JP3589740B2 - Fullerene-containing compound, resin composition and cured product thereof - Google Patents
Fullerene-containing compound, resin composition and cured product thereof Download PDFInfo
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- JP3589740B2 JP3589740B2 JP12455995A JP12455995A JP3589740B2 JP 3589740 B2 JP3589740 B2 JP 3589740B2 JP 12455995 A JP12455995 A JP 12455995A JP 12455995 A JP12455995 A JP 12455995A JP 3589740 B2 JP3589740 B2 JP 3589740B2
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- fullerene
- compound
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- containing compound
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- 150000001875 compounds Chemical class 0.000 title claims description 66
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 53
- 229910003472 fullerene Inorganic materials 0.000 title claims description 47
- 239000011342 resin composition Substances 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- -1 alkoxy compound Chemical class 0.000 description 7
- 125000005370 alkoxysilyl group Chemical group 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003495 polar organic solvent Substances 0.000 description 4
- 238000004237 preparative chromatography Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- LXGVSTJKGLJWEQ-UHFFFAOYSA-N CCC[Ti](CCC)(CCC)CCC Chemical compound CCC[Ti](CCC)(CCC)CCC LXGVSTJKGLJWEQ-UHFFFAOYSA-N 0.000 description 1
- DDRHFMPLKPRDPQ-UHFFFAOYSA-N CCC[Zr](CCC)(CCC)CCC Chemical compound CCC[Zr](CCC)(CCC)CCC DDRHFMPLKPRDPQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- MXTOFRMIIQQSOE-UHFFFAOYSA-N butane;titanium(4+) Chemical compound [Ti+4].CCC[CH2-].CCC[CH2-].CCC[CH2-].CCC[CH2-] MXTOFRMIIQQSOE-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
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- Physical Or Chemical Processes And Apparatus (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Silicon Polymers (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、光機能材料に有用なフラーレン含有化合物、該フラーレン含有化合物を必須重合成分とする高分子化合物、それらを含む樹脂組成物、及びそれを硬化してなる硬化物に関する。
【０００２】
【従来の技術】
フラーレンは、新たな非線形材料等の光機能材料として注目されている。しかしながらフラーレンは、微粉末でありそのままの状態で光機能材料に用いる事は困難であった。そこで光機能材料に用いるため、ＣＶＤ（ＣｈｅｍｉｃａｌＶａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）によるフィルム化が行われている。
【０００３】
【発明が解決しようとする課題】
しかしながら、ＣＶＤによるフィルムの調製は煩雑な操作手順を要し、歩留まりが悪いという欠点を有している。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題解決を目的に鋭意検討した結果、フラーレンにアルコキシシリル基を導入することにより、容易にフィルム等の賦形化が出来る事を見出し本発明を完成するに至った。
【０００５】
すなわち本発明は、
（１）式（１）で表されるフラーレン含有化合物、
【０００６】
【化５】
（式中、
【０００８】
【化６】
はフラーレン分子に存在する二重結合の内ｎ個が単結合になった基を表し、ｎは１以上の整数を表す。Ｒ1は直接結合または、炭素数１〜１１のアルキレン結合、あるいはアリール結合である。Ｒ2、Ｒ3、Ｒ4は、メトキシ基、エトキシ基、メチル基、あるいはエチル基を表し、互いに同一であっても異なっていてもよいが、少なくとも一つはメトキシ基、あるいはエトキシ基である。Ｘは−Ｓ−、−ＮＨ−、−ＮＲ、−Ｏ−のいずれかを表し、Ｘが−ＮＲ−である場合、Ｒは炭素１〜６のアルキル基を表す。）
（２）式（２）で表されるフラ−レン含有化合物
【００１０】
【化７】
（式中、
【００１２】
【化８】
はフラーレン分子に存在する二重結合の内ｎ個が単結合になった基を表し、ｎは１以上の整数を表す。Ｒ5は炭素数１〜３のアルキレン結合を表し、Ｒ6は炭素数１〜６のアルキレン結合を表し、Ｒ7、Ｒ8、Ｒ9はメトキシ基、エトキシ基、メチル基、あるいはエチル基を表し、互いに同一であっても異なっていてもよいが、少なくとも一つはメトキシ基、あるいはエトキシ基である。Ｘは−Ｓ−、−ＮＨ−、−ＮＲ−、−Ｏ−のいずれかを、Ｙは−Ｓ−、−ＮＨ−、−ＮＲ−、−Ｏ−のいずれかを表すがＸまたはＹが−ＮＲ−である場合は、Ｒは炭素数１〜６のアルキル基を表す。）
【００１４】
本発明のフラーレン含有化合物の合成法を以下に詳細に示す。
上記（１）または（２）記載のフラーレン含有化合物において、ｎは１以上の整数を表すが、好ましくはｎ＝１〜３０である。
本発明の出発原料としては、フラーレンであれば特に制限はなく、炭素数６０、７０、７６、７８、８２等のフラーレンが用いられるが、入手し易さから炭素数６０、７０のフラーレンが好ましい。
【００１５】
本発明におけるアルコキシシリル基は酸、あるいはアルカリ触媒下で加水分解し、ゾルゲル反応を起こすことのできる基であれば特に制限なく、メトキシ基、エトキシ基等が例示される。
【００１６】
これらアルコキシシリル基を有する化合物は、フラーレン分子中の二重結合に付加反応をさせるため、同一分子内に活性水素を有する化合物であれば特に制限はない。これら活性水素を持つ反応基の具体例として水酸基、メルカプト基、１級アミノ基、２級アミノ基等が挙げられる。
【００１７】
これらアルコキシシリル基と活性水素を有する化合物の用いうる具体例としては、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン、３−ヒドロキシプロピルトリメトキシシラン、（３−メルカプトプロピル）メチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン等が挙げられ、これらを２種以上併用する事も可能である。以下これらアルコキシシリル基と活性水素を有する化合物を化合物（Ａ）という。
【００１８】
化合物（Ａ）のフラーレンへの導入は例えば以下のようにして行う。即ち、活性水素を有する基が１級、あるいは２級アミノ基である場合には、フラーレンをトルエン、あるいはベンゼンに溶解させ溶液とする。この時の溶液のフラーレンの濃度は、通常０．１〜３重量％であり、好ましくは０．５〜２重量％である。この溶液に、化合物（Ａ）をそのまま、あるいはテトラヒドロキシフラン（ＴＨＦ）、メチルイソブチルケトン（ＭＩＢＫ）、エーテル等の非プロトン性の極性溶媒に溶解させたものを加え、１０〜１１０℃で１時間〜４８時間撹拌する事により反応を行う。化合物（Ａ）の使用量は、フラーレン１モルに対し活性水素当量で通常１〜８０当量であり、好ましくは３〜６０当量である。
【００１９】
また、反応基が水酸基、あるいはメルカプト基である場合には、例えば次のようにして反応を行う。あらかじめ脱水したＴＨＦ、ＭＩＢＫ、エーテル等の溶媒に金属ナトリウム、あるいは水素化ナトリウムを加える。そこへ化合物（Ａ）を室温、あるいは氷冷しながら滴下を行い０〜５０℃で３０分〜５時間撹拌を行い化合物（Ａ）のナトリウム塩を得る。このナトリウム塩溶液をあらかじめ脱水したトルエン、ベンゼン等の溶媒にフラーレンを溶解した溶液に、室温、あるいは氷冷しながら滴下を行い、滴下終了後１０〜８０℃で１〜４８時間撹拌する事により本発明のフラーレン含有化合物が得られる。この時のフラーレン溶液の濃度は、通常０．１〜３重量、好ましくは０．５〜２重量％である。また、この場合の化合物（Ａ）の使用量は、フラーレン１モルに対し活性水素当量で通常１〜８０当量、好ましくは３〜６０当量である。
【００２０】
本発明の高分子化合物は、上記のようにして得られた本発明フラーレン含有化合物を水中で酸あるいはアルカリを触媒としてゾルゲル反応（重合反応）を行う事により得られる。
【００２１】
本発明の高分子化合物は、本発明のフラーレン含有化合物のほかに金属アルコキシ化合物を添加し、共重合しても良い。これら金属アルコキシ化合物は水、及び必要により触媒の存在下で加水分解し、架橋反応するものであれば特に制限はなく、テトラメトキシシラン、テトラエトキシシラン、フェニルトリエトキシシラン、メチルトリエトキシシラン、ジフェニルジエトキシシラン、フェニルメチルジエトキシシラン、ジメチルジエトキシシラン、テトラプロピルチタン、テトラブチルチタン、テトラプロピルジルコニウム、テトラプロピルアルミニウム等が用いうる具体例として挙げられる。これら金属アルコキシ化合物の使用量は、フラーレン含有化合物中のアルコキシシリル基１モルに対し０．１〜３００モルであり、好ましくは１〜１００モルである。
【００２２】
本発明の高分子化合物の合成に用いられる水の使用量は、金属アルコキシ基が加水分解を起こすのに充分な量であれば特に制限はないが金属アルコキシ基１モルに対し０．１〜３０モルであり、好ましくは０．５〜２５モルである。この場合の金属アルコキシル基とは、本発明のフラーレン含有化合物中のアルコキシシリル基及び必要により用いる金属アルコキシ化合物中の金属アルコキシ基の両者をさす。以下同様。
【００２３】
本発明の高分子化合物の合成に用いられる触媒は、金属アルコキシ基の加水分解を促進させるものであれば特に制限はないが、無機酸として塩酸、硫酸、硝酸等が、有機酸として酢酸、シュウ酸等が、無機アルカリとしてアンモニア、水酸化ナトリウム、水酸化カリウム等が用いうる具体例として挙げられる。これら、触媒の使用量は金属アルコキシ基に対し０．００９〜３当量である。
【００２４】
本発明の高分子化合物の合成においては必要によりアルコール類を用いてもよい。アルコール類としては、室温で液体であれば特に制限はないが、メタノール、エタノールが好ましい具体例として挙げられる。これらアルコール類の使用量は本発明のフラーレン含有化合物及び必要により用いる金属アルコキシ化合物の合計重量１００重量部に対し、通常１０〜１００００重量部、好ましくは８０〜５０００重量部である。
【００２５】
また、フラーレン含有化合物と水、触媒との相溶性を向上させる目的で他の極性有機溶媒を添加しても良い。これら有機溶媒の用いうる具体例としてはＴＨＦ、エーテル等が挙げられる。
【００２６】
本発明の高分子化合物の合成は、上記各成分を所定の割合で均一に混合した混合物を１０〜８０℃の条件下で１〜２００時間撹拌する事により行う。
【００２７】
本発明の樹脂組成物は、本発明のフラーレン含有化合物及び／または本発明の高分子化合物を含有する。本発明の樹脂組成物が本発明のフラーレン含有化合物を含有する場合、本発明の樹脂組成物は、水及び上記触媒を含有する。
また、更に必要により上記の金属アルコキシ化合物、アルコール類、極性有機溶媒を含有してもよい。これら水、触媒、金属アルコキシ化合物、アルコール類、極性有機溶媒の使用量は、上記の本発明の高分子化合物を得る場合と同様である。
また、上記のようにして得られた本発明の高分子化合物を含有する溶液は、そのまま本発明の樹脂組成物とすることができる。この場合必要により更に溶媒（水、アルコール類、極性有機溶媒）を加えてもよいし、溶媒を加熱等により必要量除去してもよい。更に必要により本発明のフラーレン含有化合物、金属アルコキシ化合物を添加してもよい。
【００２８】
本発明の硬化物は、本発明の樹脂組成物を加熱あるいは凍結乾燥する事により得られる。加熱乾燥を行う場合、乾燥温度は２０〜２００℃が好ましい。また、本発明の樹脂組成物を基盤上にキャストし、加熱あるいは凍結乾燥してもよい。この場合、本発明の樹脂組成物は、水等の溶媒を含有する液状であるのが好ましい。また、得られた硬化物を不活性ガス中で加熱しガラス化させても良い。このときの加熱温度は６００〜１０００℃が好ましい。
【００２９】
以下に実施例を挙げて本発明を更に具体的に説明する。
【００３０】
実施例１
温度計、撹拌装置、滴下ロート、及び冷却管を取り付けた２００ｍｌの四口フラスコに炭素数６０のフラーレン（フラーレンＣ６０、以下同様）１００ｍｇ、トルエン１００ｍｌを入れ室温で撹拌しトルエン溶液とした。そこに、３−（２−アミノエチルアミノプロピル）ジメトキシメチルシランの２０重量％ＴＨＦ溶液１５ｍｌを滴下ロートから徐々に滴下した。滴下終了後、５０℃で４８時間撹拌し反応させた。反応液を分液ロートに移し、トルエンを１００ｍｌ加え、油層を水で数回洗浄した。得られたトルエン溶液を無水硫酸マグネシウムで脱水後、溶媒を減圧蒸留で除去した。得られた固形物を再びトルエンに溶解させ、分取クロマトグラフィーにより未反応物から分離精製後、溶媒を減圧蒸留で除去し茶色の粉体（本発明のフラーレン含有化合物、以下化合物（Ａ−１）という。）１８２ｍｇを得た。
【００３１】
得られた粉体は赤外線吸収スペクトル分析の結果、５７６ｃｍ−１と５２７ｃｍ−１にフラーレンＣ６０に由来する吸収、１０６０ｃｍ−１にＳｉ−Ｏ−Ｃに由来する吸収、１１００ｃｍ−１にＣ−Ｎに由来する吸収、１２６０ｃｍ−１にＳｉ−ＣＨ３に由来する吸収、３０６０ｃｍ−１にＣ−Ｈに由来する吸収、３２００ｃｍ−１にＮＨ−Ｃに由来する吸収がみられた。
【００３２】
また、１ Ｈ−ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ（ジメチルスルホキシド））による分析の結果、δ＝０．９２（ｓ，３Ｈ，ＣＨ３ ），１．２３（ｔ，２Ｈ，ＳｉＣＨ２ ），１．３２（ｍ，２Ｈ，ＣＨ２ ），２．５１（ｍ，２Ｈ，ＣＨ２ ），３．４５（ｓ，３Ｈ，ＣＨ３ ），３．６３（ｔ，２Ｈ，ＣＨ２ ），４．８３（ｔ，１Ｈ，ＮＨ），６．４５（ｓ，１Ｈ，Ｃ６０ Ｃ−Ｈ）であった。
【００３３】
また、１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＤＭＳＯ）による分析の結果、δ＝０．４８（ＳｉＣＨ３ ），１．５４（ＳｉＣＨ２ ），２３．６１（ＣＨ２ ），２６．８７（ＣＨ３ ），４８．１２（ＮＨＣＨ２ ），４９．３６（ＮＨＣＨ２ ），５０．０３（ＮＨＣＨ２ ），６２．６７（ＳｉＯＣＨ２ ），６５．４２，６７．５５，６８．６６（Ｃ６０ ＣＨ），１４１．２２〜１４４．８９（Ｃ６０Ｃ）であった。その結果、化合物（Ａ−１）は式（３）で表される構造であった。
【００３４】
【化９】
（式中ｎは整数を表し（以下式（４）〜（６）においても同じ）、
【００３６】
【化１０】
は、フラーレンＣ６０中に存在する二重結合のうちｎ個が単結合になった基を表す（以下式（４）〜（６）においても同じ）。）
【００３８】
実施例２
温度計、撹拌装置、滴下ロート、及び冷却管を取り付けた２００ｍｌの四口フラスコを窒素置換した後、炭素数６０のフラーレン１００ｍｇ、脱水トルエン１００ｍｌを投入し、室温で撹拌し溶解させた。そこに、あらかじめＮａＨでナトリウムメトキシドとした３−ヒドロキシプロピルトリエトキシシランの２０重量％ＴＨＦ溶液１２ｍｌを滴下ロートから徐々に滴下した。滴下終了後、２５℃で１２時間撹拌し反応させた。反応液を分液ロートに移し、トルエンを１００ｍｌ加え、油層を水で数回洗浄した。トルエン溶液を無水硫酸マグネシウムで脱水後、溶媒を減圧蒸留で除去した。得られた固形物を再びトルエンに溶解させ、分取クロマトグラフィーにより未反応物から分離精製後、溶媒を減圧蒸留で除去し黒色の粉体（本発明のフラーレン含有化合物、以下化合物（Ａ−２）という。）１７６ｍｇを得た。
【００３９】
得られた粉体は赤外線吸収スペクトル分析の結果、５７６ｃｍ−１と５２７ｃｍ−１にフラーレンＣ６０に由来する吸収、１０６０ｃｍ−１にＳｉ−Ｏ−Ｃに由来する吸収、１０９６ｃｍ−１、１３００ｃｍ−１にＣ−Ｏ−Ｃに由来する吸収、２９５０ｃｍ−１にＣ−Ｈに由来する吸収がみられた。
【００４０】
また、１ Ｈ−ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ）による分析の結果、δ＝０．５８（ｔ，２Ｈ，ＳｉＣＨ２ ），１．２１（ｍ，９Ｈ，ＣＨ３ ），１．４８（ｍ，２Ｈ，ＣＨ２ ），３．２１（ｔ，２Ｈ，ＣＨ２ ），３．４２（ｍ，６Ｈ，ＣＨ２ ），６．７８（ｓ，１Ｈ，Ｃ６０ Ｃ−Ｈ）であった。
【００４１】
また、１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＤＭＳＯ）による分析の結果、δ＝０．４８（ＳｉＣＨ２ ），１８．９８（ＣＨ２ ），２６．７１（ＣＨ３ ），６２．６７（ＳｉＯＣＨ２ ），７２．４２（ＯＣＨ２ ），６７．４２，６７．６５，６７．８９，６８．４７，６９．８１（Ｃ６０ ＣＨ），１４０．３３〜１４５．７２（Ｃ６０Ｃ），であった。その結果、化合物（Ａ−２）は式（４）で表される構造であった。
【００４２】
【化１１】
実施例３
温度計、撹拌装置、滴下ロート、及び冷却管を取り付けた２００ｍｌの四口フラスコに炭素数６０のフラーレン１００ｍｇ、トルエン１００ｍｌを入れ室温で撹拌しトルエン溶液とした。そこに、３−アミノプロピルメチルジエトキシシランの２０重量％ＴＨＦ溶液１５ｍｌを滴下ロートから徐々に滴下した。滴下終了後、５０℃で４８時間撹拌し反応させた。反応液を分液ロートに移し、トルエンを１００ｍｌ加え、油層を水で数回洗浄した。得られたトルエン溶液を無水硫酸マグネシウムで脱水後、凍結乾燥を行った。得られた固形物を再びトルエンに溶解させ、分取クロマトグラフィーにより未反応物から精製分離後、凍結乾燥し茶色の粉体（本発明のフラーレン含有化合物、以下化合物（Ａ−３）という。）１３１ｍｇを得た。
【００４４】
得られた粉体は赤外線吸収スペクトル分析の結果、５７６ｃｍ−１と５２７ｃｍ−１にフラーレンＣ６０に由来する吸収、１０８０ｃｍ−１にＳｉ−Ｏ−Ｃに由来する吸収、１１１０ｃｍ−１にＣ−Ｎに由来する吸収、１２５０ｃｍ−１にＳｉ−ＣＨ３に由来する吸収、３０４０ｃｍ−１にＣ−Ｈに由来する吸収、３２１０ｃｍ−１にＮＨ−Ｃに由来する吸収がみられた。
【００４５】
また、１ Ｈ−ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ）による分析の結果、δ＝０．９４（ｓ，３Ｈ，ＳｉＣＨ３ ），１．１２（ｔ，２Ｈ，ＳｉＣＨ２ ），１．１９（ｔ，３Ｈ，ＣＨ３ ），２．０４（ｍ，２Ｈ，ＣＨ２ ），３．１８（ｍ，２Ｈ，ＮＨＣＨ２ ），３．２３（ｔ，２Ｈ，ＳｉＯＣＨ２ ），３．３０（ｍ，２Ｈ，ＮＨＣＨ２ ），３．４２（ｍ，２Ｈ，ＣＨ２ ），４．８３（ｍ，１Ｈ，ＮＨ），６．２９（ｓ，１Ｈ，Ｃ６０ Ｃ−Ｈ）であった。
【００４６】
また、１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＤＭＳＯ）による分析の結果、δ＝０．４８（ＳｉＣＨ３ ），１．５４（ＳｉＣＨ２ ），２３．６１（ＣＨ２ ），２６．８７（ＣＨ３ ），４８．１２（ＮＨＣＨ２ ），６２．６７（ＳｉＯＣＨ２ ），６５．４２，６７．５５，６８．６６（Ｃ６０ ＣＨ），１４１．２２〜１４４．８９（Ｃ６０Ｃ）であった。その結果、化合物（Ａ−３）は、式（５）で表される構造であった。
【００４７】
【化１２】
実施例４
温度計、撹拌装置、滴下ロート、及び冷却管を取り付けた２００ｍｌの四口フラスコを窒素置換した後、炭素数６０のフラーレン１００ｍｇ、脱水トルエン１００ｍｌを投入し、室温で撹拌し溶解させた。そこに、あらかじめＮａＨでナトリウムメトキシドとした３−メルカプトプロピルメチルジエトキシシランの２０重量％ＴＨＦ溶液１２ｍｌを滴下ロートから徐々に滴下した。滴下終了後、２５℃で１２時間撹拌し反応させた。反応液を分液ロートに移し、トルエンを１００ｍｌ加え、油層を水で数回洗浄した。得られたトルエン溶液を無水硫酸マグネシウムで脱水後、凍結乾燥を行った。得られた固形物を再びトルエンに溶解させ、分取クロマトグラフィーにより未反応物から精製分離後、凍結乾燥し黒緑色の粉体（本発明のフラーレン含有化合物、以下化合物（Ａ−４）という。）１２５ｍｇを得た。
【００４９】
得られた粉体は赤外線吸収スペクトル分析の結果、５７６ｃｍ−１と５２７ｃｍ−１にフラーレンＣ６０に由来する吸収、１０５３ｃｍ−１にＳｉ−Ｏ−Ｃに由来する吸収、１２５３ｃｍ−１にＳｉ−ＣＨ３に由来する吸収、２９４０ｃｍ−１にＣ−Ｈに由来する吸収がみられた。
【００５０】
また、１ Ｈ−ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ）による分析の結果、δ＝０．９１（ｓ，３Ｈ，Ｓｉ−ＣＨ３ ），０．９８（ｔ，２Ｈ，ＳｉＣＨ２ ），１．２２（ｔ，３Ｈ，ＣＨ３ ），１．５９（ｍ，２Ｈ，ＣＨ２ ），２．６４（ｔ，２Ｈ，ＳＣＨ２ ），３．３１（ｔ，２Ｈ，ＳｉＯＣＨ２ ），６．１１（ｓ，１Ｈ，Ｃ６０ Ｃ−Ｈ）であった。
【００５１】
また、１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＤＭＳＯ）による分析の結果、δ＝０．４８（ＳｉＣＨ３ ），０．９５（ＳｉＣＨ２ ），１５．６１（ＣＨ２ ），２６．８７（ＣＨ３ ），３８．１２（ＳＣＨ２ ），６２．５５（ＳｉＯＣＨ２ ），６５．４２，６６．４５，６７．４１，６８．３３，６８．７１（Ｃ６０ ＣＨ），１４１．０３〜１４５．３６（Ｃ６０Ｃ）であった。その結果、化合物（Ａ−４）は式（６）で表される構造であった。
【００５２】
【化１３】
実施例５
温度計、撹拌装置、及び冷却管を取り付けた１００ｍｌの三口フラスコに実施例１で得られた化合物（Ａ−１）０．１ｇ、テトラエトキシシラン３ｇ、水酸化ナトリウム１．０ｇ，水２０ｇ，エタノール３０ｍｌを投入し、５０℃で７２時間撹拌しゾルゲル反応を行い、本発明の高分子化合物を得た。得られた反応液をガラス基板上にバーコーターを用いて塗布し、７０℃で２４時間乾燥し、膜厚０．３ｍｍの硬化膜（Ｂ−１）を得た。
【００５４】
実施例６
温度計、撹拌装置、及び冷却管を取り付けた１００ｍｌの三口フラスコに実施例２で得られた化合物（Ａ−２）０．１ｇ、テトラエトキシシラン３ｇ、１２Ｎ塩酸２．３ｍｌ、水１８ｇ、ＴＨＦ１０ｍｌ、エタノール２０ｍｌを投入し、５０℃で９６時間撹拌しゾルゲル反応を行い、本発明の高分子化合物を得た。得られた反応液をガラス基板上にバーコーターを用いて塗布し、７０℃で２４時間乾燥し、膜厚０．３ｍｍの硬化膜（Ｂ−２）を得た。
【００５５】
実施例７
温度計、撹拌装置、及び冷却管を取り付けた１００ｍｌの三口フラスコに実施例３で得られた化合物（Ａ−３）０．１ｇ、テトラエトキシシラン３ｇ、ジフェニルジエトキシシラン１ｇ、水酸化ナトリウム１．３ｇ、水２０ｇ、エタノール３０ｍｌを投入し、６０℃で７２時間撹拌しゾルゲル反応を行い、本発明の高分子化合物を得た。得られた反応液をガラス基板上にバーコーターを用いて塗布し、５０℃で２４時間乾燥し、膜厚０．３ｍｍの硬化膜（Ｂ−３）を得た。
【００５６】
実施例８
温度計、撹拌装置、及び冷却管を取り付けた１００ｍｌの三口フラスコに実施例４で得られた化合物（Ａ−４）０．１ｇ、テトラエトキシシラン４ｇ、１２Ｎ塩酸２．１ｇ、水２０ｇ、ＴＨＦ１０ｍｌ、エタノール２０ｍｌを投入し、６０℃で８０時間撹拌しゾルゲル反応を行い、本発明の高分子化合物を得た。得られた反応液をガラス基板上にバーコーターを用いて塗布し、７０℃で２４時間乾燥し、膜厚０．３ｍｍの硬化膜（Ｂ−４）を得た。
【００５７】
試験例
実施例５〜８で得られた硬化膜（Ｂ−５），（Ｂ−６），（Ｂ−７），（Ｂ−８）を分光光度計（Ｕ−３２１０形自己分光光度計（日立社製））を用いての光吸収スペクトルの測定を行った。測定結果を表１に示す。
サンプル 吸収波長（ｎｍ）
硬化膜（Ｂ−１） ３２７，２５６，２２０
硬化膜（Ｂ−２） ３２５，２８６，２１８
硬化膜（Ｂ−３） ３２４，２６１，２２１，２０５，１９０
硬化膜（Ｂ−４） ３２０，２６８，２５７，２１５
【００５８】
【発明の効果】
本発明のフラーレン含有化合物は、容易にフラーレン分子を含有する硬化膜を得る事が出来、光触媒、３次非線形光学材料等の光機能材料として有用である。[0001]
[Industrial applications]
The present invention relates to a fullerene-containing compound useful for an optical functional material, a polymer compound containing the fullerene-containing compound as an essential polymerization component, a resin composition containing them, and a cured product obtained by curing the same.
[0002]
[Prior art]
Fullerene has attracted attention as an optical functional material such as a new nonlinear material. However, fullerene is a fine powder, and it is difficult to use it as it is as an optical functional material. Therefore, a film is formed by CVD (Chemical Vapor Deposition) in order to use it as an optical functional material.
[0003]
[Problems to be solved by the invention]
However, preparation of a film by CVD requires a complicated operation procedure, and has a drawback that the yield is poor.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies for the purpose of solving the above-mentioned problems, and as a result, have found that by introducing an alkoxysilyl group into fullerene, it is possible to easily shape a film or the like, thereby completing the present invention.
[0005]
That is, the present invention
(1) a fullerene-containing compound represented by the formula (1),
[0006]
Embedded image
(Where
[0008]
Embedded image
Represents a group in which n of the double bonds present in the fullerene molecule have become a single bond, and n represents an integer of 1 or more. R 1 is a direct bond, an alkylene bond having 1 to 11 carbon atoms, or an aryl bond. R 2 , R 3 , and R 4 represent a methoxy group, an ethoxy group, a methyl group, or an ethyl group, and may be the same or different, but at least one is a methoxy group or an ethoxy group . X represents any of -S-, -NH-, -NR, -O-, and when X is -NR-, R represents an alkyl group having 1 to 6 carbon atoms. )
(2) Fullerene-containing compound represented by formula (2)
Embedded image
(Where
[0012]
Embedded image
Represents a group in which n of the double bonds present in the fullerene molecule have become a single bond, and n represents an integer of 1 or more. R 5 represents an alkylene bond having 1 to 3 carbon atoms, R 6 represents an alkylene bond having 1 to 6 carbon atoms, and R 7 , R 8 , and R 9 represent a methoxy group, an ethoxy group, a methyl group, or an ethyl group. And they may be the same or different, but at least one is a methoxy group or an ethoxy group. X represents any one of -S-, -NH-, -NR-, -O-, and Y represents any one of -S-, -NH-, -NR-, -O-, wherein X or Y is- When it is NR-, R represents an alkyl group having 1 to 6 carbon atoms. )
[0014]
The method for synthesizing the fullerene-containing compound of the present invention will be described in detail below.
In the fullerene-containing compound according to the above (1) or (2), n represents an integer of 1 or more, preferably n = 1 to 30.
The starting material of the present invention is not particularly limited as long as it is a fullerene, and a fullerene having 60, 70, 76, 78, 82 or the like is used. However, a fullerene having 60 or 70 carbon atoms is preferable in terms of availability. .
[0015]
The alkoxysilyl group in the present invention is not particularly limited as long as it can be hydrolyzed under an acid or alkali catalyst to cause a sol-gel reaction, and examples thereof include a methoxy group and an ethoxy group.
[0016]
These compounds having an alkoxysilyl group are not particularly limited as long as they have an active hydrogen in the same molecule because they cause an addition reaction to a double bond in a fullerene molecule. Specific examples of the reactive group having active hydrogen include a hydroxyl group, a mercapto group, a primary amino group, and a secondary amino group.
[0017]
Specific examples of the compounds having an alkoxysilyl group and active hydrogen that can be used include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-hydroxypropyltrimethoxysilane, (3-mercaptopropyl) methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. May be used in combination of two or more. Hereinafter, these compounds having an alkoxysilyl group and active hydrogen are referred to as compound (A).
[0018]
The compound (A) is introduced into fullerene, for example, as follows. That is, when the group having active hydrogen is a primary or secondary amino group, fullerene is dissolved in toluene or benzene to form a solution. The concentration of fullerene in the solution at this time is usually 0.1 to 3% by weight, preferably 0.5 to 2% by weight. To this solution, the compound (A) as it is or a solution prepared by dissolving the compound (A) in an aprotic polar solvent such as tetrahydroxyfuran (THF), methyl isobutyl ketone (MIBK), or ether is added, and the mixture is heated at 10 to 110 ° C. for 1 hour. The reaction is performed by stirring for ~ 48 hours. The amount of compound (A) to be used is generally 1 to 80 equivalents, preferably 3 to 60 equivalents, in terms of active hydrogen equivalent per mol of fullerene.
[0019]
When the reactive group is a hydroxyl group or a mercapto group, the reaction is performed, for example, as follows. Metallic sodium or sodium hydride is added to a solvent such as THF, MIBK, or ether which has been dehydrated in advance. The compound (A) is added dropwise thereto at room temperature or with ice cooling, and the mixture is stirred at 0 to 50 ° C. for 30 minutes to 5 hours to obtain a sodium salt of the compound (A). This sodium salt solution is added dropwise to a solution in which fullerene is dissolved in a solvent such as toluene or benzene, which has been dehydrated in advance, at room temperature or with ice cooling, and after completion of the addition, the mixture is stirred at 10 to 80 ° C. for 1 to 48 hours. The fullerene-containing compound of the invention is obtained. The concentration of the fullerene solution at this time is usually 0.1 to 3% by weight, preferably 0.5 to 2% by weight. In this case, the amount of the compound (A) to be used is generally 1 to 80 equivalents, preferably 3 to 60 equivalents in terms of active hydrogen equivalent per mol of fullerene.
[0020]
The polymer compound of the present invention can be obtained by subjecting the fullerene-containing compound of the present invention obtained as described above to a sol-gel reaction (polymerization reaction) in water using an acid or an alkali as a catalyst.
[0021]
The polymer compound of the present invention may be copolymerized by adding a metal alkoxy compound in addition to the fullerene-containing compound of the present invention. These metal alkoxy compounds are not particularly limited as long as they hydrolyze and crosslink in the presence of water and, if necessary, a catalyst. Tetramethoxysilane, tetraethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, diphenyl Specific examples that can be used include diethoxysilane, phenylmethyldiethoxysilane, dimethyldiethoxysilane, tetrapropyltitanium, tetrabutyltitanium, tetrapropylzirconium, and tetrapropylaluminum. The amount of the metal alkoxy compound to be used is 0.1 to 300 mol, preferably 1 to 100 mol, per 1 mol of the alkoxysilyl group in the fullerene-containing compound.
[0022]
The amount of water used for the synthesis of the polymer compound of the present invention is not particularly limited as long as it is an amount sufficient to cause hydrolysis of the metal alkoxy group. Mol, preferably 0.5 to 25 mol. In this case, the metal alkoxyl group refers to both the alkoxysilyl group in the fullerene-containing compound of the present invention and the metal alkoxy group in the metal alkoxy compound used as required. The same applies hereinafter.
[0023]
The catalyst used for the synthesis of the polymer compound of the present invention is not particularly limited as long as it promotes the hydrolysis of the metal alkoxy group, but hydrochloric acid, sulfuric acid, nitric acid and the like as inorganic acids, and acetic acid and sulfur as organic acids. Acids and the like are specific examples in which ammonia, sodium hydroxide, potassium hydroxide and the like can be used as the inorganic alkali. These catalysts are used in an amount of 0.009 to 3 equivalents to the metal alkoxy group.
[0024]
In the synthesis of the polymer compound of the present invention, alcohols may be used as necessary. The alcohol is not particularly limited as long as it is a liquid at room temperature, but preferred specific examples include methanol and ethanol. The amount of the alcohol to be used is generally 10 to 10000 parts by weight, preferably 80 to 5000 parts by weight, based on 100 parts by weight of the total weight of the fullerene-containing compound of the present invention and the metal alkoxy compound used as required.
[0025]
Further, another polar organic solvent may be added for the purpose of improving the compatibility between the fullerene-containing compound, water and the catalyst. Specific examples of the use of these organic solvents include THF, ether and the like.
[0026]
The synthesis of the polymer compound of the present invention is carried out by stirring a mixture obtained by uniformly mixing the above components at a predetermined ratio at a temperature of 10 to 80 ° C. for 1 to 200 hours.
[0027]
The resin composition of the present invention contains the fullerene-containing compound of the present invention and / or the polymer compound of the present invention. When the resin composition of the present invention contains the fullerene-containing compound of the present invention, the resin composition of the present invention contains water and the above catalyst.
Further, if necessary, the above-mentioned metal alkoxy compound, alcohols and polar organic solvent may be contained. The amounts of these water, catalyst, metal alkoxy compound, alcohol, and polar organic solvent used are the same as in the case of obtaining the above-mentioned polymer compound of the present invention.
Further, the solution containing the polymer compound of the present invention obtained as described above can be directly used as the resin composition of the present invention. In this case, if necessary, a solvent (water, alcohol, polar organic solvent) may be further added, or the necessary amount of the solvent may be removed by heating or the like. If necessary, the fullerene-containing compound and the metal alkoxy compound of the present invention may be added.
[0028]
The cured product of the present invention can be obtained by heating or freeze-drying the resin composition of the present invention. When performing heat drying, the drying temperature is preferably from 20 to 200 ° C. Further, the resin composition of the present invention may be cast on a substrate and heated or freeze-dried. In this case, the resin composition of the present invention is preferably a liquid containing a solvent such as water. Further, the obtained cured product may be heated in an inert gas to be vitrified. The heating temperature at this time is preferably from 600 to 1000C.
[0029]
Hereinafter, the present invention will be described more specifically with reference to examples.
[0030]
Example 1
A 200 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser was charged with 100 mg of fullerene having 60 carbon atoms (fullerene C60, the same applies hereinafter) and 100 ml of toluene, and stirred at room temperature to obtain a toluene solution. Thereto, 15 ml of a 20% by weight THF solution of 3- (2-aminoethylaminopropyl) dimethoxymethylsilane was gradually dropped from a dropping funnel. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 48 hours to be reacted. The reaction solution was transferred to a separating funnel, 100 ml of toluene was added, and the oil layer was washed several times with water. After dehydrating the obtained toluene solution with anhydrous magnesium sulfate, the solvent was removed by distillation under reduced pressure. The obtained solid was dissolved again in toluene, separated and purified from unreacted substances by preparative chromatography, and then the solvent was removed by distillation under reduced pressure to obtain a brown powder (fullerene-containing compound of the present invention; hereinafter, compound (A-1)). 182 mg.
[0031]
The resulting powder infrared absorption spectrum analysis of the results, the absorption derived from fullerene C60 to 576cm -1 and 527cm -1, absorption derived from Si-O-C in 1060 cm -1, the C-N to 1100 cm -1 derived absorption, absorption derived from Si-CH 3 in 1260 cm -1, absorption derived from CH to 3060cm -1, absorption derived from NH-C to 3200 cm -1 was observed.
[0032]
In addition, as a result of analysis by 1 H-NMR (400 MHz, DMSO (dimethyl sulfoxide)), δ = 0.92 (s, 3H, CH 3 ), 1.23 (t, 2H, SiCH 2 ), 1.32 ( m, 2H, CH 2), 2.51 (m, 2H, CH 2), 3.45 (s, 3H, CH 3), 3.63 (t, 2H, CH 2), 4.83 (t, 1H, NH), 6.45 (s, 1H, C60 CH).
[0033]
Further, as a result of analysis by 13 C-NMR (100 MHz, DMSO), δ = 0.48 (SiCH 3 ), 1.54 (SiCH 2 ), 23.61 (CH 2 ), 26.87 (CH 3 ), 48.12 (NHCH 2 ), 49.36 (NHCH 2 ), 50.03 (NHCH 2 ), 62.67 (SiOCH 2 ), 65.42, 67.55, 68.66 (C60 CH), 141. 22 to 144.89 (C60C). As a result, compound (A-1) had a structure represented by formula (3).
[0034]
Embedded image
(In the formula, n represents an integer (the same applies to formulas (4) to (6) below),
[0036]
Embedded image
Represents a group in which n of the double bonds present in the fullerene C60 have become single bonds (the same applies to the following formulas (4) to (6)). )
[0038]
Example 2
After replacing a 200-ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with nitrogen, 100 mg of fullerene having 60 carbon atoms and 100 ml of dehydrated toluene were added, and the mixture was stirred and dissolved at room temperature. To this, 12 ml of a 20% by weight THF solution of 3-hydroxypropyltriethoxysilane previously converted to sodium methoxide with NaH was gradually dropped from a dropping funnel. After the completion of the dropwise addition, the mixture was reacted by stirring at 25 ° C. for 12 hours. The reaction solution was transferred to a separating funnel, 100 ml of toluene was added, and the oil layer was washed several times with water. After dehydrating the toluene solution with anhydrous magnesium sulfate, the solvent was removed by distillation under reduced pressure. The obtained solid was dissolved again in toluene, separated and purified from unreacted substances by preparative chromatography, and then the solvent was removed by distillation under reduced pressure to obtain a black powder (fullerene-containing compound of the present invention; hereinafter referred to as compound (A-2)). ) Was obtained.
[0039]
The resulting powder infrared absorption spectrum analysis of the results, the absorption derived from fullerene C60 to 576cm -1 and 527cm -1, absorption derived from Si-O-C in 1060cm -1, 1096cm -1, to 1300 cm -1 Absorption derived from C—O—C and absorption derived from C—H were observed at 2950 cm −1 .
[0040]
In addition, as a result of analysis by 1 H-NMR (400 MHz, DMSO), δ = 0.58 (t, 2H, SiCH 2 ), 1.21 (m, 9H, CH 3 ), 1.48 (m, 2H, CH 2), 3.21 (t, 2H, CH 2), 3.42 (m, 6H, CH 2), was 6.78 (s, 1H, C60 CH ).
[0041]
Further, as a result of analysis by 13 C-NMR (100 MHz, DMSO), δ = 0.48 (SiCH 2 ), 18.98 (CH 2 ), 26.71 (CH 3 ), 62.67 (SiOCH 2 ), 72.42 (OCH 2), 67.42,67.65,67.89,68.47,69.81 ( C60 CH), 140.33~145.72 (C60C), was. As a result, compound (A-2) had a structure represented by formula (4).
[0042]
Embedded image
Example 3
A 200 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser was charged with 100 mg of fullerene having 60 carbon atoms and 100 ml of toluene, and stirred at room temperature to obtain a toluene solution. Thereto, 15 ml of a 20% by weight THF solution of 3-aminopropylmethyldiethoxysilane was gradually dropped from a dropping funnel. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 48 hours to be reacted. The reaction solution was transferred to a separating funnel, 100 ml of toluene was added, and the oil layer was washed several times with water. The obtained toluene solution was dehydrated with anhydrous magnesium sulfate, and then freeze-dried. The obtained solid was dissolved again in toluene, purified and separated from unreacted substances by preparative chromatography, and then freeze-dried to obtain a brown powder (fullerene-containing compound of the present invention, hereinafter referred to as compound (A-3)). 131 mg were obtained.
[0044]
The resulting powder infrared absorption spectrum analysis of the results, the absorption derived from fullerene C60 to 576cm -1 and 527cm -1, absorption derived from Si-O-C in 1080 cm -1, the C-N to 1110 cm -1 At 1,250 cm −1 , absorption attributable to Si—CH 3 was observed, at 3040 cm −1 , absorption attributable to C—H, and at 3210 cm −1 , absorption attributable to NH—C was observed.
[0045]
Further, as a result of analysis by 1 H-NMR (400 MHz, DMSO), δ = 0.94 (s, 3H, SiCH 3 ), 1.12 (t, 2H, SiCH 2 ), 1.19 (t, 3H, CH 3), 2.04 (m, 2H, CH 2), 3.18 (m, 2H, NHCH 2), 3.23 (t, 2H, SiOCH 2), 3.30 (m, 2H, NHCH 2 ), 3.42 (m, 2H, CH 2), 4.83 (m, 1H, NH), was 6.29 (s, 1H, C60 CH ).
[0046]
Further, as a result of analysis by 13 C-NMR (100 MHz, DMSO), δ = 0.48 (SiCH 3 ), 1.54 (SiCH 2 ), 23.61 (CH 2 ), 26.87 (CH 3 ), 48.12 (NHCH 2 ), 62.67 (SiOCH 2 ), 65.42, 67.55, 68.66 (C60 CH), 141.22 to 144.89 (C60C). As a result, compound (A-3) had a structure represented by formula (5).
[0047]
Embedded image
Example 4
After replacing a 200-ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with nitrogen, 100 mg of fullerene having 60 carbon atoms and 100 ml of dehydrated toluene were added, and the mixture was stirred and dissolved at room temperature. To this, 12 ml of a 20% by weight THF solution of 3-mercaptopropylmethyldiethoxysilane previously converted to sodium methoxide with NaH was gradually dropped from a dropping funnel. After the completion of the dropwise addition, the mixture was reacted by stirring at 25 ° C. for 12 hours. The reaction solution was transferred to a separating funnel, 100 ml of toluene was added, and the oil layer was washed several times with water. The obtained toluene solution was dehydrated with anhydrous magnesium sulfate, and then freeze-dried. The obtained solid was dissolved again in toluene, purified and separated from unreacted substances by preparative chromatography, freeze-dried, and then turned into a blackish green powder (fullerene-containing compound of the present invention, hereinafter referred to as compound (A-4)). ) 125 mg.
[0049]
The resulting powder infrared absorption spectrum analysis of the results, the absorption derived from fullerene C60 to 576cm -1 and 527cm -1, absorption derived from Si-O-C in 1053cm -1, Si-CH 3 in 1253Cm -1 , And absorption at 2940 cm −1 due to C—H.
[0050]
Also, as a result of analysis by 1 H-NMR (400 MHz, DMSO), δ = 0.91 (s, 3H, Si—CH 3 ), 0.98 (t, 2H, SiCH 2 ), 1.22 (t, 3H, CH 3), 1.59 ( m, 2H, CH 2), 2.64 (t, 2H, SCH 2), 3.31 (t, 2H, SiOCH 2), 6.11 (s, 1H, C60 CH).
[0051]
As a result of analysis by 13 C-NMR (100 MHz, DMSO), δ = 0.48 (SiCH 3 ), 0.95 (SiCH 2 ), 15.61 (CH 2 ), 26.87 (CH 3 ), 38.12 (SCH 2), 62.55 ( SiOCH 2), 65.42,66.45,67.41,68.33,68.71 (C60 CH), 141.03~145.36 (C60C) Met. As a result, the compound (A-4) had a structure represented by the formula (6).
[0052]
Embedded image
Example 5
0.1 g of the compound (A-1) obtained in Example 1, 3 g of tetraethoxysilane, 1.0 g of sodium hydroxide, 20 g of water, 20 g of ethanol in a 100 ml three-necked flask equipped with a thermometer, a stirrer, and a condenser. 30 ml was charged, and the mixture was stirred at 50 ° C. for 72 hours to perform a sol-gel reaction, thereby obtaining a polymer compound of the present invention. The obtained reaction liquid was applied on a glass substrate using a bar coater and dried at 70 ° C. for 24 hours to obtain a cured film (B-1) having a thickness of 0.3 mm.
[0054]
Example 6
0.1 g of the compound (A-2) obtained in Example 2, 3 g of tetraethoxysilane, 2.3 ml of 12N hydrochloric acid, 18 g of water, 10 ml of THF were placed in a 100 ml three-necked flask equipped with a thermometer, a stirrer, and a condenser. 20 ml of ethanol was added, and the mixture was stirred at 50 ° C. for 96 hours to perform a sol-gel reaction, thereby obtaining a polymer compound of the present invention. The obtained reaction solution was applied on a glass substrate using a bar coater, and dried at 70 ° C. for 24 hours to obtain a cured film (B-2) having a thickness of 0.3 mm.
[0055]
Example 7
0.1 g of the compound (A-3) obtained in Example 3, 3 g of tetraethoxysilane, 1 g of diphenyldiethoxysilane, 1 g of sodium hydroxide in a 100 ml three-necked flask equipped with a thermometer, a stirrer, and a condenser. 3 g, 20 g of water and 30 ml of ethanol were added, and the mixture was stirred at 60 ° C. for 72 hours to perform a sol-gel reaction, thereby obtaining a polymer compound of the present invention. The obtained reaction liquid was applied on a glass substrate using a bar coater, and dried at 50 ° C. for 24 hours to obtain a cured film (B-3) having a thickness of 0.3 mm.
[0056]
Example 8
0.1 g of the compound (A-4) obtained in Example 4, 4 g of tetraethoxysilane, 2.1 g of 12N hydrochloric acid, 20 g of water, 20 g of THF, 10 ml of THF were placed in a 100 ml three-necked flask equipped with a thermometer, a stirrer, and a condenser. 20 ml of ethanol was added, and the mixture was stirred at 60 ° C. for 80 hours to perform a sol-gel reaction, thereby obtaining a polymer compound of the present invention. The obtained reaction liquid was applied on a glass substrate using a bar coater, and dried at 70 ° C. for 24 hours to obtain a cured film (B-4) having a thickness of 0.3 mm.
[0057]
Test Example The cured films (B-5), (B-6), (B-7), and (B-8) obtained in Examples 5 to 8 were used as spectrophotometers (U-3210 type self-spectrophotometers). The light absorption spectrum was measured using Hitachi). Table 1 shows the measurement results.
Sample absorption wavelength (nm)
Cured film (B-1) 327, 256, 220
Cured film (B-2) 325, 286, 218
Cured film (B-3) 324, 261, 221, 205, 190
Cured film (B-4) 320, 268, 257, 215
[0058]
【The invention's effect】
The fullerene-containing compound of the present invention can easily obtain a cured film containing fullerene molecules and is useful as an optical functional material such as a photocatalyst and a third-order nonlinear optical material.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP12455995A JP3589740B2 (en) | 1995-04-26 | 1995-04-26 | Fullerene-containing compound, resin composition and cured product thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12455995A JP3589740B2 (en) | 1995-04-26 | 1995-04-26 | Fullerene-containing compound, resin composition and cured product thereof |
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| Publication Number | Publication Date |
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| JPH08295694A JPH08295694A (en) | 1996-11-12 |
| JP3589740B2 true JP3589740B2 (en) | 2004-11-17 |
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