 11 is a hydrocarbon group, three R 11 may be the same or different), and q is an integer of 1 or more].
  • hydrocarbon group when R 6 and R 7 are hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, preferably 4 or more carbon atoms, aryl groups containing aromatic rings, and alkylaryl
  • specific examples of the hydrocarbon group when R 6 and R 7 are hydrocarbon groups include, for example, a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group Etc.
  • R 6 and R 7 when R 9 is a hydrocarbon group, the hydrocarbon group includes a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, an aryl An alkylene group and the like; Further, in R 6 and R 7 , the hydrocarbon group in the case where R 10 and R 11 are hydrocarbon groups is the same as in the case of R 4 and R 5 , and q is 1 to 10. preferable.
  • R 6 and R 7 are — (R 9 O) n —R 10 group include, for example, (Wherein X represents a —SO 3 group or the like).
  • the organic protonic acid (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III) (hereinafter referred to as sulfosuccinic acid derivative (III)).
  • sulfosuccinic acid derivative (III) HO 3 SCH (CH 2 COOR 12 ) COOR 13 (III)
  • R 12 and R 13 are each independently a hydrocarbon group or — (R 14 O) r —R 15 group [where R 14 is a hydrocarbon group or a silylene group, R 15 is a hydrogen atom, a hydrocarbon (wherein, R 16 is a hydrocarbon group, and three R 16 may be the same or may be different) group or R 16 3 Si- groups are, r is 1 or more is an integer.
  • the hydrocarbon group when R 12 and R 13 are hydrocarbon groups is the same as R 6 and R 7 .
  • R 12 and R 13 the hydrocarbon group in the case where R 14 is a hydrocarbon group is the same as R 9 described above. In R 12 and R 13 , the hydrocarbon group in the case where R 15 and R 16 are hydrocarbon groups is the same as R 4 and R 5 described above. r is preferably from 1 to 10.
  • R 12 and R 13 are — (R 14 O) q —R 15 group is the same as — (R 9 O) n —R 10 in R 6 and R 7 .
  • the hydrocarbon group is the same as R 6 and R 7 and is preferably a butyl group, a hexyl group, a 2-ethylhexyl group, a decyl group, or the like.
  • inorganic acids doped into the polyaniline composite include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.
  • the phenolic compound used in the composition of the present invention is not particularly limited, and any compound having an aromatic hydroxyl group can be suitably used without any particular limitation. That is, substituted phenols, polyhydric phenols, bisphenols, biphenols, and polymers having a phenolic hydroxyl group are suitably used according to the purpose.
  • Phenols polyhydric phenolic compounds such as catechol and resorcinol, 4,4′-isopropylidenediphenol (Bis-A), 2-methylenebis (4-methylphenol), 4- (2-phenylpropan-2-yl ) Bisphenols such as benzene-1,3diol, 4,4′dihydroxybiphenol, 4,4′dihydroxybenzophenone, 4,4′dihydroxydiphenyl ether, 4,4′dihydroxydiphenylsulfone, and the like; and phenol resins, polyphenols And polymer compounds such as poly (hydroxystyrene).
  • the phenolic compound is present not as a solvent but as a dopant.
  • the fact that the phenolic compound is a dopant means that the molded product produced from the composition of the present invention to which the phenolic compound is added has a very high electrical conductivity compared to the molded product to which this compound is not added, and an organic solvent.
  • the UV-vis (ultraviolet-visible) spectrum in which the molded product obtained from the conductive polyaniline composition of the present invention containing a phenolic compound and the molded product obtained from a polyaniline composite containing no phenolic compound after removal is different. It is clear that the phenolic compound remains in the molded product after the organic solvent is removed.
  • phenolic and cresol solvents as described above as phenolic compounds suitably used in the present invention, but usually solvents such as naphthol and 2-methylenebis (4-methylphenol) are generally used. It is also clear from the compounds that are not recognized. That is, these phenolic compounds have a strong molecular interaction with the polyaniline complex of the present invention and form a new composition that exhibits high conductivity.
  • the molar concentration of the phenolic compound relative to 1 g of the polyaniline complex is preferably in the range of 0.01 mmol / g to 50 mmol / g. If the amount of this compound added is too small, the effect of improving the electrical conductivity may not be obtained. Moreover, when too much, there exists a possibility that the uniformity of a composition may be impaired or it may become a material by which the transparency and the electrical property were impaired by the influence of the excess phenolic compound. In particular, it is preferably in the range of 0.05 mmol / g to 20 mmol / g.
  • the phenolic compound preferably has two or more aromatic rings, and more preferably has two aromatic rings.
  • the phenolic compound having two or more aromatic rings is not particularly limited as long as it has aromaticity, for example, two or more aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a pyrrole ring. And having at least one phenolic hydroxyl group can be used.
  • a compound represented by the following formula (IV) can be preferably used.
  • Ar-X-Ar '(IV) [Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom, and Ar and Ar ′ are aromatic ring groups, which may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, a cyano group, and a carbonyl group. ]
  • X is a single bond, oxygen atom, —NH—, —NHCO—, —COO—, —CO—, —COCH 2 —, —OCO—, —CH 2 —, —C 2 H 4 —, —C 3 H 6- and the like.
  • preferred examples of X include an oxygen atom.
  • One or two X can be present in the phenolic compound. When two are present, the two Xs may be the same or different. Examples of such a structure include a fluorene structure having a single bond and —CH 2 — as X.
  • examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group.
  • examples of other substituents for Ar and Ar ′ include halogen, amino group, cyano group, nitro group, nitrile group, and carbonyl group.
  • a plurality of Ar or Ar ′ substituents may be bonded to each other to form a ring.
  • Examples of the ring structure include a cyclohexyl ring, a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a pyrrole ring.
  • a phenolic compound other than the compound of the formula (IV) in which two aromatic rings are bonded via X a phenolic compound in which a hydroxyl group is added to a polycyclic aromatic ring such as a naphthalene ring or an anthracene ring is used.
  • a polycyclic aromatic ring such as a naphthalene ring or an anthracene ring.
  • Such a compound is preferable in that it exhibits heat resistance and high conductivity. Examples of such a compound include ⁇ -naphthol and ⁇ -naphthol.
  • the phenolic compound containing two or more aromatic rings is preferably a phenolic compound having a melting point of room temperature or higher or a boiling point of 200 ° C. or higher at room temperature. Particularly preferred are 2-, 3-, or 4-hydroxybiphenyl, 2-, 3-, or 4-phenoxyphenol, 1- or 2-naphthol, and the like.
  • the organic solvent contained in the polyaniline composition may be a solvent in which the organic solvent is not substantially miscible with water (water-immiscible organic solvent) or a water-soluble organic solvent.
  • water-immiscible organic solvents include aromatic solvents such as toluene, xylene, ethylbenzene, tetralin, and styrene derivatives (such as styrene and divinylbenzene), halogen-containing solvents such as chloroform and dichloromethane, ethyl acetate, and butyl acetate.
  • Ester solvents methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ketones having 4 or more carbon atoms such as cyclohexanone, alcohols having 5 or more carbon atoms such as pentanol and benzyl alcohol, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, etc.
  • An acrylic derivative is mentioned.
  • water-soluble organic solvent examples include water-soluble alcohols such as methanol, ethanol, isopropyl alcohol, butanol and 2-methoxyethanol, water-soluble ketones such as acetone and gamma-butyrolactone, water-soluble oxygen-containing ring derivatives such as tetrahydrofuran, N-methyl
  • water-soluble alcohols such as methanol, ethanol, isopropyl alcohol, butanol and 2-methoxyethanol
  • water-soluble ketones such as acetone and gamma-butyrolactone
  • water-soluble oxygen-containing ring derivatives such as tetrahydrofuran
  • N-methyl examples include aprotic polar solvents such as pyrrolidone, dimethylformamide, and dimethyl sulfoxide.
  • the polyaniline complex and phenolic compound of the present invention are soluble in alcohols such as 2-butanol, 2-pentanol, and benzyl alcohol. Alcohol is preferable from the viewpoint of reducing environmental burden unlike toluene.
  • a mixed organic solvent of a water-immiscible organic solvent and a water-soluble organic solvent is used in a mass ratio of 99 to 50: 1 to 50, whereby the polyaniline complex solution obtained in the present invention is obtained.
  • it is preferable in terms of long-term storage because it can prevent generation of gels and the like.
  • the ratio of the polyaniline complex in the organic solvent is usually 900 g / L or less, preferably 0.01 to 300 g / L or less, depending on the type of the organic solvent. If the content of the polyaniline complex is too high, the solution state cannot be maintained, and it becomes difficult to handle the molded body, the uniformity of the molded body is impaired, and consequently the electrical properties and mechanical strength of the molded body. , Resulting in a decrease in transparency. On the other hand, if the content of the polyaniline complex is too small, only a very thin film can be produced when the film is formed by the method described later, which may make it difficult to produce a uniform conductive film.
  • the polyaniline composition of the present invention is electrically conductive, and the conductivity can be widely controlled depending on the properties of the polyaniline complex and the type and amount of the compound having a phenolic hydroxyl group to be used. However, it is usually 1.0 S / cm or more, preferably 50 S / cm or more, and more preferably 100 S / cm.
  • resins inorganic materials, curing agents, plasticizers and the like may be added to the polyaniline composition of the present invention depending on the purpose.
  • Other resins are added for the purpose of, for example, a binder base material, a plasticizer, a matrix base material, and specific examples thereof include, for example, polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrenes, polyesters, polyamides, polyacetals. , Polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol and the like. A chlorinated polyolefin is preferred.
  • styrene derivatives such as styrene and divinylbenzene, or acrylic derivatives such as methyl methacrylate, ethyl methacrylate, and cyclohexyl methacrylate can be used as the soluble organic medium.
  • the organic medium having these reactive functional groups and polyaniline are homogeneously mixed and dissolved, and then the organic medium having these reactive functional groups is reacted by an arbitrary method, whereby various kinds of conductive materials are obtained. It means that a complex is obtained. That is, for example, a thermosetting or UV curable conductive curable resin can be provided according to a required application.
  • Inorganic materials are added for the purpose of, for example, improving strength, surface hardness, dimensional stability and other mechanical properties.
  • Specific examples thereof include silica (silicon dioxide), titania (titanium oxide), alumina ( Aluminum oxide) and the like.
  • the curing agent is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, and specific examples thereof include, for example, thermosetting agents such as phenol resins, acrylate monomers and photopolymerization. Examples thereof include a photo-curing agent using a property initiator.
  • the plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength, and specific examples thereof include phthalates and phosphates.
  • the conductive polyaniline composition of the present invention is produced by reacting with a phenolic compound after producing a substituted or unsubstituted polyaniline complex as follows.
  • the substituted or unsubstituted aniline is polymerized in the first step at a temperature of ⁇ 10 ° C. to 20 ° C. with an organic acid or a salt thereof, and an inorganic acid or a salt thereof, and further at a temperature 5 ° C. or more higher than the above temperature.
  • Polymerization is performed in the second and subsequent steps with a stirring power of ⁇ 2000 w / m 3 to produce a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid.
  • the polymerization temperature in the first stage is ⁇ 10 ° C. to 20 ° C.
  • the polymerization temperature in the second stage and thereafter is 15 ° C. to 40 ° C.
  • the polymerization temperature after the second stage is 5 ° C. or more, preferably 20 to 30 ° C. higher than the polymerization temperature of the first stage.
  • the dope rate can be adjusted by the polymerization temperature after the second stage. That is, when the polymerization temperature is raised, the doping rate approaches the ideal value of 0.5, and the doping rate of the inorganic dopant tends to increase.
  • the first stage stirring power is 50 to 300 w / m 3 .
  • the stirring power after the second stage is 4 to 1000 w / m 3 .
  • the molecular weight distribution can be adjusted by the stirring power after the second stage. That is, when the stirring power is reduced, the molecular weight distribution tends to be reduced.
  • molecular weight can be adjusted by changing the oxidizing agent density
  • the polymerization time for each stage can be set as appropriate. For example, the polymerization time for the first stage is 5 to 25 hours, and the polymerization time for each stage after the second stage is 0.5 to 4 hours.
  • the number of stages of polymerization of the polyaniline complex is not particularly limited, but can be efficiently produced by two-stage polymerization.
  • a polyaniline complex is produced by such multistage polymerization, a polyaniline complex can be produced stably and reproducibly.
  • a polyaniline complex when manufactured using a water-immiscible organic solvent, a polyaniline complex can be manufactured in a two-phase system of a water-immiscible organic solvent and an aqueous solution.
  • surfactant when manufacturing by the two-phase system of a water-immiscible organic solvent and aqueous solution, surfactant can be added as needed and the reaction rate and a yield improvement can be aimed at.
  • the surfactant to be used is not particularly limited, and anionic, cationic, and nonionic surfactants are widely and suitably used. Of these, cationic and nonionic surfactants are preferred.
  • the addition amount of the organic acid or salt thereof and the inorganic acid or salt thereof with respect to the substituted or unsubstituted aniline can be appropriately set.
  • the organic acid or salt thereof is 1 to 50 mol% with respect to the substituted or unsubstituted aniline.
  • the polyaniline complex is polymerized by, for example, a chemical oxidative polymerization method or an electrolytic polymerization method.
  • the organic acid or a salt thereof is preferably an organic protonic acid or a salt thereof represented by the following formula (I ′).
  • M (XARn) m (I ′) wherein M is a hydrogen atom or an organic or inorganic free radical, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently- R 1 , —OR 1 , —COR 1 , —COOR 1 , —CO (COR 1 ), —CO (COOR 1 ) [wherein R 1 is a hydrocarbon group which may contain a substituent having 4 or more carbon atoms.
  • a silyl group, — (R 2 O) x—R 3 group, or — (OSiR 3 2 ) x—OR 3 group R 2 is an alkylene group, and R 3 may be the same or different hydrocarbon groups, respectively.
  • x is an integer greater than or equal to 1)]
  • n is an integer greater than or equal to 2
  • m is the valence of M ⁇
  • M is a hydrogen atom or an organic or inorganic free radical.
  • the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group
  • examples of the inorganic free radical include sodium, lithium, potassium, cesium, ammonium, and the like.
  • m is the valence of M.
  • X, A, R, and n are the same as in the above formula (I).
  • dialkylbenzene sulfonic acid dialkyl naphthalene sulfonic acid, sulfophthalic acid ester, and a compound represented by the following formula (II ′) can be preferably used.
  • M XCR 4 (CR 5 2 COOR 6 ) COOR 7
  • p is the valence of M.
  • the organic protonic acid or a salt thereof (II ′) is more preferably a sulfosuccinic acid derivative represented by the following formula (III ′) (hereinafter referred to as sulfosuccinic acid derivative (III ′)).
  • M and m are the same as in the above formula (I ′).
  • R 12 and R 13 are the same as in the above formula (III).
  • the polyaniline complex When the polyaniline complex is produced in a water-immiscible organic solvent, it can be produced by adding a phenolic compound to the polyaniline complex dissolved in the water-immiscible organic solvent.
  • a conductive molded body can be obtained from the polyaniline composition of the present invention. Specifically, a conductive molded body is obtained by molding the polyaniline composition of the present invention and removing the organic solvent.
  • the thickness thereof is usually 1 mm or less, preferably in the range of 10 nm to 50 ⁇ m.
  • a film having a thickness in this range is advantageous in that it does not easily crack during film formation and has uniform electrical characteristics.
  • the conductive polyaniline composition of the present invention is formed into a film, a tough and flexible self-supporting conductive film can be obtained.
  • This film can have a tensile elongation of 10% or more at a pulling speed of 1 mm / min.
  • a conductive film (surface conductive article) can be produced by applying the conductive polyaniline composition of the present invention to a substrate such as glass, a resin film, a sheet or a nonwoven fabric having a desired shape and removing the organic solvent. .
  • a method for applying the composition to a substrate known general methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a barcode method, a spin coating method, an electrospinning method, screen printing, and a gravure printing method are used. Can be used.
  • the organic solvent may be volatilized by heating.
  • heating is performed at a temperature of 250 ° C. or less, preferably 50 to 200 ° C. in an air stream, and further, heating is performed under reduced pressure as necessary.
  • the heating temperature and the heating time are not particularly limited and may be appropriately selected according to the material used.
  • the polyaniline composition of the present invention may be mixed with a base material to form a conductive article.
  • Thermoplastics such as polyolefin such as polyethylene and polypropylene, chlorinated polyolefin, polystyrene, polyester, polyamide, polyacetal, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol
  • thermosetting resins such as resins, epoxy resins, phenol resins, and urethane resins.
  • the molded article of the present invention can be a self-supporting molded article having no substrate.
  • a molded body having a desired mechanical strength can be obtained when the composition contains the other resin described above.
  • Example 1 [Production of polyaniline complex] 1.8 g of AOT (sodium diisooctylsulfosuccinate) was dissolved in 50 mL of toluene, and the solution was put into a 500 mL separable flask placed under a nitrogen stream, and 1.8 mL of aniline was further added to this solution. Thereafter, 150 mL of 1N hydrochloric acid was added to the solution, and the solution temperature was cooled to 5 ° C.
  • AOT sodium diisooctylsulfosuccinate
  • this complex solution was removed with # 5C filter paper, and a toluene solution of the polyaniline complex was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate and remove volatile components to obtain 1.25 g of a polyaniline complex.
  • the obtained polyaniline composition solution was formed on an ITO substrate by a spin coating method, and the intrinsic conductivity was measured by a four-terminal method. The results are shown in Table 2.
  • Example 2 A polyaniline complex was obtained in the same manner as in Example 1 except that the polymerization temperature in the first stage was changed to 0 ° C. in Example 1. Furthermore, using this polyaniline composite, the same procedures and operations as in Example 1 were followed, and the organic acid, inorganic acid dope rate, molecular weight, molecular weight distribution, intrinsic conductivity of the polyaniline composite, and a composition with a phenolic compound The intrinsic conductivity of was measured. The results are shown in Tables 1 and 2.
  • Example 3 A polyaniline complex was obtained in the same manner as in Example 1 except that the polymerization temperature in the second stage was 10 ° C. in Example 1. Furthermore, using this polyaniline composite, the same procedures and operations as in Example 1 were followed, and the organic acid, inorganic acid dope rate, molecular weight, molecular weight distribution, intrinsic conductivity of the polyaniline composite, and a composition with a phenolic compound The intrinsic conductivity of was measured. The results are shown in Tables 1 and 2.
  • Example 4 A polyaniline complex was obtained in the same manner as in Example 1 except that the hydrochloric acid concentration used in Example 1 was changed to 0.5N. Furthermore, using this polyaniline composite, the same procedures and operations as in Example 1 were followed, and the organic acid, inorganic acid dope rate, molecular weight, molecular weight distribution, intrinsic conductivity of the polyaniline composite, and a composition with a phenolic compound The intrinsic conductivity of was measured. The results are shown in Tables 1 and 2.
  • Comparative Example 1 AOT 1.8g was melt
  • the reaction was carried out while maintaining the internal temperature of the solution at 5 ° C. for 18 hours from the start of dropping. Thereafter, the aqueous phase separated into two phases by standing was separated, and the toluene phase was washed twice with 50 mL of ion-exchanged water and once with 50 mL of 1N hydrochloric acid to obtain a polyaniline complex toluene solution.
  • this complex solution was removed with # 5C filter paper, and a toluene solution of the polyaniline complex was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate and remove volatile components, whereby 1.05 g of a polyaniline complex was obtained.
  • the intrinsic conductivity, doping rate, molecular weight, and molecular weight distribution of the obtained polyaniline composite were measured in the same manner as in Example 1. Moreover, the intrinsic conductivity of the composition with the phenolic compound was measured. The results are shown in Tables 1 and 2.
  • Comparative Example 2 AOT 1.8g was melt
  • the doping rate, molecular weight, molecular weight distribution, and intrinsic conductivity were measured in the same manner as in Example 1. Moreover, the intrinsic conductivity of the composition with the phenolic compound was measured. The results are shown in Tables 1 and 2.
  • Comparative Example 3 Polymerization of the polyaniline complex was carried out in the same manner as in Example 1 except that the amount of AOT used for polymerization was changed to 0.9 g in Example 1. However, in this case, the polyaniline complex was hardly recovered from the toluene phase side, and most was recovered as an insoluble matter. This insoluble matter was separated by filtration, washed several times with water and dried, and further purified twice by washing with hexane. This was subjected to elemental analysis in the same manner as in Example 1, and the dope rate was measured.
  • the polyaniline complex obtained at the same time was mixed with a 1N aqueous sodium hydroxide solution in the same manner as in Example 1, and after re-recovery, it was subjected to GPC measurement to measure molecular weight and molecular weight distribution. Further, the obtained polyaniline complex was redissolved in toluene in the same manner as in Example 1 and an attempt was made to measure the intrinsic conductivity.
  • Comparative Example 4 A polyaniline composite was obtained in the same manner as in Example 1 except that the stirring strength in the second stage polymerization was changed to 2200 w / m 3 in Example 1. Thereafter, the organic acid and inorganic acid topo rate, molecular weight, molecular weight distribution, intrinsic conductivity of the polyaniline complex, and intrinsic conductivity of the composition with the phenolic compound were measured by the same procedure and operation as in Example 1. did. This product was poor in re-solubility in toluene, and only a part of the insoluble component was confirmed.
  • Example 5 1 g of the polyaniline complex obtained in Example 1 was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution. Here, 1 g of 2-naphthol was added instead of m-cresol to obtain a polyaniline composition. This solution was formed on an ITO substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method. The obtained coating film had an intrinsic conductivity of 108 S / cm.
  • Example 6 A polyaniline composition was obtained in the same manner as in Example 5, except that 1 g of 2-methylenebis (4-methylphenol) was used instead of 2-naphthol. This solution was formed on an ITO substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method. The obtained coating film had an intrinsic conductivity of 46 S / cm.
  • Example 7 The specific conductivity was measured in the same manner as in Example 1 except that 1 g of the polyaniline complex obtained in Example 1 was dissolved in 20 ml of an alcohol solvent. Table 3 shows the solvents used and the intrinsic conductivity obtained.
  • Example 8 1 g of the polyaniline complex obtained in Example 1 was dissolved again in 20 ml of toluene solution to prepare a polyaniline complex solution, and further 2 ml of m-cresol was added to obtain a polyaniline composition.
  • This composition was spread on a glass substrate in a range of 14 mm ⁇ 52 mm, and dried at 80 ° C. for 30 minutes in an air stream to form a conductive film having a thickness of 16 ⁇ m.
  • the obtained conductive film was measured using a tensile tester in accordance with DIN 53504-53, with a tensile speed of 1 mm / min. A tensile test was carried out. As a result, the elongation at break was 27%.
  • Example 9 The polyaniline composition obtained in Example 8 was applied to a glass substrate by a spin coating method, and this substrate was held at 105 ° C. for 500 hours in a nitrogen atmosphere to measure a change in surface resistance value. The results are shown in Table 4.
  • Example 10 The polyaniline complex obtained in Example 1 was dissolved in toluene to prepare a 5 wt% polyaniline complex solution. To 5 g of this solution, 1.25 g of chlorinated polyethylene resin Super Clone HE-505 (manufactured by Nippon Paper Chemicals Co., Ltd.) was added, and 2 mL of m-cresol was added to obtain a uniform solution to obtain a polyaniline composition.
  • chlorinated polyethylene resin Super Clone HE-505 manufactured by Nippon Paper Chemicals Co., Ltd.
  • composition prepared above was applied to a 0.3 mm thick super pure array sheet (SG-140TC, manufactured by Idemitsu Unitech) using a bar coater and dried in an oven at 80 ° C. for 5 minutes to obtain a conductive sheet. .
  • the surface resistance of this sheet was 1.0 ⁇ 10 2 ⁇ / ⁇ .
  • Example 11 The same operation as in Example 10 was performed except that HE910 (manufactured by Nippon Paper Chemicals Co., Ltd.) was used as the chlorinated polyethylene resin in Example 10 instead of Super Clone HE505, under a nitrogen atmosphere at 105 ° C., The change of the surface resistance value was measured by holding for 500 hours. The results are shown in Table 4. As shown in Table 4, the resistance stability under high temperature exposure is greatly improved in the polyaniline composition to which chlorinated polyolefin is added.
  • HE910 manufactured by Nippon Paper Chemicals Co., Ltd.
  • Example 12 (1) Synthesis of sodium 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonate 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) ester (manufactured by Tokyo Chemical Industry Co., Ltd.) under an argon gas stream 80 g and 900 mL of isopropyl alcohol were charged, and a solution of 42.3 g of sodium hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) in 660 mL of water was added. The solution was heated to reflux temperature and stirred at 80-83 ° C. for 16 hours.
  • Example 13 The polyaniline complex obtained in Example 1 was dissolved in chloroform to prepare a 5 wt% polyaniline complex solution. To 200 g of the solution, 6 g of polyethylene oxide (Aldrich) having a weight average molecular weight (Mw) of 900,000 was added, and 20 g of m-cresol and 150 g of isopropyl alcohol were added to obtain a uniform solution to obtain a composition.
  • polyethylene oxide Aldrich
  • Mw weight average molecular weight
  • This solution was electrospun using Nanospider NS LAB 200S (manufactured by Elmarco) at a distance between electrodes of 160 mm, a voltage of 50 kV, a cylinder rotation speed of 3.5 rpm, and a winding speed of 8 cm / min.
  • a composition was obtained.
  • a polypropylene sheet having a thickness of 0.3 mm and a width of 40 cm and a polypropylene nonwoven fabric having a basis weight of 20 g / m 2 and a width of 40 cm were used as the base material.
  • the amount of the polyaniline composition attached to the polypropylene sheet and the polypropylene nonwoven fabric was determined by measuring the weight difference before and after electrospinning. As a result, the adhesion amount of the polyaniline composition was 0.4 to 0.8 g / m 2 in all cases.
  • Example 14 The polyaniline complex obtained in Example 1 was dissolved in chloroform to prepare a 5 wt% polyaniline complex solution. To 410 g of the solution, 1 g of polyethylene oxide (Aldrich) having a weight average molecular weight (Mw) of 900,000 was added, and 20 g of m-cresol and 210 g of isopropyl alcohol were added to obtain a uniform solution to obtain a composition.
  • Aldrich polyethylene oxide having a weight average molecular weight (Mw) of 900,000 was added, and 20 g of m-cresol and 210 g of isopropyl alcohol were added to obtain a uniform solution to obtain a composition.
  • This solution was electrospun with Nanospider NS LAB 200S (manufactured by Elmarco) at a distance between electrodes of 160 mm, a voltage of 73 kV, a cylinder rotation speed of 3 rpm, and a winding speed of 8 cm / min to obtain a filamentous composition having a diameter of 300 nm or less. It was.
  • the base material used was a polypropylene sheet having a thickness of 0.3 mm and a width of 40 cm, a PET sheet having a thickness of 0.1 mm and a width of 40 cm, and a polypropylene nonwoven fabric having a basis weight of 30 g / m 2 and a width of 40 cm.
  • the amount of the polyaniline composition attached to the polypropylene sheet, the PET sheet, and the polypropylene nonwoven fabric was determined by measuring the weight difference before and after electrospinning. As a result, the adhesion amount of the polyaniline composition was 0.4 to 0.8 g / m 2 in all cases.
  • Example 15 5 parts by mass of the polyaniline complex obtained in Example 1 was dissolved in 95 parts by mass of chloroform or toluene. To this solution, 10 parts by mass of m-cresol and 1 to 90 parts by mass of various highly polar organic solvents shown in Table 6 were added to prepare a polyaniline composition solution. The obtained polyaniline composition solution was formed on an ITO substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method. The results shown in Table 6 were obtained. Further, when the storage stability of each obtained polyaniline composition solution was examined, no gel was observed even after storage for 10 days.
  • the polyaniline composite, conductive polyaniline composition, and molded product of the present invention are used in the field of power electronics and optoelectronics. Electrostatic / antistatic materials, transparent electrodes and conductive film materials, electroluminescent element materials, circuit materials, antenna materials It can be used for electromagnetic shielding materials, capacitor electrodes / dielectrics / electrolytes, electrode materials for solar cells and secondary batteries, fuel cell separator materials, actuators, various sensor substrates, etc., plating base materials, and rust inhibitors.

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Abstract

La présente invention concerne une composition de polyaniline électriquement conductrice comprenant un solvant organique, un complexe de polyaniline substitué ou non substitué dopé avec un acide organique et un acide inorganique, et un composé ayant un groupe hydroxy phénolique, le taux de dopage total (a) qui est la somme totale du taux de dopage du complexe de polyaniline avec l'acide organique et du taux de dopage du complexe de polyaniline avec l'acide inorganique étant supérieur à 0,4 et inférieur à 0,6, le rapport entre le taux de dopage (b) du complexe de polyaniline avec l'acide inorganique et le taux de dopage total (a) (c'est-à-dire b/a) étant de 0,02 ou plus, et le complexe de polyaniline ayant une masse moléculaire moyenne en poids de 20000 ou plus et une distribution des masses moléculaires inférieure à 5,0.
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JP2020059791A (ja) * 2018-10-09 2020-04-16 国立大学法人 東京大学 熱硬化体形成用組成物、熱硬化体、熱硬化体を有する構造体
JP2020107840A (ja) * 2018-12-28 2020-07-09 出光興産株式会社 成形用又は延伸用フィルム、成形体及び延伸フィルム
JP2020145278A (ja) * 2019-03-05 2020-09-10 出光興産株式会社 電磁波吸収シート及びその製造方法
JP2020143202A (ja) * 2019-03-05 2020-09-10 信越ポリマー株式会社 導電性高分子含有液及びその製造方法、並びに導電性フィルム及びその製造方法
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JP2020059791A (ja) * 2018-10-09 2020-04-16 国立大学法人 東京大学 熱硬化体形成用組成物、熱硬化体、熱硬化体を有する構造体
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CN114015173A (zh) * 2021-11-19 2022-02-08 广东腐蚀科学与技术创新研究院 一种掺杂改性聚苯胺／聚酰胺填料复合的导电共混物及其制备方法

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