JP5257708B2 - ナノ複合体およびそれを含む分散液 - Google Patents
ナノ複合体およびそれを含む分散液 Download PDFInfo
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- JP5257708B2 JP5257708B2 JP2010188097A JP2010188097A JP5257708B2 JP 5257708 B2 JP5257708 B2 JP 5257708B2 JP 2010188097 A JP2010188097 A JP 2010188097A JP 2010188097 A JP2010188097 A JP 2010188097A JP 5257708 B2 JP5257708 B2 JP 5257708B2
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- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical class BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical group C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
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- DBEZFSYFMIFACG-UHFFFAOYSA-N dimethyl-[3-(prop-2-enoylamino)propyl]-(3-sulfopropyl)azanium;hydroxide Chemical compound [OH-].OS(=O)(=O)CCC[N+](C)(C)CCCNC(=O)C=C DBEZFSYFMIFACG-UHFFFAOYSA-N 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- UMSGVWVBUHUHEH-UHFFFAOYSA-M ethyl(trimethyl)azanium;bromide Chemical compound [Br-].CC[N+](C)(C)C UMSGVWVBUHUHEH-UHFFFAOYSA-M 0.000 description 1
- UXYBXUYUKHUNOM-UHFFFAOYSA-M ethyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)C UXYBXUYUKHUNOM-UHFFFAOYSA-M 0.000 description 1
- RHSSOBQGZQVTHC-UHFFFAOYSA-L ethyl(trimethyl)azanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CC[N+](C)(C)C.CC[N+](C)(C)C RHSSOBQGZQVTHC-UHFFFAOYSA-L 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- ZPEBBUBSCOELHI-UHFFFAOYSA-M ethyltrimethylammonium iodide Chemical compound [I-].CC[N+](C)(C)C ZPEBBUBSCOELHI-UHFFFAOYSA-M 0.000 description 1
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- 239000012065 filter cake Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
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- 238000013038 hand mixing Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 238000000608 laser ablation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- KSKTVNNRMXUMIY-UHFFFAOYSA-N n,n-dimethylethanamine;hydrochloride Chemical compound Cl.CCN(C)C KSKTVNNRMXUMIY-UHFFFAOYSA-N 0.000 description 1
- AQHOKHIQNCYFTI-UHFFFAOYSA-N n,n-dimethylethanamine;sulfuric acid Chemical compound CCN(C)C.OS(O)(=O)=O AQHOKHIQNCYFTI-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
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- 239000002074 nanoribbon Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003904 phospholipids Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920001464 poly(sodium 4-styrenesulfonate) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002495 polyphenylene ethynylene polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
を備えており、前記カーボン系ナノフィラー100質量部に対して前記共重合体の吸着量が0.1質量部以上200質量部以下であることを特徴とするものである。また、本発明の分散液は、このようなナノ複合体と溶媒とを含有することを特徴とするものである。
を溶媒中で混合して前記カーボン系ナノフィラー100質量部に対して0.1質量部以上200質量部以下の前記共重合体を吸着させることを特徴とするものである。
本発明に用いられるナノ構造体としては特に制限はないは、例えば、カーボンナノファイバー、カーボンナノホーン、カーボンナノコーン、カーボンナノチューブ、カーボンナノコイル、カーボンマイクロコイル、カーボンナノウォール、カーボンナノチャプレット、フラーレン、グラファイト、グラフェン、グラフェンナノリボン、ナノグラフェン、ナノグラファイト、カーボンブラック、カーボンナノフレークといったカーボン系ナノフィラー;カーボンナノチューブの一部の炭素原子を窒素原子やホウ素原子で置換したBCNナノチューブや窒化ホウ素(BN)ナノチューブといった窒化ホウ素系ナノフィラーなどのナノフィラーが挙げられる。これらのナノ構造体は1種を単独で使用しても2種以上を併用してもよい。
本発明に用いられる共重合体は、下記式(1):
で表される双性イオンモノマー単位およびカチオン性モノマー単位からなる群から選択される少なくとも1種のイオン性モノマー単位と、このようなイオン性モノマー単位以外のその他のモノマー単位とを含有するものである。このような双性イオンモノマー単位および/またはカチオン性モノマー単位を含有する共重合体は、非イオン性モノマー単位および/またはアニオン性モノマー単位を含有する共重合体と比較して、高温下において、水系溶媒との親和性に優れているため、ナノ複合体同士の凝集を抑制し、高温下の水系溶媒中においてもナノ複合体の優れた分散性を維持することができる。
で表される双性イオンモノマーまたはカチオン性モノマーから誘導されるモノマー単位であるが、前記式(1)で表されるモノマー単位であれば前記双性イオンモノマーから誘導されるものに限定されない。
2−((メタ)アクリロイルオキシ)エチルジメチルアミンのメチルクロライド塩、2−((メタ)アクリロイルオキシ)エチルジメチルアミンのメチルブロマイド塩、2−((メタ)アクリロイルオキシ)エチルジメチルアミンのベンジルクロライド塩といった第3級アミンをハロゲン化炭化水素で4級化した塩;2−((メタ)アクリロイルオキシ)エチルジメチルアミンの硫酸塩、2−((メタ)アクリロイルオキシ)エチルジメチルアミンの塩酸塩といった第3級アンモニウム塩が挙げられる。
で表されるマレイミド系モノマー単位、下記式(5):
で表されるグルタルイミド基含有構成単位、ならびに、
N−アルケニルイミド単位およびその誘導体単位等が挙げられる。
本発明のナノ複合体は、前記ナノ構造体に前記共重合体が吸着したものである。従来、前記ナノ構造体は、溶媒中や樹脂中に分散させることは困難であったが、前記ナノ構造体に前記共重合体を吸着させることによって、樹脂中や溶媒中、特に高温下においても水系溶媒中に均一に分散させることが可能となる。
本発明のナノ複合体の製造方法としては、前記ナノ構造体に前記共重合体を吸着させることが可能な方法であれば特に制限はないが、例えば、以下の方法が挙げられる。
(i)前記ナノ構造体と前記共重合体とを溶媒中で混合する方法。
(ii)前記ナノ構造体と前記共重合体とを溶媒を使用せずに混合する方法。
(iii)前記ナノ構造体と溶融させた前記共重合体とを混合する方法。
(iv)前記ナノ構造体と前記共重合体とを溶媒を使用せずに混合した後、前記共重合体を溶融させる方法。
(v)前記ナノ構造体の存在下で、必要に応じて溶媒を用いて前記共重合体を重合により合成する方法。
本発明の分散液は、本発明のナノ複合体および溶媒を含むものである。前記溶媒としては前記混合方法において例示したものが挙げられる。本発明においては、カーボンナノ複合体を溶媒中で調製してそのまま分散液として使用することもできるが、本発明のカーボンナノ複合体が再分散性に優れているため、カーボンナノ複合体を溶媒に添加して超音波処理などを施すことにより分散液を製造することもできる。
共重合体を重水に溶解し、30℃、400MHzの条件で1H−NMR測定を実施した。そして、測定結果から、下記表1に記載した化学シフトに従って各構成単位のプロトンの積分値を求め、これらの比から共重合体における各構成単位のモル比を決定した。
先ず、ナノフィラーおよび共重合体をそれぞれ真空乾燥して残留溶媒などの揮発分を除去した後、それぞれについて熱重量分析装置(理学電機(株)製「Thermo plus TG8120」)を用いて窒素雰囲気下、昇温速度20℃/分で室温から600℃まで加熱して熱重量分析(TGA)を実施し、ナノフィラーおよび共重合体の熱分解開始温度および熱分解終了温度を測定した。なお、通常、質量減少が開始した時点の温度を熱分解開始温度とし、質量減少が終了した時点の温度を熱分解終了温度としたが、600℃の時点で質量減少が終了していない場合には質量減少が終了するまでさらに昇温して熱分解終了温度を測定した。
各実施例で得られたナノフィラー複合体を含有する分散液に、室温で遠心分離(相対遠心加速度1220Gで1時間)を施し、その上澄み液についてUV−可視光吸収スペクトルを室温で測定し、600nmの吸光度により分散性を評価した。この吸光度の値が高いものほど、分散液に遠心分離を施しても、ナノフィラー複合体は、沈降しにくく、室温での分散性に優れたものであることを意味する。
各実施例で得られたナノフィラー複合体を含有する分散液を容量50mLのオートクレーブに入れ、160℃の温度に保持した熱風乾燥機で1時間熱処理(160℃)を施した。この分散液を室温まで冷却した後、得られた分散液に室温で遠心分離(相対遠心加速度1220Gで1時間)を施し、その上澄み液についてUV−可視光吸収スペクトルを室温で測定し、600nmの吸光度により分散性を評価した。この吸光度の値が高いものほど、ナノフィラー複合体は、高温処理による凝集が起こりにくく、高温下での分散性に優れたものであることを意味する。
カーボン系ナノフィラー(a−1):
単層カーボンナノチューブ(CNI社製「HiPco−SWNT」、平均直径1.0nm、アスペクト比100超過、G/D値:16.0、窒素雰囲気下での熱分解温度は600℃超過)。
カーボン系ナノフィラー(a−2):
多層カーボンナノチューブ(ナノシル社製「Nanocyl7000」、平均直径9.5nm、アスペクト比100超過、G/D値:0.7、窒素雰囲気下での熱分解温度は600℃超過)。
メタクリル酸1−ピレニルブチルの調製:
1−ピレンブタノール5.0gおよびトリエチルアミン3.68gをテトラヒドロフラン100mlに溶解し、0℃で塩化メタクリロイル1.90gを滴下した後、室温で1時間撹拌した。析出物を酢酸エチルで洗浄しながら濾過し、濾液と洗浄液とを混合してこれを硫酸マグネシウムで乾燥した後、溶媒を減圧留去した。残渣をカラムクロマトグラフ(シリカゲル、ヘキサン:酢酸エチル=10:1)で精製し、真空乾燥してメタクリル酸1−ピレニルブチルを得た。
共重合体(b−1)の調製:
撹拌機を備えた反応缶中において、下記式(6):
で表される、本発明にかかる双性イオンモノマー単位を含有するものであることがわかった。
共重合体(b−2)の調製:
撹拌機を備えた反応缶中において、下記式(8):
で表される、本発明にかかるカチオン性モノマー単位を含有するものであることがわかった。
共重合体(p−1)の調製:
攪拌機を備えた反応缶中において、メトキシポリエチレングリコールモノメタクリレート(新中村化学工業(株)製「NKエステルM230G」、ラジカル重合性基がメタクリロキシ基であり、高分子鎖部分の高分子鎖がポリエチレングリコールであるもの、数平均分子量1100)40モル%、メタクリル酸1−ピレニルブチル25モル%およびメタクリル酸メチル35モル%からなる混合物100質量部と、2,2’−アゾビスイソブチロニトリル1.0質量部とを無水トルエン250質量部に溶解させて溶液を得た。次に、前記溶液を、窒素気流下、200rpmで攪拌しながら75℃まで昇温し、75℃で4時間保つことによりモノマーを重合させた。次いで、モノマーを重合させた後の前記溶液を30℃まで冷却した後、5倍当量のヘキサンに注ぎ込み、再沈殿により精製を行い、乾燥により溶媒を完全に留去して共重合体(p−1)を得た。
で表されるものであることがわかった。
単独重合体(p−2)の調製:
撹拌機を備えた反応缶中において、2−メタクリロイルオキシエチルホスホリルコリン(MPC)100質量部と、2,2’−アゾビスイソブチロニトリル0.5質量部と、n−ドデシルメルカプタン0.5質量部とをクロロホルム750質量部に溶解させて溶液を得た。次に、前記溶液を、窒素気流下、室温で15分間攪拌した後、窒素雰囲気下、200rpmで攪拌しながら55℃まで昇温し、55℃で6時間保つことによりモノマーを重合させた。次いで、モノマーを重合させた後の前記溶液を室温まで冷却した後、メタノールを投入して重合体を溶解させ、この溶液をテトラヒドロフランに注ぎ込み、再沈殿により精製を行い、80℃で12時間真空乾燥を行って単独重合体(p−2)を得た。
共重合体(p−3)の調製:
撹拌機を備えた反応缶中において、60質量%のジアリルジメチルアンモニウムクロリド水溶液97質量部および蒸留水80質量部を仕込み、塩酸でpH3〜4に調整した。次に、この溶液に、メタクリル酸1−ピレニルブチル13.68質量部をジメチルホルムアミド600質量部に溶解させた溶液と、次亜リン酸ナトリウム0.72質量部とを加えて、50℃で攪拌して溶解させて溶液を得た。次いで、前記溶液を60℃まで昇温した後、28.5質量%の過硫酸アンモニウム水溶液1.24質量部を添加した。溶液の温度を60〜65℃に4時間保持した後、28.5質量%の過硫酸アンモニウム水溶液2.48質量部をさらに添加した。その後、60℃で24時間保温した後、室温まで冷却して共重合体(p−3)を得た。
で表されるものであることがわかった。
単独重合体(p−4):
ポリ(ジアリルジメチルアンモニウムクロリド)(アルドリッチ社製、固形分濃度20質量%の水溶液、中分子量)。
単独重合体(p−5):
ポリ(4−スチレンスルホン酸ナトリウム)(アルドリッチ社製、固形分濃度30質量%の水溶液、分子量20万)。
化合物(c−1):
2−メタクリロイルオキシエチルホスホリルコリン(東京化成工業(株)製)。
化合物(c−2):
セチルトリメチルアンモニウムブロミド(東京化成工業(株)製)。
調製例2で得られた本発明にかかる双性イオンモノマー単位を含有する共重合体(b−1)25mgをイオン交換水25mlに溶解させ、得られた溶液にカーボン系ナノフィラー(a−1)5mgを添加し、超音波処理(BRANSON社製卓上型超音波洗浄機「BRANSONIC B−220」を使用、発振周波数45kHz)を1時間施して分散液を調製した。この分散液に分散しているカーボンナノ複合体において、カーボン系ナノフィラー(a−1)への共重合体(b−1)の吸着量を前記(2)に記載の方法に従って測定したところ、34.8質量部であった。また、前記カーボンナノ複合体の分散性を前記(3)および(4)に記載の方法に従って測定した。その結果を表2に示す。
共重合体(b−1)の代わりに調製例3で得られた本発明にかかるカチオン性モノマー単位を含有する共重合体(b−2)25mgを用いた以外は実施例1と同様にして分散液を調製した。この分散液に分散しているカーボンナノ複合体において、カーボン系ナノフィラー(a−1)への共重合体(b−2)の吸着量を前記(2)に記載の方法に従って測定したところ、36.5質量部であった。また、前記カーボンナノ複合体の分散性を前記(3)および(4)に記載の方法に従って測定した。その結果を表2に示す。
カーボン系ナノフィラー(a−1)の代わりにカーボン系ナノフィラー(a−2)5mgを用いた以外は実施例1と同様にして分散液を調製した。この分散液に分散しているカーボンナノ複合体において、カーボン系ナノフィラー(a−2)への本発明にかかる双性イオンモノマー単位を含有する共重合体(b−1)の吸着量を前記(2)に記載の方法に従って測定したところ、33.0質量部であった。また、前記カーボンナノ複合体の分散性を前記(3)および(4)に記載の方法に従って測定した。その結果を表2に示す。
共重合体(b−1)の代わりに調製例3で得られた本発明にかかるカチオン性モノマー単位を含有する共重合体(b−2)25mgを用いた以外は実施例3と同様にして分散液を調製した。この分散液に分散しているカーボンナノ複合体において、カーボン系ナノフィラー(a−2)への共重合体(b−2)の吸着量を前記(2)に記載の方法に従って測定したところ、32.6質量部であった。また、前記カーボンナノ複合体の分散性を前記(3)および(4)に記載の方法に従って測定した。その結果を表2に示す。
共重合体(b−1)の代わりに、調製例4で得られた共重合体(p−1)、単独重合体(p−4)、単独重合体(p−5)、化合物(c−1)または化合物(c−2)をそれぞれ25mg用いた以外は実施例1と同様にして分散液を調製した。この分散液に分散しているカーボンナノ複合体の分散性を前記(3)および(4)に記載の方法に従って測定した。その結果を表2に示す。
共重合体(b−1)の代わりに、調製例4で得られた共重合体(p−1)、調製例5で得られた単独重合体(p−2)、調製例6で得られた共重合体(p−3)、または化合物(c−2)をそれぞれ25mg用いた以外は実施例3と同様にして分散液を調製した。この分散液に分散しているカーボンナノ複合体の分散性を前記(3)および(4)に記載の方法に従って測定した。その結果を表2に示す。
Claims (6)
- カーボン系ナノフィラーと、
下記式(1):
で表される双性イオンモノマー単位およびカチオン性モノマー単位からなる群から選択される少なくとも1種のイオン性モノマー単位と、下記式(3):
で表される多環芳香族基含有ビニル系モノマー単位およびイミド環含有ビニル系モノマー単位からなる群から選択される少なくとも1種の前記イオン性モノマー単位以外のその他のモノマー単位とを含有し且つ前記カーボン系ナノフィラーに吸着している共重合体と、を備えており、
前記カーボン系ナノフィラー100質量部に対して前記共重合体の吸着量が0.1質量部以上200質量部以下であることを特徴とするナノ複合体。 - 前記イオン性モノマー単位が前記双性イオンモノマー単位であることを特徴とする請求項1に記載のナノ複合体。
- 前記イオン性モノマー単位が前記カチオン性モノマー単位であることを特徴とする請求項1に記載のナノ複合体。
- 前記その他のモノマー単位が前記式(3)で表される多環芳香族基含有ビニル系モノマー単位であることを特徴とする請求項1〜3のうちのいずれか一項に記載のナノ複合体。
- 請求項1〜4のうちのいずれか一項に記載のナノ複合体と溶媒とを含有することを特徴とする分散液。
- カーボン系ナノフィラーと、
下記式(1):
で表される双性イオンモノマー単位およびカチオン性モノマー単位からなる群から選択される少なくとも1種のイオン性モノマー単位と、下記式(3):
で表される多環芳香族基含有ビニル系モノマー単位およびイミド環含有ビニル系モノマー単位からなる群から選択される少なくとも1種の前記イオン性モノマー単位以外のその他のモノマー単位とを含有する共重合体と、
を溶媒中で混合して前記カーボン系ナノフィラー100質量部に対して0.1質量部以上200質量部以下の前記共重合体を吸着させることを特徴とするナノ複合体の製造方法。
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