平成 21 年度
九州地域戦略産業イノベーション創出事業
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平成 22 年 3 月
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平成
21年度 九州地域戦略産業イノベーション創出事業 事業創出研究成果報告書平成
22年３月 財団法人 九州産業技術センター
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ၸ⢈ࠍΆᢱߣߔࠆኾΆࡏࠗߩ㐿⊒
ᾢᧄᄢቇᄢቇ㒮⥄ὼ⑼ቇ⎇ⓥ⑼ ↥ᬺഃㅧᎿቇኾ ᢎ 㠽ዬୃ৻
ἑᶦᯏᎿࢃ Ᏹോข✦ᓎ ἑᶦᵗ
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Ꮏ႐㐳 ᧲ේᔒ
1㧚✜⸒
᷷ᥦൻ㒐ᱛࠍ⋡ᜰߒߡ✦⚿ߐࠇߚ੩ㇺ⼏ቯᦠߩ⋡ᮡ୯ࠍ㆐ᚑߔࠆߚߦࠈࠈߥขࠅ⚵
ߺ߇ߥߐࠇߡ߅ࠅޔࡃࠗࠝࡑࠬ↪ߪࠞࡏࡦ࠾ࡘ࠻࡞ߣ߁ὐߢᄢᄌലߢࠆߩߢޔࡃ
ࠗࠝࡑࠬߩࠛࡀ࡞ࠡᄌ឵ࠍଦㅴߔࠆขࠅ⚵ߺߪᓟ⋉ޘ㊀ⷐߦߥࠆޕฦ⒳ࡃࠗࠝࡑࠬߦ߅ߡޔ ᐔᚑ16ᐕ11ࠃࠅኅ⇓ឃߖߟ‛▤ℂߩㆡᱜൻ߅ࠃ߮↪ଦㅴߦ㑐ߔࠆᴺᓞ߇ᣉⴕߐࠇߚ߇ޔ
ੱ⚻༡ߩ⇓↥ㄘኅߪޔឃߖߟ‛ߩਛ߳ߩᶐㅘࠍ㒐ߋ◲ᤃߥ߽ߩࠍ⸳⟎ߒߡࠆߩ߇⁁ߢࠅޔ
࿐߳ߩᖡ⥇ߩᩮᧄ⊛ߥⅣႺ㗴ߪ⸃ߐࠇߡߥޕ
ߐߡޔኅ⇓♮ߩᵴ↪ࠍ⋡⊛ߣߒޔ⊒↢႐ߢߪၸ⢈ߩ↢↥߇ᵴ⊒ߦⴕࠊࠇߡࠆ߇ޔᏒ႐ߢ ߪޔၸ⢈ߩଏ⛎ߦኻߒߡଏ⛎ㆊᄙߣߥߞߡࠆߩ߇⁁ߢࠆޕߘߎߢᧄ⎇ⓥߪޔၸ⢈ࠍࡏ
ࠗΆᢱߣߒߚᾲᵴ↪ࠍ⋡⊛ߣߒޔߘߩᦨㆡΆ․ᕈࠍࠄ߆ߦߔࠆߣหᤨߦޔၸ⢈ࠍኾ
ߢ߈ࠆࡏࠗࠍ㐿⊒ߔࠆޕᦝߦޔၸ⢈ߩ‛ᕈ୯ޔහߜޔ⊒ᾲ㊂ޔ᳓₸ࠍᛠីߔࠆߎߣߢޔኻ
⽎ߣߥࠆၸ⢈ࠍᦨㆡߦΆߐߖࠆߚߩᠲ᧦ઙࠍዉߊޕ
㧞㧚ታ㛎ⵝ⟎㧔ߘߩ㧝㧕
ߚ⢈Άታ㛎ⵝ⟎ࠍ࿑㧝ߦ␜ߔޕታ㛎ⵝ⟎ߪޔߚ⢈ΆἹ↪ࡃ࠽㧔Ἱ↪ᾲ↪㧕ޔⓨ᳇ᵹ
㊂ⵝ⟎ޔⓨ᳇ᝌ↪ࡉࡠࠕޔߚ⢈ᛩ↪ⵝ⟎ޔ᷷ᐲ⸘᷹ⵝ⟎߆ࠄߥࠆޕ
߹ߕޔἮᴤࡃ࠽㧔KATOH ࡃ࠽㧕ߢߚ⢈ΆἹࠍ੍ᾲߔࠆޕහߜޔࡃ࠽ࠍߞ ߡἹౝࠍචಽߦ੍ᾲߔࠆߎߣߢޔߚ⢈߇Ἱౝߦᛩߐࠇߚ㓙ޔߘߩᾲߢߚ⢈߇⥄Άߔࠆࠃ߁ ߦߔࠆޕߘߩᓟޔⓨ᳇ᵹ㊂ࠍ⺞ᢛᑯߢ⺞ᢛߒߥ߇ࠄޔࡈࡠᑼᵹ㊂⸘ߢᵹ㊂ࠍ৻ቯ୯ߦ⸳ቯߒߚ ᓟޔߚ⢈ࠍᛩⵝ⟎߆ࠄἹౝߦᛩߔࠆޕߎߎߢޔߚ⢈ߩᛩ㊂ߪ੍ታ㛎ߢޔⵝ⟎ߦ⸳⟎
ߒߡࠆ࠳ࠗࡗ࡞ࠍ࿁ォߔࠆߎߣߦࠃߞߡޔ㧝ಽ㑆ᒰߚࠅߩߚ⢈ᛩ㊂߇ᄌൻߔࠆࠃ߁ߦߥߞ ߡࠆޕ࿑㧞ߪߚ⢈ᛩ㊂ߣ࠳ࠗࡗ࡞ߩ࿁ォᢙߩ㑐ଥࠍ߹ߣߚ߽ߩߢࠆޕ
ᛩߐࠇߚߚ⢈ߪ੍ᾲߐࠇߚἹౝߢ⥄Άߒߡޔᄢ᳇߳ΆࠟࠬߪߐࠇࠆޕἹౝߩΆࠟ
᷷ࠬᐲߪ㧷ဳᾲ㔚ኻࠍ↪ߒߡ᷹ቯߒޔߘߩ⸳⟎⟎ࠍ࿑㧟ߦ߹ߣߡࠆޕ࿑ਛߢ␜ߔࠃ߁ߦޔ 㧷㧝㧔ΆἹญ㧕߆ࠄ㧷㧝㧝߹ߢߩᾲ㔚ኻࠍἹౝߦ⸳⟎ߒߡࠆޕ
↪ߔࠆΆᢱߣߒߡޔ㧞⒳㘃ߩ⇣ߥߞߚߚ⢈ࠍ↪ߒߚޕ੍ታ㛎ߣߒߡޔ↪ߔࠆߚ⢈
ߩ⊒ᾲ㊂ߣ᳓₸ߪߘࠇߙࠇޔ࿑㧠ߦ␜ߔፉᵤΆ⎇ᑼ⥄േࡏࡦࡌᾲ㊂⸘㧔SHIMAZU CA-4AJ㧕ޔ
᳓₸᷹ቯⵝ⟎㧔AND MF-50㧕ߢ᷹ቯߒߚޕ
࿑㧝 ታ㛎ⵝ⟎
࿑㧞 ߚ⢈ᛩ㊂ߣⵝ⟎ౝㇱߩࠪࡖࡈ࠻ߩ࿁ォᢙߣߩ㑐ଥ
㫐㩷㪔㩷㪈㪋㪅㪊㪈㪈㫏㩷㪂㩷㪍㪅㪍㪋㪉
㪇 㪌㪇 㪈㪇㪇 㪈㪌㪇 㪉㪇㪇 㪉㪌㪇
㪇 㪌 㪈㪇 㪈㪌 㪉㪇
䉲䊞䊐䊃࿁ォᢙ㩷㪲㫉㫇㫄㪴
Άᢱ㊀㊂㩷 㪲㪾 㪴
࿑㧟 ߚ⢈ΆἹౝㇱߩ᷷ᐲ⸘᷹ࡦࠨ㧔㧷ဳᾲ㔚ኻ㧕ߩ⸳⟎⟎
㪌㪇㪇 㪍㪊㪇
㪊㪊㪇
㪉㪎㪇
㪉㪇㪇
㪎㪇
㪈㪏㪇 㪉㪏㪇
㪌㪇㪇
㪊㪐㪇
㪊㪋㪇㩷㫄㫄
㪈㪏㪇 㪉㪏㪇
㪌㪇㪇
㪊㪐㪇
㪈㪏㪇 㪉㪏㪇
㪌㪇㪇
㪊㪐㪇
㪉㪇㪇㩷㫄㫄
㪈㪏㪇 㪉㪏㪇
㪌㪇㪇
㪊㪐㪇
㪎㪇㩷㫄㫄 㪢㪈
㪢㪏 㪢㪈㪈
㪢㪈㪇 㪢㪐
㪢㪎 㪢㪍
㪢㪌 㪢㪋
㪢㪉
㪉㪎㪇㩷㫄㫄
㪊㪍㪌
Άᢱᛩญ
䈐ⓣ
Άᢱᛩญ
࿁ォ䊄䊤䊛
㪈㪏㪇 㪉㪏㪇
㪌㪇㪇
㪊㪐㪇
㪢㪊 㪢㪍
㪢㪋 㪢㪌
㪢㪊
㪢㪈㪇 㪢㪈㪈 㪢㪐
㪢㪏 㪢㪎
᷹ቯߒߚ⊒ᾲ㊂ߣ᳓₸ࠍએਅߦ߹ߣࠆޕ
ߚ⢈㧝㧔ήශ㧕㧦 㧟㧥㧣㧞 kcal/kgޔ㧞㧞㧚㧠㧡㧑㧔᳓₸㧕 ߚ⢈㧞㧔1-10㧕㧦 㧟㧣㧢㧡 kcal/kgޔ㧝㧞㧚㧣㧜㧑㧔᳓₸㧕
Ἱౝߢ⊒↢ߒߚΆࠟࠬߩࠟࠬಽᨆߦߪޔࠟࠬࠢࡠࡑ࠻ࠣࡈᴺࠍ↪ߚࠟࠬಽᨆⵝ⟎㧔ࡄ࠰
࠽࡞ࠟࠬࠢࡠࡑ࠻ࠣࡈ GC-8AޔSHIMADZU)ࠍ↪ߒߚ㧔࿑㧡㧕ޕ
࿑㧡 ࠟࠬಽᨆⵝ⟎
㧟㧚ታ㛎⚿ᨐ㧔ߘߩ㧝㧕 㧟㧙㧝 ߚ⢈㧝
࿑㧢ߪฦᾲ㔚ኻ⟎ߢߩΆ᷷ࠟࠬᐲࠍ␜ߒߚ߽ߩߢޔߚ⢈ᛩⵝ⟎࿁ォᢙߣⓨ᳇ᵹ㊂ࠍᄌ ൻߐߖߚ႐วߩ⚿ᨐࠍ߹ߣߡࠆޕⓨ᳇ᵹ㊂߮ߚ⢈ᛩ㊂߇ᄙߊߥࠆߦߟߡޔΆࠟࠬ
ߪἹౝߢߒߡࠆޕᦝߦޔἹౝߢߩΆ᷷ࠟࠬᐲߪᦨᄢߢ㧣㧜㧜ᐲߦ㆐ߒޔⓨ᳇ᵹ㊂߮ߚ
⢈ᛩ㊂ߦࠃߞߡߪޔΆ᷷ࠟࠬᐲߪ㧤㧜㧜ᐲߦ㆐ߒߡࠆޕ
࿑㧢 ΆἹౝㇱߩΆ᷷ࠟࠬᐲಽᏓ
㪇 㪈㪇㪇 㪉㪇㪇 㪊㪇㪇 㪋㪇㪇 㪌㪇㪇 㪍㪇㪇 㪎㪇㪇 㪏㪇㪇 㪐㪇㪇
㪇 㪉 㪋 㪍 㪏 㪈㪇 㪈㪉 㪈㪋
ᾲ㔚ኻ⸳⟎႐ᚲ䇭㪚㪁㪁
᷷ᐲ㩷㷄
㪊㫉㫇㫄㪄㪉㪇㪣㪆㫄㫀㫅 㪊㫉㫇㫄㪄㪏㪌㪣㪆㫄㫀㫅 㪉㫉㫇㫄㪄㪈㪇㪇㪣㪆㫄㫀㫅 㪉㫉㫇㫄㪄㪉㪈㪇㪣㪆㫄㫀㫅 㪊㫉㫇㫄㪄㪈㪇㪇㪣㪆㫄㫀㫅 㪊㫉㫇㫄㪄㪉㪈㪇㪣㪆㫄㫀㫅 㪈㪇㫉㫇㫄㪄㪊㪍㪇㪣㪆㫄㫀㫅
࿑㧣ߪΆࠟࠬਛߩ৻㉄ൻੑ⓸⚛ߩഀวࠍ␜ߒߡࠆޕߎߎߢޔΆࠟࠬߣߒߡᵈ⋡ߒߚߩߪ৻
㉄ൻੑ⓸⚛ߢࠆ߇ޔߎߩࠟࠬߪ᷷ቶലᨐࠟࠬߣߒߡലᨐ߇ᄢ߈ߊޔࡃࠗࠝࡑࠬΆᢱࠍ↪ߔࠆ 㓙ޔᄙߊ⊒↢ߔࠆߣᜰ៰ߐࠇߡࠆޕΆᢱଏ⛎㊂㧔ࠪࡖࡈ࠻࿁ォᢙ㧕߇ᄢ߈ߊߥࠆߦߟࠇߡޔ৻
㉄ൻੑ⓸⚛ߩ⊒↢㊂߽ᄙዋჇടߒߡࠆޕ
࿑㧣 ৻㉄ൻੑ⓸⚛ߩ⊒↢ഀว
㧟㧙㧞 ߚ⢈㧞
ฦᾲ㔚ኻ⟎ߢߩΆ᷷ࠟࠬᐲࠍ␜ߒߚ߽ߩߢޔߚ⢈ᛩⵝ⟎࿁ォᢙߣⓨ᳇ᵹ㊂ࠍᄌൻߐߖ ߚ႐วߩ⚿ᨐࠍ࿑㧢ߣหߓᒻᑼߢ࿑㧤ߦ߹ߣߡࠆޕߚ⢈ᛩ㊂ߣⓨ᳇ᛩ㊂߇Ⴧടߔࠆߦ ߟࠇߡΆ᷷ࠟࠬᐲߪߒߡ߅ࠅޔߘߩะߪἹౝోߢ↢ߓߡࠆޕἹౝΆ᷷ࠟࠬᐲ߇㜞 ߊߥߞߚߩߪޔⓨ᳇ᵹ㊂߇ 360L/min ߢߪޔߚ⢈ᛩ㊂ߪߚ⢈ᛩⵝ⟎ߩࠪࡖࡈ࠻࿁ォᢙ߇ 㧠࿁ォ߆ࠄ㧢࿁ォߢ㆐ᚑߒߡࠆߎߣ߇ಽ߆ࠆޕහߜޔΆ᷷ࠟࠬᐲߪⓨ᳇ᵹ㊂ߣߚ⢈ᛩ㊂ ߩ㑐ଥߦࠃߞߡᓇ㗀ߐࠇࠆޔ
࿑㧤 ΆἹౝㇱߩΆ᷷ࠟࠬᐲಽᏓ 0
5 10 15
0 3 6 9 12 15
fuel supply rate [rpm]
Concentration of N2O [%]
㪇 㪈㪇㪇 㪉㪇㪇 㪊㪇㪇 㪋㪇㪇 㪌㪇㪇 㪍㪇㪇 㪎㪇㪇 㪏㪇㪇 㪐㪇㪇
㪇 㪉 㪋 㪍 㪏 㪈㪇 㪈㪉 㪈㪋
᷷ᐲ㷄
ᾲ㔚ኻ⸳⟎႐ᚲ 㪚㪁㪁
㪉㫉㫇㫄㪄㪈㪇㪇㪣㪆㫄㫀㫅 㪉㫉㫇㫄㪄㪉㪈㪇㪣㪆㫄㫀㫅 㪉㫉㫇㫄㪄㪊㪍㪇㪣㪆㫄㫀㫅 㪋㫉㫇㫄㪄㪈㪇㪇㪣㪆㫄㫀㫅 㪋㫉㫇㫄㪄㪉㪈㪇㪣㪆㫄㫀㫅 㪋㫉㫇㫄㪄㪊㪍㪇㪣㪆㫄㫀㫅 㪎㫉㫇㫄㪄㪈㪇㪇㪣㪆㫄㫀㫅 㪎㫉㫇㫄㪄㪉㪈㪇㪣㪆㫄㫀㫅 㪎㫉㫇㫄㪄㪊㪍㪇㪣㪆㫄㫀㫅 㪈㪇㫉㫇㫄㪄㪈㪇㪇㪣㪆㫄㫀㫅 㪈㪇㫉㫇㫄㪄㪉㪈㪇㪣㪆㫄㫀㫅 㪈㪇㫉㫇㫄㪄㪊㪍㪇㪣㪆㫄㫀㫅
㧠㧚ታ㛎ⵝ⟎㧔ߘߩ㧞㧕
వߩ⚿ᨐߢߪޔἹౝΆ᷷ࠟࠬᐲ߇㧝㧜㧜㧜ᐲࠍ߃ࠆࠃ߁ߥߎߣߪߥ߆ߞߚޕߎࠇߪἹౝኈ
㊂㧔Ἱౝⓨ㑆ࠍᒛߔࠆ㧕ࠍᄢ߈ߊߔࠆߎߣߦࠃߞߡޔහߜޔΆࠟࠬߩṛ⇐ᤨ㑆ࠍᄢ߈ߊߣࠆ ߎߣߦࠃߞߡޔΆ᷷ࠟࠬᐲࠍߔࠆߎߣ߇ᦼᓙߢ߈ࠆޕߘߎߢޔߎߩὐࠍᡷ⦟ߒߥ߇ࠄޔἹ ߩ⠴ਭᕈࠍะߔࠆߎߣࠍ⋡⊛ߣߒߡⵝ⟎ࠍᡷ⦟ߒߚޕ࿑㧥ߪޔవߩᡷ⦟ὐࠍ⠨ᘦߒߡᡷㅧߒߚ ⵝ⟎ࠍ␜ߒߡࠆޕએ೨ߩⵝ⟎ߦߪޔⵝ⟎ౝㇱߦߚ⢈ࠍᡬᜈߐߖࠆ⠀ᩮゞࠍⵝ⌕ߒߡߚޕߒ ߆ߒޔ㜞᷷ⅣႺߢ↪ߐࠇߡߚߚߦޔ⠀ᩮゞ߇߽ࠈߊߥࠅ⎕უߐࠇߡߒ߹ߞߚޕහߜޔߎߩ ᣇᑼߢߚ⢈ࠍἹౝߢᡬᜈߐߖࠆߎߣߦߪ㒢⇇߇ࠆߎߣ߇ಽ߆ߞߚߩߢޔᡷ⦟ဳⵝ⟎ߢߪޔߚ
⢈ࠍⓨ᳇ߢἹౝߦャㅍߐߖߥ߇ࠄ㧔ߎࠇࠍ࿕᳇ᷙ⋧ᵹߣ߁㧕ޔἹౝߢᣓ࿁ߐߖࠆߎߣߢޔߚ
⢈ࠍΆἹౝߢචಽኻᵹߐߖࠆࠃ߁ߦߥߞߡࠆޕᡷ⦟ဳߚ⢈Άⵝ⟎ߪޔߚ⢈ΆἹ↪ࡃ
࠽㧔Ἱ↪ᾲ↪㧕ޔⓨ᳇ᵹ㊂ⵝ⟎ޔⓨ᳇ᝌ↪ࡉࡠࠕޔߚ⢈ᛩ↪ⵝ⟎㧔ⓨ᳇ߣߚ⢈߇ᷙ
ว⁁ᘒߣߥࠆⵝ⟎㧕ޔ᷷ᐲ⸘᷹ⵝ⟎߆ࠄߥࠆޕ
వߩታ㛎ߣห᭽ߦޔἮᴤࡃ࠽㧔KATOH ࡃ࠽㧕ߢߚ⢈ΆἹࠍ੍ᾲߔࠆޕߘߩᓟޔ
ⓨ᳇ᵹ㊂ࠍ⺞ᢛᑯߢ⺞ᢛߒߥ߇ࠄޔࡈࡠᑼᵹ㊂⸘ߢᵹ㊂ࠍ৻ቯ୯ߦ⸳ቯߒߚᓟޔߚ⢈ߣⓨ᳇
ߩᷙวᇦࠍἹౝߦᛩߔࠆޕᛩߐࠇߚߚ⢈ߪ੍ᾲߐࠇߚἹౝߢ⥄Άߒߡޔᄢ᳇߳Άࠟࠬ
ߪߐࠇࠆޕἹౝߩΆ᷷ࠟࠬᐲߪ㧷ဳᾲ㔚ኻࠍ↪ߒߡ᷹ቯߔࠆޕᾲ㔚ኻߩ⟎ࠍ࿑㧝㧜ߦ
␜ߔޕ↪ߔࠆΆᢱߣߒߡޔ㧝⒳㘃ߩߚ⢈ࠍ↪ߒߚޕߎߎߢޔ↪ߔࠆߚ⢈ߩ⊒ᾲ㊂ߣ
᳓₸ߪፉᵤΆ⎇ᑼ⥄േࡏࡦࡌᾲ㊂⸘㧔SHIMAZU CA-4AJ㧕ޔ᳓₸᷹ቯⵝ⟎㧔AND MF-50㧕 ߢ᷹ቯߒޔߘࠇߙࠇޔ3972kca/kgޔ22.5㧑ߢߞߚޕ
࿑㧥 ᣂဳߚ⢈ΆἹ
࿑㧝㧜 ᣂဳߚ⢈ΆἹౝߩᾲ㔚ኻߩ⟎
㧡㧚ታ㛎⚿ᨐ㧔ߘߩ㧞㧕
࿑㧝㧝ߪߚ⢈ࠍᛩߒߚ㓙ߩἹౝߦ࿕ቯߒߚᾲ㔚ኻ⟎ߢߩΆ᷷ࠟࠬᐲࠍ␜ߒߡࠆޕἹ
ౝߩౝ╴ㇱ߮ౝ╴ਅㇱߦ߅ߡޔΆ᷷ࠟࠬᐲߪ 1200 ᐲએߦ㆐ߒߡࠆߎߣ߇ಽ߆ࠆޕ හߜޔΆࠟࠬߩṛ⇐ᤨ㑆ࠍᄢ߈ߊߣࠆࠃ߁ߦἹౝㇱࠍᡷ⦟ߒߚߎߣ߇ޔߚ⢈߇චಽߦΆߐ ࠇࠆߎߣ߇น⢻ߣߥࠅޔ㜞᷷Άࠟࠬ߇↢ᚑߐࠇࠆࠃ߁ߦߥߞߚߣᕁࠊࠇࠆޕ
࿑㧝㧝 ᣂဳߚ⢈ΆἹౝߩΆ᷷ࠟࠬᐲಽᏓ
㧢㧚߹ߣ
ߚ⢈߇ΆἹౝߢචಽߥṛ⇐ᤨ㑆߇⏕ߢ߈ࠆࠃ߁ߦޔߚ⢈ΆἹߩౝㇱࠍᡷ⦟ߔࠆߎߣ ߢޔΆ᷷ࠟࠬᐲࠍ㜞᷷ߦߔࠆߎߣ߇㆐ᚑߢ߈ߚޕᦝߦޔߚ⢈ࠍⓨ᳇ャㅍߢἹౝߦᝌߔࠆࠃ ߁ߦߒߚߎߣߢޔἹߩ⠴ਭᕈ߇ᄢ߈ߊะߒߚޕ
㧣㧚ᓟߩᣇ㊎
߹ߢޔၸ⢈ࠍΆᢱߣߒߡ↪ߢ߈ࠆኾࡏࠗߪሽߒߥ߇ޔ࿁㐿⊒ߒߚΆἹߪ ၸ⢈ࠍᾲࠛࡀ࡞ࠡߣߒߡᵴ↪ߔࠆߎߣ߇น⢻ߦߥߞߚޕ႐ߢ⊒↢ߒߡࠆၸ⢈ߩᵴ
↪ߦޔᾲࠛࡀ࡞ࠡ⊒↢↪Άᢱߣߒߡߩᵴ↪ࡈࡠ߇ߢ߈ࠆߩߢޔ⇓↥ᬺߩ⊒ዷ߇ᦼᓙߢ߈ࠆޕ
႐ߢ⊒↢ߔࠆ⇓↥ᑄ᫈‛߇ࠝࡦࠨࠗ࠻ߢᾲࠛࡀ࡞ࠡߣߒߡᵴ↪ߢ߈ࠆߩߢޔ⇓↥ᬺߩᣂߚ ߥዷ㐿߇ᦼᓙߢ߈ࠆޕහߜޔΆࠟࠬࠍๆᑼ಄ಓᯏߩᾲḮߣߒޔኅ⇓⥢ߩ಄ᾲߪ᷷ᾲߣߒߡ
↪ߢ߈ࠆޕၸ⢈ߪࡃࠗࠝࡑࠬߢࠅޔߎࠇ߇Άᢱߣߒߡ↪ߢ߈ࠆࠃ߁ߦߥࠇ߫ޔൻ⍹Άᢱߩ シᷫߦ❬߇ࠆޕߎࠇߪ᷷ቶലᨐࠟࠬߩᷫߦነਈߒޔⅣႺࡆࠫࡀࠬߩዷ㐿߇ᦼᓙߢ߈ࠆޕ ᓥߞߡޔ႐ߢ⊒↢ߔࠆߚ⢈ࠍࠝࡦࠨࠗ࠻ߢΆᢱߣߒߡ↪ߢ߈ࠆΆἹߩࡊࡠ࠻࠲ࠗࡊࠍ
ߒߡታ㛎ࠍ㊀ߨޔߚ⢈ኾࡏࠗࠍቢᚑߐߖࠆޕ
1㸬3 ᮏࡢ㛗㙐ࣝ࢟ࣝᇶࢆഃ㙐᭷ࡍࡿ࣏࣑ࣜࢻࡢྜᡂ≀ᛶ
㸯㸬⥴ゝ
࣏࣑ࣜࢻࡣ⧞ࡾ㏉ࡋ༢࣑ࢻ⤖ྜࢆᣢ ࡘ㧗ศᏊ࡛ࠊ๛┤࡞ᵓ㐀ࢆ᭷ࡍࡿࡓࡵࠊඃࢀࡓ⪏
⇕ᛶࢆ♧ࡍࠋࡋࡋࠊ୍⯡ⓗ࡞࣏࣑ࣜࢻࡣ⁐፹
⁐࡛࣑ࢻࡢ㝿ࡢရ㉁⟶⌮ࡀ㞴ࡋࡃࠊᆒ୍
࡞ࣇ࣒ࣝࢆసࡿࡇࡀ࡛ࡁ࡞࠸ࡇࡀ㞴Ⅼ࡛
࠶ࡗࡓࠋ
ᮏ◊✲࡛ࡣഃ㙐3ᮏࡢ㛗㙐ࣝ࢟ࣝᇶࢆᣢࡘ ࢪ࣑ࣥࢆ࣏࣑ࣜࢻ㦵᱁ᑟධࡋࠊ⁐ゎᛶࢆྥ
ୖࡉࡏࡓࠋࡲࡓࠊ㛗㙐ࣝ࢟ࣝᇶࢆᑟධࡋࡓ࣏ࣜ
࣑ࢻࣇ࣒ࣝ⣸እ⥺ࢆ↷ᑕࡋࠊ⾲㠃≀ᛶࡢࢥ
ࣥࢺ࣮ࣟࣝࢆ᳨ウࡋࡓࠋ 㸰㸬⤖ᯝཬࡧ⪃ᐹ 1㸧࣏࣑ࣜࢻࡢྜᡂ
DDE , Cyclohexene-DA(ࡲࡓࡣDSDA)ࠊ3ᮏࡢ 㛗 㙐 ࣝ ࢟ ࣝ ᇶ ࢆ ྵ ࡴ ࢪ ࣑ ࣥ (12G1-AG-Terphenyldiamine)ࢆඹ㔜ྜࡍࡿࡇ
ࡼࡾࠊ࣏࣑ࣜࢻࢆᚓࡓࠋඹ㔜ྜࡣࠊ12G1
DDE ࡢࣔࣝẚࢆኚ࠼࡚5 ✀㢮㸦0㸣ࠊ25㸣ࠊ 50㸣ࠊ75㸣ࠊ100㸣㸧ࡢ⤌ᡂࢆ᳨ウࡋࡓࠋ
CH3 O
O O O
O
O
O(CH2)11CH3
O(CH2)11CH3 H3C(H2C)11O
O O
O NH
NH2
H2N cyclohexene-DA
12G1-AG-Terphrnyldiamine H2N
O
NH2 DDE
(x+y) (x)
(y)
O O O
S O O
O O
DSDA O
1) r.t. , 24h, in NMP 2) Pyridine , Ac2O 120Υ, 4h, in NMP O(CH2)11CH3
O(CH2)11CH3 H3C(H2C)11O
O O
O NH
N
*
CH3 N O
O
O
O
* x
n O
* N
N
O O
O O
*
CH3 y
m copolyimide
2㸧࣏࣑ࣜࢻࡢ≀ᛶ
ྜᡂࡋࡓ࣏࣑ࣜࢻࡢ㹌㹋㹎ᑐࡍࡿ⁐ゎᛶࠊ ᑐ ᩘ ⢓ ᗘ ࠊ ศ Ꮚ 㔞(SEC, 40Υ, 10mM LiBr inNMP)ࡣ௨ୗ♧ࡍ࠾ࡾ࡛࠶ࡿࠋࡲࡓࠊ10㸣 㔜㔞ῶᑡ ᗘ (Ꮫⓗ⪏⇕ᛶ) ࡣ✵Ẽ୰࡛ 404㹼
436Υࡢ⠊ᅖࠊ❅⣲୰࡛400㹼430Υࡢ⠊ᅖ࠶ࡿ
ࡇࡀุ᫂ࡋࡓࠋ
㻰㼕㼍㼚㼔㼥㼐㼞㼕㼐㼑 㼟㼛㼘㼡㼎㼕㼘㼕㼠㼥 䃖㼕㼚㼔
㼙㼛㼘㻑 㼕㼚㻺㻹㻼 㼐㻸㻙㻝 㻹㼚 㻹㼣㻌 㻹㼣㻛㻹㼚
㼏㼥㼏㻙㻰㻭 㻝㻞㻳㻝 㻰㻰㻱
㻝㻜㻜 㻜 㻝㻜㻜 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻟㻠 㻝㻞㻥㻜㻜 㻟㻥㻟㻜㻜 㻟㻚㻜
㻝㻜㻜 㻞㻡 㻣㻡 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻞㻟 㻝㻜㻤㻜㻜 㻞㻣㻠㻜㻜 㻞㻚㻡
㻝㻜㻜 㻡㻜 㻡㻜 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻝㻣 㻤㻡㻜㻜 㻝㻤㻣㻜㻜 㻞㻚㻞
㻝㻜㻜 㻣㻡 㻞㻡 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻜㻥 㻣㻞㻜㻜 㻝㻣㻥㻜㻜 㻞㻚㻝
㻝㻜㻜 㻝㻜㻜 㻜 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻝㻝 㻣㻜㻜㻜 㻝㻠㻜㻜㻜 㻞㻚㻜
㻰㻿㻰㻭 㻝㻞㻳㻝 㻰㻰㻱
㻝㻜㻜 㻜 㻝㻜㻜 㼕㼚㼟㼛㼘㼡㼎㼡㼘㼑
㻝㻜㻜 㻞㻡 㻣㻡 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻡㻜 㻞㻠㻣㻜㻜 㻤㻤㻟㻜㻜 㻟㻚㻢
㻝㻜㻜 㻡㻜 㻡㻜 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻠㻟 㻠㻥㻝㻜㻜 㻥㻤㻤㻜㻜 㻞㻚㻜
㻝㻜㻜 㻣㻡 㻞㻡 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻟㻢 㻡㻠㻥㻜㻜 㻝㻜㻝㻜㻜㻜 㻝㻚㻤
㻝㻜㻜 㻝㻜㻜 㻜 㼟㼛㼘㼡㼎㼡㼘㼑 㻜㻚㻞㻤 㻡㻜㻝㻜㻜 㻤㻝㻥㻜㻜 㻝㻚㻢
㼀㼍㼎㼘㼑㻝㻚䝫䝸䜲䝭䝗䛾≀ᛶ 㻼㼛㼘㼥㼕㼙㼕㼐㼑
㻰㼕㼍㼙㼕㼚㼑 㻹㼛㼘㼑㼏㼡㼘㼍㼞㼃㼑㼕㼓㼔㼠
㼙㼛㼘㻑 㻹㼛㼚㼛㼙㼑㼞
3㸧ග↷ᑕࡢ⤖ᯝ
㛗㙐ࣝ࢟ࣝᇶࢆ᭷ࡍࡿ࣏࣑ࣜࢻࡢⷧ⭷
254nm ࡢ⣸እ⥺ࢆ↷ᑕࡍࡿỈᑐࡍࡿ᥋ゐゅ
ࡀ 90㹼100r⛬ᗘ (↷ᑕ๓)ࡽ 30㹼40r⛬ᗘ (8J↷ᑕᚋ) ࡁࡃኚࡍࡿࡇࡀุ᫂ࡋࡓࠋ
4㸧⪃ᐹ
≉ᐃࡢἼ㛗ࡢ⣸እ⥺ࢆ↷ᑕࡍࡿࡇࡼࡾࠊ᥋ ゐゅࡀኚࡋࡓࠋࡇࢀࡣࠊ⣸እ⥺ࡢ↷ᑕࡼࡾ㛗 㙐ࣝ࢟ࣝᇶࡀษ᩿ࡉࢀࠊ⾲㠃ࡀぶἜᛶࡽぶỈ ᛶኚࡋࡓࡓࡵࡔ⪃࠼ࡽࢀࠊATRࡼࡾ⾲
㠃ᵓ㐀ࡢኚࡶ☜ㄆࡋ࡚࠸ࡿࠋ 㸱㸬⤖ゝ
ᮏ◊✲ࡼࡾࠊ㛗㙐ࣝ࢟ࣝᇶࡢຠᯝ࡛⪏⇕ᛶ
ࢆ⥔ᣢࡋࡓࡲࡲྍ⁐ᛶࡀྥୖࡍࡿࡇࡀ☜ㄆ࡛
ࡁࡓࠋࡲࡓࠊ⾲㠃ࡢ≀ᛶࡶࢥࣥࢺ࣮ࣟࣝࡍࡿࡇ
0㹈 8㹈
ᕞᆅᇦᡓ␎⏘ᴗࣀ࣮࣋ࢩࣙࣥฟᴗ
ࠕගᛂᛶ࣭⁐፹ྍ⁐ᆺ࣏࣑ࣜࢻᮦᩱࡢ㛤Ⓨ㟁Ꮚᮦᩱࡢᛂ⏝ࠖ
ᴗฟ◊✲ሗ࿌᭩࣭ヲ⣽∧
2㸬ࢪࣝ࢟ࣝ࣋ࣥࢰࣇ࢙ࣀࣥ㦵᱁ࢆ᭷ࡍࡿ࣏࣑ࣜࢻࡢྜᡂ≀ᛶ (1)
㸯㸬⥴ゝ
࣏࣑ࣜࢻࡣ㟁Ꮚᮦᩱ࡞⏝࠸ࡽࢀࡿ⪏⇕ᛶ
࣏࣐࣮࡛ࣜ࠶ࡿࡀࠊ୍⯡᭷ᶵ⁐⁐࡛࠶ࡿࠋ ࡇࡢࡓࡵࠊ๓㥑య࡛࠶ࡿ⁐፹ྍ⁐ࡢ࣏࣑ࣜࢵࢡ㓟 ࡢẁ㝵࡛ሬᕸࡋࠊ300Υ㹼350Υ࡛⁐፹ࡢⓎྠ
࣑ࢻ⾜࠸ࠊ࣏࣑ࣜࢻࣇ࣒ࣝࢆᚓࡿ࠸
࠺᪉ἲࡀࡽࢀ࡚࠸ࡿࠋࡇࡢ᪉ἲ࡛ࡣ㧗 ࢆᚲせ
ࡍࡿࠊရ㉁⟶⌮ࡀ㞴ࡋ࠸࡞ࡢḞⅬࡀ࠶ࡾࠊ᭷ᶵ⁐
፹⁐ゎࡍࡿྍ⁐ᛶ࣏࣑ࣜࢻࡀᮃࡲࢀ࡚࠸ࡿࠋ ᮏ◊✲࡛ࡣࣃࣛⅣ⣲ᩘ 8ࡢࣝ࢟ࣝᇶࢆᑟධ ࡋࡓࢪࣝ࢟ࣝ࣋ࣥࢰࣇ࢙ࣀࣥ㦵᱁ࢆ᭷ࡍࡿࢪ
࣑ࣥ(p-C8-BPDA)ࢆྜᡂࡋࠊࡇࡢࢪ࣑ࣥࣔࣀ࣐
࣮ࢆ⏝࠸ࡓ࣏࣑ࣜࢻࡢྜᡂ≀ᛶࠊ≉࣏ࣜ
࣑ࢻࣇ࣒ࣝගࢆ↷ᑕࡍࡿࡇࡼࡾ⾲㠃≀ᛶ ࡢࢥࣥࢺ࣮ࣟࣝࢆ᳨ウࡋࡓࠋ
㸰㸬⤖ᯝཬࡧ⪃ᐹ 2.1 p-C8-BPDAࡢྜᡂ
1,4-dioctylbenzene ((1)ࢆ⏝࠸࡚3,5ࢪࢽࢺࣟᏳ ᜥ 㤶 㓟 ࢡ ࣟ ࣜ ࢻ ࡢ ࣝ ࢫ 㓟 ゐ ፹ ୗ ࡛ Friedel-Crafts ᛂࡼࡾࢪࢽࢺࣟయ ((2)ࢆᚓ࡚ࠊ ࡇࢀࢆ᥋ゐỈ⣲㑏ඖࡋp-C8-BPDAࢆᚓࡓࠋၥ㢟࡞
ࡃ ᪂ つ ࢪ ࣑ ࣥ ࣔ ࣀ ࣐ ࣮ ࢆ ྜ ᡂ ࡛ ࡁ ࡓ ࠋ
AlCl3 in CH3NO2
H2 Pd/C
in THF/EtOH 80䉝,2h
50䉝,1h,0.3MPa Yeild 84%
Yeild 53%
1,4-dioctylbenzene((1) 䝆䝙䝖䝻య(2)
p-C8-BPDA
O
NH2 H2N
R
R
O
NO2 O2N
R
R
R
R
NO2 O2N
O Cl
R=(CH2)7CH3
2.2࣏࣑ࣜࢻࡢྜᡂ
䝔䝖䝷䜹䝹䝪䞁㓟↓Ỉ≀䛻 DSDA ࡶࡋࡃࡣ cyclohexene-DAࢆࠊࢪ࣑ࣥࣔࣀ࣐࣮ỗ⏝ࡢࣔ
ࣀ࣐࣮࡛࠶ࡿDDE᪂つྜᡂࡋࡓp-C8-BPDA
ࢆ⏝࠸࡚ඹ㔜ྜࢆ⾜ࡗࡓࠋ 2.3࣏࣑ࣜࢻࡢ≀ᛶ
ྜᡂࡋࡓྛ࣏࣐࣮ࣜࡢNMPᑐࡍࡿྍ⁐ᛶࠊᑐ
ᩘ⢓ᗘࠊศᏊ㔞(SEC, 40Υ, 10mM LiBr in NMP)
ࢆ ᐃࡋࡓࠋp-C8-BPDA ࢆ⏝࠸࡚㔜ྜࡋࡓ࣏ࣜ
࣑ࢻࡣ⁐ゎᛶࡢྥୖࡀ☜ㄆࡉࢀࡓࠋࢸࢺࣛ࢝ࣝ
࣎ࣥ㓟↓Ỉ≀ࡢ㐪࠸ࡼࡿศᏊ㔞ࡢᕪࡣᛂ ᛶࡀᙳ㡪ࡋ࡚࠸ࡿ⪃࠼ࡽࢀࡿࠋ
Dianhydride Solubility Ljinh
NMP dLg-1 Mn Mw Mw/Mn DSDA p-C8-BPDA DDE
100 100 0 soluble 0.11 10000 26000 2.5 100 50 50 soluble 0.19 11000 27000 2.5
100 0 100 insoluble - - - -
cyclo-DA p-C8-BPDA DDE
100 100 0 soluble 0.07 3100 5700 1.8 100 50 50 soluble 0.07 4900 10000 2.0 100 0 100 soluble 0.33 13000 41000 3.3
mol%
Diamine Monomer
Molecular Weight Polyimide
࣏࣑ࣜࢻࣇ࣒ࣝࡢỈᑐࡍࡿ᥋ゐゅࢆ
ᐃࡋࡓࠋࣇ࣒ࣝUVࢆ↷ᑕࡍࡿࡑࡢ࢚ࢿࣝ
ࢠ࣮ࡢቑຍᚑࡗ࡚᥋ゐゅࡣῶᑡࡋࡓࠋࡇࢀࡣ࣋
ࣥࢰࣇ࢙ࣀࣥ㦵᱁ࡢ࢝ࣝ࣎ࢽࣝࡀษ᩿ࡉࢀࠊぶỈ ᛶኚࡋࡓ⪃࠼ࡽࢀࡿࠋ
㸱㸬⤖ゝ
p-C8-BPDAࢆྜᡂࡋࠊp-C8-BPDAࢆᑟධࡍࡿࡇ
࡛ྍ⁐ᛶ࣏࣑ࣜࢻࢆྜᡂ࡛ࡁࡓࠋ᥋ゐゅ ᐃ
ࡼࡾ⾲㠃≀ᛶࡀࢥࣥࢺ࣮࡛ࣟࣝࡁࡿࡇࡀุ
᫂ࡋࡓࠋ ཧ⪃ᩥ⊩
ὠ⏣♸㍜ࠊ➨9⠇࣭࣏࣑ࣜࢻࡢ⁐ゎᛶྥୖࠊࠕ࣏
࣑ࣜࢻࡢ㧗ᶵ⬟ᛂ⏝ᢏ⾡ࠖࠊ pp.161-175ࠊ ࢧ࢚ࣥࢫ㸤ࢸࢡࣀࣟࢪ࣮♫ (2008).
A B C
D E F
0 20 40 60 80 100
0 2 4 6 8
UV irradiation energy [J]
Contact angle [-]
D E F
0 20 40 60 80 100
0 2 4 6 8
UV irradiation energy [J]
Contact angle [-]
A B
3㸬ࢪࣝ࢟ࣝ࣋ࣥࢰࣇ࢙ࣀࣥ㦵᱁ࢆ᭷ࡍࡿ࣏࣑ࣜࢻࡢྜᡂ≀ᛶ(2)
1㸬⥴ゝ
࣏࣑ࣜࢻࡣⰾ㤶⎔࣑ࢻ⤖ྜࢆᣢࡘ๛
┤࡞ᵓ㐀ࡢ㧗ศᏊ࡛࠶ࡿࠋࡲࡓᶵᲔⓗᛶ㉁ඃࢀࠊ ᕤᴗⓗࡣᾮᬗ㓄ྥ⭷ࡸ㟁Ꮚᅇ㊰ࡢ⤯⦕ࣇࣝ
࣒࡞ࡢ㟁Ꮚ㒊ᮦ⏝ࡉࢀ࡚࠸ࡿࠋࡋࡋࠊ࣏
࣑ࣜࢻࡣ୍⯡᭷ᶵ⁐፹⁐࡛࠶ࡿ࠸࠺
ḞⅬࡀ࠶ࡿࠋࡇࡢၥ㢟ࢆゎỴࡍࡿࡓࡵ᭷ᶵ⁐፹
⁐ゎᛶࢆᣢࡘ࣏࣑ࣜࢻࡢ◊✲ࡀࡉࢀ࡚࠸ࡿࠋ ᮏ◊✲࡛ࡣ2 ᮏࡢ㛗㙐ࣝ࢟ࣝᇶ (C12)ࢆᣢࡗ ࡓ࣋ࣥࢰࣇ࢙ࣀࣥ㦵᱁ࡢࢪ࣑ࣥࣔࣀ࣐࣮ࢆྜ
ᡂࡋࠊࡑࡢࢪ࣑ࣥࣔࣀ࣐࣮ࢆ⏝࠸ࡓ࣏࣑ࣜࢻ ࡢྜᡂ≀ᛶ᳨ウࢆ⾜࡞ࡗࡓࠋ
2㸬⤖ᯝཬࡧ⪃ᐹ
2-1 ࢪ࣑ࣥࣔࣀ࣐࣮p-C12-BPDAࡢྜᡂ
1,4-ࢪࢻࢹࢩࣝ࣋ࣥࢮࣥ (ᵏ) 3,5-ࢪࢽࢺࣟᏳ ᜥ㤶㓟ࢡࣟࣜࢻ (ᵐ)ࢆ Friedel-Crafts ࢩࣝ
ᛂࢆ⾜࠸ࠊࢣࢺࣥ㐃⤖ࡉࡏࢪࢽࢺࣟయ (ᵑ)ࢆᚓࡓࠋ ࢪࢽࢺࣟయ (ᵑ)ࢆ᥋ゐỈ⣲㑏ඖࡋࠊp-C12-BPDA (ᵒ)ࢆᚓࡓࠋ
2-2 ࣏࣑ࣜࢻࡢྜᡂ
Cyclohexene-DA (ᵓ), DSDA (ᵔ)ࡢ2✀ࡢࢸࢺࣛ
࢝ ࣝ ࣎ ࣥ 㓟 ↓ Ỉ ≀ ࢆ ⏝ ࠸ ࠊp-C12-BPDA (ᵒ), DDE (ᵕ)ࡢ2✀ࡢࢪ࣑ࣥࡢΰྜẚࢆኚ࠼࡚ඹ㔜
ྜࢆ⾜࡞ࡗࡓࠋΰྜ
ẚࡣ⾲1♧ࡋࡓࠋ
2-3 ᪂つ࣏࣑ࣜࢻࡢ≀ᛶホ౯
㓟↓Ỉ≀ 㼀㼓 㼀㼐㻝㻜䈜㻝 䃖㼕㼚㼔䈜㻞
䉝 㼕㼚㻌㻭㼕㼞㻌 䝫䝸䜰䝭䝑䜽㓟 㻹㼚 㻹㼣 㻹㼣㻛㻹㼚 㻺㻹㻼 㼀㻴㻲 㻯㻴㻯㼘㻟
㻯㼥㼏㼘㼛㼔㼑㼤㼑㼚㼑㻙㻰㻭 㼜 㻙㻯㻝㻞㻙㻮㻼㻰㻭 㻰㻰㻱 䉝
㻝㻜㻜 㻝㻜㻜 㻜 㻞㻤㻠㻚㻝㻣 㻠㻡㻜㻚㻡㻞 㻜㻚㻜㻝㻠㻟 㻞㻝㻜㻜 㻟㻤㻜㻜 㻝㻚㻤 㻿 㻿 㻿 㻝㻜㻜 㻡㻜 㻡㻜 㻞㻥㻜㻚㻡㻠 㻠㻡㻞㻚㻤㻟 㻜㻚㻜㻡㻣㻟 㻟㻞㻜㻜 㻢㻠㻜㻜 㻞㻚㻜 㻿 㻿 㻿 㻝㻜㻜 㻜 㻝㻜㻜 㻞㻥㻠㻚㻢㻝 㻠㻡㻟㻚㻤㻠 㻝㻚㻞㻤㻟㻢 㻞㻡㻟㻜㻜 㻤㻜㻣㻜㻜 㻟㻚㻞 㻿 㻵 㻼㻿 㻰㻿㻰㻭 㼜 㻙㻯㻝㻞㻙㻮㻼㻰㻭 㻰㻰㻱
㻝㻜㻜 㻝㻜㻜 㻜 㻞㻝㻥㻚㻤㻥 㻠㻠㻣㻚㻣㻡 㻜㻚㻝㻝㻤㻥 㻝㻜㻝㻜㻜 㻞㻣㻟㻜㻜 㻞㻚㻣 㻿 㻿 㻿 㻝㻜㻜 㻡㻜 㻡㻜 㻞㻠㻥㻚㻠㻥 㻠㻡㻣㻚㻝㻟 㻜㻚㻠㻠㻞㻢 㻝㻥㻤㻜㻜 㻤㻜㻥㻜㻜 㻠㻚㻝 㻿 㻵 㻼㻿
㻝㻜㻜 㻜 㻝㻜㻜 㻞㻤㻞㻚㻤㻥 㻡㻤㻞㻚㻜㻤 㻜㻚㻠㻢㻣㻡 㻙 㻙 㻙 㻵 㻵 㻵
⾲㻞䚷䝫䝸䜲䝭䝗䛾䛺≀ᛶ
䈜㻝䚷㻝㻜㻌㼣㼠㻑㻌⇕㔜㔞ῶᑡ ᗘ䚷䚷䚷䚷䚷䚷䚷䈜㻞䚷㻜㻚㻡㻌㼓㻛㼐㼘㻌㼕㼚㻌㻺㻹㻼㻌䚷㻟㻜䉝䛷 ᐃ䚷䚷䚷䚷䚷 䈜㻟䚷㻿㻱㻯䛷 ᐃ䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷䚷㻌㻌䚷䈜㻠䚷䝫䝸䜲䝭䝗㻜㻚㻡㻌㼣㼠㻑䚷㻿㻦㻌⁐ゎ䚷㻼㻿㻦㻌୍㒊⁐ゎ䚷㻵㻦㻌⁐
㼙㼛㼘㻑
⁐ゎᛶ䈜㻠 䝫䝸䜲䝭䝗
䝰䝜䝬䞊
䝆䜰䝭䞁 ศᏊ㔞䈜㻟
᪂つ࣏࣑ࣜࢻࡢ࡞≀ᛶࢆ⾲2♧ࡋࡓࠋ Cyclohexene-DA ࡢඹ㔜ྜ࡛p-C12-BPDA ࢆ ᑟධࡋࡓࡶࡢࡣศᏊ㔞ࡀపࡗࡓࠋࡇࢀࡣ㛗㙐
ࣝ࢟ࣝࡼࡿ❧య㞀ᐖࡀཎᅉᛮࢃࢀࡿࠋࡋࡋ ᡂ⭷ᛶࢆ᭷ࡍࡿࡇࡸࠊ⪏⇕ᛶࡶ࠶ࡿࡇࡽࠊ ᐇ㝿ࡣSEC࡛ ᐃࡋࡓ್ࡼࡾࡶ㧗࠸ࡢ࡛ࡣ࡞
࠸⪃࠼ࡽࢀࡿࠋ
Cyclohexene-DA, DSDA ࡕࡽࡢඹ㔜ྜ࡛ࡶ
p-C12-BPDA ࢆᑟධࡋࡓࡇࡼࡗ࡚⁐ゎᛶࡀ
ྥୖࡋࡓࠋࡲࡓࠊ⣸እ⥺ࢆ↷ᑕࡍࡿࡇࡼࡗ࡚ࠊ
⾲㠃ࡀẁ㝵ⓗぶỈᛶኚࡋࡓ (ᅗ1, ᅗ2)ࠋ ࡇࢀࡣ⣸እ⥺↷ᑕࡼࡗ࡚㛗㙐ࣝ࢟ࣝᇶ➼ࡀ ษ᩿ࡉࢀࡓࡓࡵ⪃࠼ࡽࢀࠊIR (ATR) ᐃࡢ⤖ᯝ
ࡶࡇࡢ᥎ㄽࢆᨭᣢࡋ࡚࠸ࡿࠋ
㸱㸬⤖ゝ
p-C12-BPDA p-C12-BPDA ࢆᑟධࡋࡓ࣏ࣜ
࣑ࢻࢆྜᡂࡍࡿࡇᡂຌࡋࡓࠋࡲࡓࠊ⪏⇕ᛶࠊ
⁐ゎᛶࡀ࠶ࡾࠊග↷ᑕࡼࡗ࡚⾲㠃≀ᛶࡢࢥࣥࢺ
䝔䝖䝷䜹䝹䝪䞁㓟↓Ỉ≀
㻯㼥㼏㼘㼛㼔㼑㼤㼑㼚㼑㻙㻰㻭㻌㼛㼞㻌㻰㻿㻰㻭 㼜 㻙㻯㻝㻞㻙㻮㻼㻰㻭 㻰㻰㻱
㻝㻜㻜 㻝㻜㻜 㻜
㻝㻜㻜 㻡㻜 㻡㻜
㻝㻜㻜 㻜 㻝㻜㻜
㼙㼛㼘㻑
䝆䜰䝭䞁
⾲㻝䚷ඹ㔜ྜ䛾ΰྜẚ
(CH2)11CH3
(CH2)11CH3 O Cl
NO2
NO2
(CH2)11CH3
(CH2)11CH3 O
NO2
NO2 AlCl3 CH3NO2
reflux80Υ 2h
+
ᾀᴾ ᵐᴾ ᵑᴾ
(CH2)11CH3
(CH2)11CH3 O
NH2
NH2 H2 Pd/C
0.3Mpa 50 ḥ 1.5h
ᵒᴾ
Yield 84%
Yield 73%
50Υ
O O
O O
O
O
O O
O S
O O
O O
O
O (CH2)11CH3
(CH2)11CH3 N H2
N H2 N
H2 O N H2
ᵓᴾ
ᵔᴾ
ᵒᴾ ᵕᴾ
(X) (Y)
(X+Y)
+ +
O O O
(CH2)11CH3
H3C(H2C)11
1) r.t. 24h in NMP 2) pyridine , acetic anhydride
100Υ 4h in NMP
ᅗ㻞䚷㻰㻿㻰㻭㻌㻦㻌㼜㻙㻯㻝㻞㻙㻮㻼㻰㻭㻌㻦㻌㻰㻰㻱
㻜㻚㻜 㻞㻜㻚㻜 㻠㻜㻚㻜 㻢㻜㻚㻜 㻤㻜㻚㻜 㻝㻜㻜㻚㻜 㻝㻞㻜㻚㻜
㻜 㻞 㻠 㻢 㻤
↷ᑕ䜶䝛䝹䜼䞊㻌㼇㻶㼉 ᥋
ゐ ゅ㻔 Ỉ㻕㼇
㼻㼉 㻝㻜㻜㻌㻦㻌㻝㻜㻜㻌㻦㻌㻌㻌㻜
㻝㻜㻜㻌㻦㻌㻌㻡㻜㻌㻦㻌㻌㻡㻜
ᅗ㻝㻌㼏㼥㼏㼘㼛㻙㻰㻭㻌㻦㻌㼜㻙㻯㻝㻞㻙㻮㻼㻰㻭㻌㻦㻌㻰㻰㻱
㻜㻚㻜 㻞㻜㻚㻜 㻠㻜㻚㻜 㻢㻜㻚㻜 㻤㻜㻚㻜 㻝㻜㻜㻚㻜 㻝㻞㻜㻚㻜
㻜 㻞 㻠 㻢 㻤
↷ᑕ䜶䝛䝹䜼䞊㻌㼇㻶㼉 ᥋
ゐ ゅ㻔 Ỉ㻕㼇
㼻㼉
㻝㻜㻜㻌㻦㻌㻝㻜㻜㻌㻦㻌㻌㻌㻜 㻝㻜㻜㻌㻦㻌㻌㻡㻜㻌㻦㻌㻌㻡㻜 㻝㻜㻜㻌㻦㻌㻌㻌㻜㻌㻦㻌㻝㻜㻜
4 㸬ഃ㙐ศᒱࣝ࢟ࣝᇶࢆ᭷ࡍࡿ࣏࣑ࣜࢻࡢྜᡂ≀ᛶ
1. ⥴ゝ㻌
㻌 䝫䝸䜲䝭䝗䛸䛿䚸䜲䝭䝗⎔䜢᭷䛩䜛ඃ䜜䛯⪏⇕ᛶ㧗ศ Ꮚ䛷䛒䜛䛜䚸๛┤ᵓ㐀䛾䛯䜑䚸୍⯡䛻᭷ᶵ⁐፹䛻
⁐䛷䛒䜛䛸䛔䛖ḞⅬ䛜䛒䜛䚹ᮏ◊✲ᐊ䛷䛿䚸㛗㙐䜰䝹 䜻䝹ᇶ䜢ᑟධ䛧䚸⪏⇕ᛶ䜢ಖᣢ䛧䛯䜎䜎⁐፹䛻ྍ⁐
䛺䝫䝸䜲䝭䝗䛾◊✲䜢⾜䛳䛶䛔䜛䚹䛥䜙䛻䚸㛗㙐䜰䝹䜻 䝹ᇶ䜢ᑟධ䛧䛯䝫䝸䜲䝭䝗䝣䜱䝹䝮䛻UV䜢↷ᑕ䛩䜛䛸䚸 㛗㙐䜰䝹䜻䝹ᇶ䛜ษ᩿䛥䜜䚸䝣䜱䝹䝮⾲㠃䛜Ỉᛶ 䛛䜙ぶỈᛶ䛻ኚ䛩䜛䛣䛸䛜ุ᫂䛧䛶䛔䜛䚹㻌
㻌 ᮏᐇ㦂䛷䛿䚸ഃ㙐䛻ศᒱ䜰䝹䜻䝹ᇶ䜢ᑟධ䛧䛯ⰾ 㤶᪘䝆䜰䝭䞁䛾ྜᡂ䛸䚸䝫䝸䜲䝭䝗䛾⪏⇕ᛶ䚸UV↷ᑕ 䛻䜘䜛⾲㠃≀ᛶ䛾ኚ䜢᳨ウ䛧䛯䚹㻌
2.㻌 ⤖ᯝཬ䜃⪃ᐹ㻌
2.1㻌DBAE-20䠄8-12䠅 䛾ྜᡂ㻌
2-䜸䜽䝏䝹-1-䝗䝕䜹䝜䞊䝹㻌(1) 䜢ฟⓎཎᩱ䛸䛧䛶䚸 㻟㻘㻡 䝆䝙䝖䝻䝧䞁䝌䜲䝹䜽䝻䝷䜲䝗㻌(2) 䛸㐃⤖䛥䛫䚸䝆 䝙䝖䝻య㻌(3) 䜢ᚓ䛯䚹㻌
(CH2)9CH3 (CH2)7CH3 CH2CH (CH2)9CH3
(CH2)7CH3 HOCH2CH
O O
NO2 O2N
O Cl NO2 O2N
reflux 75Υ THF, TEA
䝆䝙䝖䝻య㻔㻔㻟㻕䜢᥋ゐỈ⣲㑏ඖ䛧䚸䝆䜰䝭䞁య㻔㻔㻠㻕䜢ᚓ 䛯䚹㻌
(CH2)9CH3 (CH2)7CH3 CH2CH
O O
NO2 O2N
Pd/C, 0.3MPa
(CH2)9CH3 (CH2)7CH3 CH2CH
O O
NH2 H2N
2.2㻌 䝫䝸䜲䝭䝗䛾ྜᡂ㻌
䝔䝖䝷䜹䝹䝪䞁㓟↓Ỉ≀䛻䚸cyclohexene-DA䜎 䛯䛿DSDA䜢䚸ⰾ㤶᪘䝆䜰䝭䞁䛸䛧䛶DDE䛸 DBAE-20(8-12) 䜢⏝䛔䛶ඹ㔜ྜ䜢䛚䛣䛺䛳䛯䚹
O O
O
CH3 O O
O
DDE
O
H2N NH2
(CH2)9CH3 (CH2)7CH3 CH2CH
O O
NH2 H2N
DBAE-20(8-12)
O O
O
O
O
O S O O
DSDA
2) Pyridine, Ac2O ,120Υ,4h in NMP
O O
N O
O N
O
CH3 O m
N O
O N
O
O O
CH3 n
(CH2)9CH3 (CH2)7CH3 CH2CH
x y
cyclohexene-DA
1) r.t.24 in NMP
㻌
2.3䝫䝸䜲䝭䝗䛾≀ᛶ 2.3.1㻌 ศᏊ㔞䚸⪏⇕ᛶ㻌
㻌 ᪂つ䝆䜰䝭䞁䜢⏝䛔䛯ඹ㔜ྜ䛷ᚓ䛯䝫䝸䝬䞊䛾⁐ゎ ᛶ䚸ᑐᩘ⢓ᗘ䚸ศᏊ㔞㻌 㻔SEC㻘㻌40䉝㻘㻌NMP 10ml LiBr㻕㻌 䛾 ᐃ⤖ᯝ䜢Table 1䛻䚸⪏⇕ᛶヨ㦂䛾 ᐃ
⤖ᯝ䜢Table 2䛻♧䛩䚹㻌
Dianhydride Solubility Șinh
a)
NMP dLg-1 Mn Mw Mw/Mn
Cyclohexene-DA DBAE-20(8-12) DDE
100 0 soluble 0.06 3100 6000 1.94
50 50 soluble 0.12 5400 11500 2.13
0 100 insolble 0.48 23500 73400 3.10
DSDA DBAE-20(8-12) DDE
100 0 soluble 0.24 16300 52300 3.20
50 50 soluble 0.46 55200 125200 2.27
0 100 insolble - - - -
a) Measured at 0.5gdL-1 in NMP at 30䉝.
100
100
Table 1䚷Polyimides䚷based on DBAE-20(8-12 )
b) Determined by SEC in NMP containing 10mM LiBr calibrated with a series of polystyrene Monomer
Diamine Molecular Weightb)
mol%
Polyimide
Dianhydride
䉝 (in Air)䉝 (under N2) 䉝 (in Air)䉝 (under N2) Cylohexene-DA DBAE-20䠄8-12䠅 DDE
100 0 377 375 386 387
50 50 379 377 389 392
0 100 337 442 458 457
DSDA DBAE-20䠄8-12䠅 DDE
100 0 383 379 390 390
50 50 368 387 416 401
Td10b)
100
100
Diamine mol%
a) 5% weight loss temperature, b) 10% weight loss temperature.
Table 2䚷Thermal stability of polyimides
Monomer Polyimide
Td5a)
2.3.2㻌UV↷ᑕ䛻䛚䛡䜛⾲㠃ศᯒ㻌
࣏࣑ࣜࢻࣇ࣒ࣝUV (254 nm) ࢆ↷ᑕࡋࠊ
ྛ↷ᑕ࢚ࢿࣝࢠ࣮࠾ࡅࡿࣇ࣒ࣝ⾲㠃ࡢỈ
ᑐࡍࡿ᥋ゐゅࠊ࠾ࡼࡧ⾲㠃ࡢᵓ㐀ኚࢆATRࡼ
ࡾ ᐃࡋࡓࠋྛ⤌ᡂࡢ࣏࣑ࣜࢻࡢ᥋ゐゅࡢ⤖ᯝ
ࡣTable 3♧ࡍ㏻ࡾ࡞ࡗࡓࠋ
Dianhydride
0J 2J 4J 6J 8J
Cyclohexene-DA DBAE-20(8-12) DDE
100 0 111 98 88 88 88
50 50 112 91 89 82 77
DSDA DBAE-20(8-12) DDE
100 0 97 92 89 68 59
50 50 93 94 89 90 65
100
100
Monomer Diamine
Water contactangle after UV irradiation UV irradition time mol%
Table 3䚷Water contact angle of Polyimides
ࡲࡓࠊATRࡼࡾ↷ᑕ࢚ࢿࣝࢠ࣮ࡀቑຍࡍࡿࡘࢀ
2920cm-1 2850cm-1ࡢࣝ࢟ࣝᇶࡢࣆ࣮ࢡࡀ ῶᑡࡋࠊ2750-3700cm-1ࡢỈ㓟ᇶࡢࣆ࣮ࢡࡀቑຍ ࡋ࡚࠸ࡿࡇࡀุ᫂ࡋࡓࠋ
3. ⤖ゝ
௨ୖࡢࡇࡼࡾࠊศᒱࣝ࢟ࣝࢆ᭷ࡍࡿࢪ࣑
ࣥࡢྜᡂࠊࡑࡢ᪂つࢪ࣑ࣥࢆᑟධࡋࡓྍ⁐ᛶ
࣏࣑ࣜࢻࡢྜᡂᡂຌࡋࡓࠋࡉࡽࠊUV↷ᑕ
ࡼࡿ᥋ゐゅࡢపୗࠊATRࡼࡾ⾲㠃ࡢᵓ㐀ኚ
ࢆ☜ㄆࡍࡿࡇࡀ࡛ࡁࡓࠋᚋࡣࠊ┤㙐ࣝ࢟ࣝ
ᇶࡢẚ㍑ࢆ᳨ウࡍࡿᚲせࡀ࠶ࡿࠋ
1 2 3
4 3
Yield 74%
Yield 63%
5㸬ഃ㙐㛗㙐ࣝ࢟ࣝᇶࢆࣇ࢙ࢽ࢚ࣝࢫࢸࣝ⤖ྜ࡛ᑟධࡋࡓྍ⁐ᛶ࣏࣑ࣜࢻࡢྜᡂ≀ᛶ
1. ⥴ゝ
࣏࣑ࣜࢻࡣ⧞ࡾ㏉ࡋ༢࣑ࢻ⤖ྜࢆྵࡴ㧗ศᏊ
࡛࠶ࡾࠊⰾ㤶᪘ⰾ㤶᪘ࡀ࣑ࢻ⤖ྜࢆࡋ࡚ඹᙺᵓ㐀ࢆ
ᣢࡘࡓࡵࠊ๛┤࡛ᙉᅛ࡞ศᏊᵓ㐀ࢆᣢࡕࠊࡘ࣑ࢻ⤖ྜ
ࡀᙉ࠸ศᏊ㛫ຊࢆᣢࡘࡓࡵࡍ࡚ࡢ㧗ศᏊ୰࡛᭱㧗ࣞ
࣋ࣝࡢ⪏⇕ᛶࠊᶵᲔⓗࠊᏛⓗᛶ㉁ࢆ♧ࡍࠋࡋࡋࠊࡑࡢ
๛┤࡞ᵓ㐀ࡢࡓࡵ୍⯡᭷ᶵ⁐፹⁐࡛࠶ࡿ࠸࠺
ḞⅬࡀ࠶ࡿࠋࡇࡢࡇࡽࠊ࣏࣑ࣜࢻࡢࢇࡣࠊྍ
⁐ᛶ๓㥑య࣏࣐࣮࡛ࣜ࠶ࡿ࣏࣑ࣜࢵࢡ㓟⁐ᾮࢆᇶᯈୖ
ሬᕸࡋࡓᚋࠊ300㹼350Υ࡛ᩘ㛫ຍ⇕ฎ⌮ࡋ࡚࣏࣑ࣜ
ࢻࣇ࣒ࣝᡂᙧࡍࡿ࠸࠺᪉ἲࡀࡽࢀ࡚࠸ࡿࠋࡋࡋࠊ ࡇࡢ᪉ἲ࡛ࡣ࣑ࢻ⋡ࡢࢥࣥࢺ࣮ࣟࣝࡀ㞴ࡋ࠸࠸ࡗ ࡓḞⅬࡀ࠶ࡿࠋࡇࡢࡼ࠺࡞⌮⏤ࡽ⪏⇕ᛶࢆಖᣢࡋࡓࡲࡲ
᭷ᶵ⁐፹ྍ⁐࡞࣏࣑ࣜࢻࡢ◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿࠋ ᮏ◊✲ᐊ࡛ࡣࠊᵓ㐀ෆ㛗㙐ࣝ࢟ࣝᇶࢆ᭷ࡍࡿᵝࠎ࡞
ࢪ࣑ࣥࣔࣀ࣐࣮ࢆྜᡂࡋࠊࡇࢀࡽࡢࢪ࣑ࣥࣔࣀ࣐࣮ࢆ
࣏࣑ࣜࢻ㦵᱁ᑟධࡍࡿࡇࡼࡗ࡚࣏࣑ࣜࢻࡢ⁐
ゎᛶࢆྥୖࡉࡏࡿ◊✲ࡀ⾜ࢃࢀࠊᐇ㝿ࡑࡢຠᯝࡀ☜ㄆࡉ
ࢀ࡚ࡁࡓ(1)-(6)ࠋ
ᮏ◊✲࡛ࡣࠊFig. 1♧ࡍ ࢹࢩࣝᇶࢆ3ಶ᭷ࡋࠊࡲࡓ2 ࡘࡢࣇ࢙ࢽ࢚ࣝࢫࢸࣝ⤖ྜ
ࢆᣢࡘ᪂つࡢࢪ࣑ࣥࣔࣀ
࣐࣮࡛࠶ࡿࠊ4-(3,5-diamino phenylcarbo)phenyl 3,4,5-tris (decyloxy)benzoate 㸦 ␎ ⛠ 10G1-DPCPBA㸧ࢆ┠ⓗ≀
ࡋ࡚ྜᡂࢆ⾜ࡗࡓࠋࡲࡓࠊࡇࡢࢪ࣑ࣥࣔࣀ࣐࣮ࢆ⏝࠸ࡓ
࣏࣑ࣜࢻࡢྜᡂㅖ≀ᛶࢆ᳨ウࡋࡓࠋ
2. ᐇ㦂⤖ᯝ⪃ᐹ 2.1 10G1-DPCPBAࡢྜᡂ
ฟⓎཎᩱࡋ࡚࢞ࣜࢵࢡ㓟࣓ࢳࣝ㸦㸦1㸧ࢆ⏝࠸࡚ࠊ1-ࣈ
ࣟࣔࢹ࢝ࣥࡢ࣒࢘ࣜࢯ࢚࣮ࣥࢸࣝࡼࡾࢹࢩࣝ
ᇶࢆᑟධࡋࡓ࢚ࢫࢸࣝయ㸦㸦2㸧ࢆᚓࡓࠋࡉࡽࠊỈ㓟࢝
࣒࡛ࣜ࢘ຍỈศゎࡍࡿࡇࡼࡾ࢝ࣝ࣎ࣥ㓟య㸦㸦3㸧ࢆᚓ ࡓ(Scheme 1)ࠋ
ᙜึࠊࣄࢻࣟ࢟ࣀࣥࢆྜᡂヨ⸆ࡋ࡚ࣄࢻࣟ࢟ࣀࣥࡢ୧ OHᇶ࢝ࣝ࣎ࣥ㓟య㸦㸦3㸧࠾ࡼࡧࢪࢽࢺࣟᏳᜥ㤶㓟㸦㸦7㸧
ࢆ୍ಶࡎࡘ㑅ᢥⓗ⤖ྜࡉࡏࡿࡇࢆヨࡳࡓࡀࠊOHᇶࡢ
∦ഃ㑅ᢥⓗ⤖ྜࡉࡏࡿࡢࡀᅔ㞴࡛࠶ࡾࠊ⤖ᒁࠊ࣋ࣥࢪ
ࣝಖㆤᇶࢆ⏝࠸ࡿ᪉ἲࡼࡾ࢝ࣝ࣎ࣥ㓟య㸦㸦3㸧4-࣋ࣥ
ࢪࣝ࢜࢟ࢩࣇ࢙ࣀ࣮ࣝ㸦㸦4㸧ࡢ㐃⤖ࡼࡾᡂຌࡋࡓࠋ
࣋ࣥࢪࣝಖㆤᇶయ㸦㸦5㸧ࢆຍỈ⣲ศゎࡼࡾ⬺ಖㆤࡋࠊ ᚓࡽࢀࡓࣇ࢙ࣀ࣮ࣝయ㸦㸦6㸧3,5-ࢪࢽࢺࣟᏳᜥ㤶㓟㸦㸦7㸧
ࢆ㐃⤖ࡋࢪࢽࢺࣟయ㸦㸦8㸧ࢆᚓࡓࠋ᭱ᚋ᥋ゐỈ⣲㑏ඖࢆ
ᚓࡽࢀࡓ10G1-DPCPBAࡘ࠸࡚ࠊ1H NMRIRࡼ
ࡾࢫ࣌ࢡࢺࣝ ᐃࢆ⾜࠸ࠊᵓ㐀Ỵᐃࢆ⾜ࡗࡓ(Fig.2)ࠋ
IR (KBr) : 2800~2950cm-1(decyl group)
3300~3500cm-1(-NH2), 1730cm-1 (C=O) Fig.2 Characterization of 10G1-DPCPBA
2.2 ࣏࣑ࣜࢻࡢྜᡂ
ࢸࢺࣛ࢝ࣝ࣎ࣥ㓟↓Ỉ≀cyclo-DA 㸦DSDA㸧ࢆ⏝
࠸ࠊࢪ࣑ࣥࣔࣀ࣐࣮ࡣỗ⏝ࡢࣔࣀ࣐࣮࡛࠶ࡿDDE ᪂つྜᡂࡋࡓ 10G1-DPCPBA ࢆ⏝࠸࡚ඹ㔜ྜࢆ⾜ࡗࡓ (Scheme 3)ࠋ
O O
O
O
O
CH3 O
N N
O
O
O
H2N O NH2
O O
O O
O O
NH2 H2N R
R OR
+ +
O O
O O
O O R
R O R
N N
O
O
O O
cyclo-DA DDE
10G1-DPCPBA
(x+y) (x) (y)
(x) (y)
1) r.t. , 24h, in NMP 2) Pyridine , Ac2O 120䉝 4h, in NMP S
O O
O
O
O
O O O DSDA
R = -(CH2)9CH3 O
O
O O
OH R
R OR
O O
O O
O R R
OR
O2N NO2 HO O
Pd / C MeOH / CH2Cl2
DCC / DMAP in CH2Cl2
O O
O O
O O
NH2 H2N R R
OR O
O
O O
O O
NO2 O2N R
R OR
Pd / C EtOH / THF
Scheme 2
5 Y.85%
6 Y.95%
7
8 Y.84%
HO O
DCC / DMAP in CH2Cl2 4
10G1-DPCPBA Y.91%
O O
O OH R R
OR
3
R = -(CH2)9CH3
O O
O O
O O
NH2 H2N (CH2)9CH3 H3C(H2C)9
O (CH2)9CH3
Fig.1 Structure of 10G1-DPCPBA
O O
O OCH3 R R
OR OH
HO
O OCH3 OH
O O
O OH R R
OR 3 RBr
DMF
KOH EtOH
R = -(CH2)9CH3
1 2
Y.95%
3 Y.91%
O HA
HA O HB HC HB O
HC HD HD O
H2N HE
H2N
O CH2 O
O CH2 CH2
CH2(CH2)7 CH2
(CH2)7 CH2
(CH2)7 CH3
CH3 CH3 O
HA
HA O HB HC HB O
HC HD HD O
H2N HE
H2N
O CH2 O
O CH2 CH2
CH2(CH2)7 CH2
(CH2)7 CH2
(CH2)7 CH3
CH3 CH3
