docq-poly (CMS-co-DVB)
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q-poly (CMS-co-DVB)
! ϯᏢπำࣴ!܌ز ᅺγᏢՏፕЎʳ ʳ ճҔϯᏢᇨว࣬ϩᚆᇙഢ ਼ϯᗋচགෳ܄ᖓጢ Synthesis of Oxidoreduction-Sensitive Films by Chemically Induced Phase Separation Method ࣴزғǺ܃উ! ! ࡰᏤ௲Ǻᎄ୯۸!റγ! ʳ ʳ ʳ ʳ ύ҇୯ΐΜϤԃϤД! ! ᄔ!ा! ! ፕЎӜᆀǺճҔϯᏢᇨว࣬ϩᚆᇙഢ਼ϯᗋচགෳ܄ᖓጢ ।ኧ;106 !!!!!!!!!!!! ਠ܌ձǺ୯ҥѠчࣽמεᏢϯᏢπำࣴ!܌ز ਔ໔ǺΐΜϖᏢԃࡋಃΒᏢය !!!!!!!!!!!ᏢՏ;ᅺγ! ࣴزғǺ܃উ!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!ࡰᏤ௲Ǻᎄ୯۸! ! ᜢᗖຒǺϯᏢᇨว࣬ϩᚆǵ߄य़ࠠᄊǵѭёᎇㄽữǵ਼ϯᗋচགෳ܄ᖓጢ! ҁ ࣴ زஒ 4- ෛ Ҙ ୷ श Ό (4-chloromethylstyrenf Ǵ CMS) ǵ Β Ό श (divinylbenzenfǴDVB)Ϸ2,2-ଽේᚈ౦୷㶮(2,2-azobisisobutyronitrileAIBN)аڰ ۓವԸКٯషӝǴӆуΕᕉρ₧(cyclohexane)բྋᏊǴᇙഢӭϾ܄ᖓጢǶၸу ҬᖄϸᔈࡕջёளډଯϩηᖓጢǴӧჴᡍύׯᡂྋᏊᕉρ₧֖ޑໆǴёளډό ӕ߄य़ࠠᄊϷϾሜ่ᄬޑᖓጢǴϐࡕஒᖓጢᆶѭёᎇㄽữ(nicotinamide)ޑΟભữ Չׯ፦ϸᔈႣයёளڀډԖ਼ϯᗋচ܄ϐᖓጢǶҁჴᡍճҔόӕᐚࡋޑᗋচ Ꮚ(H2S2O3)ǵ਼ϯᏊ(H2O2)ǵဟᑗНྋనϷѐᚆηН(pH=7)ჹᖓጢբௗفໆෳǴ ٠Кၨׯ፦ࡕᖓጢޑௗفৡ౦Ƕวׯ፦ࡕޑᖓጢڀԖၨӳޑᒃН܄ǴЪჹ ᐚࡋόӕޑᗋচᏊԖόӕޑዎᔸݩǴଯᐚࡋޑᗋচᏊჹܭᖓጢԖၨλޑௗ فǴեᐚࡋᗋচᏊ߾ϸϐǶᗋচᏊǵ਼ϯᏊǵဟᑗНྋనϷѐᚆηНѤޣύǴ а਼ϯᏊჹׯܭ፦ࡕᖓጢޑዎᔸࣁݩനৡǴځௗفനεǶՠࢂόӕᐚࡋ਼ޑ ϯᏊჹځܭௗفᡂϯ߾όᡉǶႣයჹ਼ܭϯᗋচᏊڀԖᒧ܄ǵᡫ௵ޑ܄ଯ ϩηᖓጢёаวࣁඵችࠠ٠ᔈҔܭғ܈ނϯᏢགෳᏔǶ I ABSTRACT TitleǺSynthesis of Oxidoreduction-Sensitive Films by Chemically Induced Phase Separation Method PagesǺ106 SchoolǺNational Taipei University of Technology DepartmentǺChemical Engineering DegreeǺMaster! TimeǺJune,2007 AdvisorǺKuo-Chung Cheng ResearcherǺYi-Lun Hsu KeywordǺchemically induced phase separation methodǵsurface morphologyǵ nicotinamideǵoxidoreduction-sensitive films Poly (4-chloromethylstyrene - co- divinylbenzene) films were made from polymerizing 4-chloromethylstyrene crosslinking with divinylbenzene by chemically induced phase separation method. The surface morphology of films is controlled by the volume percentage of solvent. The pore size increases with increasing the amount of solvent. Poly (4-chloromethylstyrene - co- divinylbenzene) films were further modified by nicotinamide; then oxidoreduction-sensitive films were formed. The surface properties of films were characterized by surface contact angle with oxidant, H2O2, reductant, H2S2O3, glucose, and!water, H2O(pH=7). The change of surface contact angle of the films were observed by an optical microscope.It indicates that the films are oxidoreduction-sensitive. The present study demonstrated a new signal responsive materials for bio- or chemical sensors. II ᇞ!ᖴ! ! !!!!ޑךᅺγғࢲஒӧԜჄΠѡဦǶӧ೭ٿԃޑਔӀύǴкᅈзךᜤޑבᗺᗺ ᅀᅀǴԶךஒ೭٤ᏫǴᝩុޑךΓғਓǶࡐགᖴεৎୖޑᆶǴᡣך ޑғڮᆸѠ׳уᆒߍǶ! !!!!ाགᖴޑΓԖӳӭӳӭǴ२ӃࢂࡰޑךᏤ௲ȉᎄ୯۸ԴৣǴᖴᖴԴৣ๏ϒ ޑך௲ᏤᆶԋߏǴӧஒٰޑᙍךոΚǴόᡣ 401 ჴᡍ࠻ᆾಚޑǶךΨाઔ ᅽ 401 ჴᡍ࠻ԖԴৣޑሦΠǴஒԖࡐऍӳޑ҂ٰǶௗΠٰाགᖴࢂޑα၂ہȉ Ў҅௲ǵЦεሎ௲ᆶྷ௲ǴᖴᖴԴৣॺӧԭԆϐύኘޜᏼҺᏢғޑ α၂ہǴ٠๏ϒࡐךӭགྷࡌکݤǴᡣޑךፕЎёа׳уֹ๓ǶٌधΑӚՏԴ ৣǶ! 401 ჴᡍ࠻ࢂךಃΒঁৎǴ401 ӕՔॺഉՔوךၸ೭ٿԃǴԖျᏢߏǵܴণ ᏢߏǵᏢᅺᏢߏǵܴᒑᏢߏǵ܃ԢᏢߏǵ්ᝬᏢߏǵৎᆪӕᏢǵ܃ԟӕᏢǵந ӕᏢǵγӕᏢǵ߷ԋӕᏢǵࡏำᏢǵయᏢϷ଼ֻᏢǴӳӭԋഽǼࡐ ໒ЈᇡգॺǴᖴᖴգॺӧ࡙ךආޑਔং๏ޑךᚎǴᖴᖴգॺӧךᜤၸޑਔং ๏ޑךᜢЈǴᖴᖴգॺǶࡕǴӣᏫѝԖ໒ЈޑǴεৎӧଆޑਔךڅ ᚶޑۺǶךᗋाᖴᖴ 402 Ϸ 406 ჴᡍ࠻ޑᏢߏکӕᏢǴԖԴӃғޑᔅԆǵӕᏢॺ ޑЈᡫ໒ᏤǴԖգॺӳǶϺΠคόණޑᆈৢǴಖزᗋࢂाၟգॺၰձǴεৎߥ ख़ΑǼǼ! !!!!ޑךӳܻ϶ฐǵធሺǵҸ൏ǴॺךᚆଯύςӳᇿᇻΑǴՠࢂ۶Ԝᗋ ࢂٗሶޑዕǴٗሶޑԖᓨࠨǶᖴᖴգॺᕴࢂ๏ྕךཪᆶӼኃǴךӳ഻ၟգॺ ӧଆǴॺךाவӳܻ϶ᡂԋԴܻ϶Ǵ҉ډޔᇻǶ!!!!! !!!!നࡕǴाགᖴࢂޑനхޑךৎΓǴךाךעޑ഻৹๏գॺǴݿޑך ݿǵޑך༰༰ǵޑךεޑךکۊΒۊǶᗨฅாӧޑךڂᘶલৢΑǴՠࢂ࣬ך ߞாޕၰޑǴாޕၰךΑǴாඹךགࡐډ໒ЈޑǴךݿݿངாǶ!! ! !!! III ! Ҟ!ᒵ! ! ᄔ!ा ................................................................................................................................ I ABSTRACT..................................................................................................................... II ᇞ!ᖴ ..............................................................................................................................III Ҟ!ᒵ ............................................................................................................................. IV ߄Ҟᒵ ........................................................................................................................... VI კҞᒵ .......................................................................................................................... VII ಃക ᆣፕ ....................................................................................................................1 ಃΒക চϷЎӣ៝ ................................................................................................3 2.1!ᖓጢϐᙁϟ ...............................................................................................3 2.1.1 ᖓጢϐ่ᄬᆶ܄፦ ........................................................................4 2.1.2 ᖓጢϐᇙഢ ....................................................................................4 2.1.3 ᖓጢϐׯ፦ ............................................................................................7 2.2 ӭϾ܄ଯϩηϐᇙഢ ...............................................................................8 2.2.1 ճҔᡏౢғଯϩηวݰᡏ ................................................................9 2.2.2 ٢ϯԶౢғଯϩηวݰᡏ ..................................................................11 2.2.3!ճҔ࣬ϩᚆᇙഢӭϾ܄ ..............................................................12 2.3!ଯϩη࣬ ܄................................................................................................13 2.4 ଯϩηྋనΚᏢ ........................................................................................14 2.5 Flory-Huggins theory ......................................................................................15 2.6 ࣬ϩᚆၸำޑԄڮکӜ .............................................................................16 2.6.1 ྕࡋᇨᏤ࣬ϩᚆȐTIPSȑ ..................................................................16 2.6.2 Binodal Curve .....................................................................................18 2.6.3 Spinodal Curve...................................................................................18 2.6.4 Critical Point .......................................................................................19 2.6.5 ϯᏢᇨว࣬ϩᚆȐCIPSȑ ..................................................................19 2.7 ׯ፦Ꮚޑϟಏ(nicotinamide)..........................................................................25 IV 2.7.1 ճҔׯ፦ೌמᇙഢфૈ܄ᖓጢ ..........................................................26 2.7.2 RedoxӅᆫޑނᔈҔ(nicotinamide) ..................................................26 ಃΟക!ჴᡍБ ݤ..........................................................................................................36 3.1 ჴᡍᛰࠔ .........................................................................................................36 3.2 ჴᡍሺᏔ .........................................................................................................38 3.3 ჴᡍࢬำᆶᡯ .............................................................................................40 3.3.1 ჴᡍࢬำ ..............................................................................................40 3.3.2!ჴᡍᡯ ..............................................................................................42 3.3.3 ჴᡍϸᔈԄ ..........................................................................................44 3.4 ჴᡍϩ .........................................................................................................45 ಃѤക ่݀ᆶፕ ......................................................................................................46 4.1 ྋᏊ֖ໆჹܭҬᖄଯϩηᖓጢϐቹៜ .........................................................46 4.1.1 ྋᏊ֖ໆჹܭpoly(CMS-co-DVB)ᖓጢࠠᄊϐቹៜ .........................46 4.1.2 ྋᏊ֖ໆჹܭpoly(CMS-co-DVB)ᖓጢ܄፦ϐቹៜ .....................48 4.2 ճҔѭёᎇㄽữׯ፦poly(CMS-co-DVB)ᖓጢ ........................................49 4.2.1 ᢀჸpoly(CMS-co-DVB)ᖓጢׯ፦ࡕޑ܄Ϸࠠᄊ .........................49 4.2.2 ѭёᎇㄽữჹܭpoly(CMS-co-DVB)ᖓጢׯޑ፦ .........................50 q-poly(CMS-co-DVB)่ޑᄬ᠘ ۓ......................................................50 q-poly(CMS-co-DVB)ׯޑ፦ ..........................................................50 4.2.3 Кၨpoly(CMS-co-DVB)ᖓጢׯ፦ࡕޑ܄፦ .............................51 4.3 ਼ϯᗋচᏊჹܭᖓጢޑௗف .............................................................52 4.3.1 ਼ϯᗋচᏊܭpoly(CMS-co-DVB)ᖓጢϐௗ ف.............................52 4.3.2 ਼ϯᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢϐௗ ف..........................53 4.3.3 ဟᑗНྋనܭpoly(CMS-co-DVB)ᖓጢϷq-poly...........................55 (CMS-co-DVB)ᖓጢϐௗفКၨ ....................................................55 ಃϖക ่ፕ ..................................................................................................................92 ୖԵЎ ........................................................................................................................93 ߕᒵ ................................................................................................................................99 ! V ! ߄Ҟᒵ! ߄ 2.1 ϯᏢᇨว࣬ϩᚆݤᇙഢӭϾ܄ଯϩηϐЎ߄……………………....28 ߄ 2.2 4-ෛҘ୷शΌϷѭёᎇㄽữ࣬ᜢϐЎ߄…………………........32 ߄ 3.1 ኬࠔޑжဦᆶಔԋԋϩ…………………………………………………..…..42 ߄ 3.2 ᖓጢׯ፦ࡕޑжဦ…………………………………………………..……..43 ߄ 4.1 poly(CMS-co-DVB)ᖓጢޑѦᢀ܄Ϸ༾ᢀࠠᄊ...........................................46 ߄ 4.2 poly(CMS-co-DVB)ᖓጢख़ϩኧᏵ………………………………..…….48 ߄ 4.3 q-poly(CMS-co-DVB)ᖓጢޑѦᢀ܄Ϸ༾ᢀࠠᄊ.......................................49 ߄ 4.4 q-poly(CMS-co-DVB)ᖓጢׯޑ፦………………………………….……..51 ߄ 4.5 ѐᚆηНჹܭᖓጢޑௗ…………………………………………ف..……..53 ! ! ! ! ! ! ! ! ! ! ! ! ! VI ! კҞᒵ! ! კ 2.1 ᇙഢᏱԖѮϾࠠϾࢰޑ܄ڰϐϯᏢᇨว࣬ϩᚆำ……ׇ...…...5 კ 2.2!!షӝԾҗૈࣁᡏᑈϩϐڄኧკ....................................................................14! კ 2.3 ཷा࣬ޑკ߄Ң UCST کLCST Չࣁ………………………………..……....17 კ 2.4 spinodal decomposition (SD)ᐒ………………………………………ڋ..…...18 კ 2.5 ྋှࡋୖኧޑӛໆკ߄ Ȑq ࣁᙯϯȑ ………………………………….……21 კ 2.6 ϯᏢᇨว࣬ϩᚆϐ࣬კ…………………………………………………..…..22 კ 2.7 ᔈҔϯᏢᇨว࣬ϩᚆݤᇙഢ܄ڰଯϩηᖓጢܭόӕᄊϐ࣬კ……....24 კ 2.8 ԋਡԋߏೲᒿ࣬ϩᚆၸำᄽϯޑკ…………………………………..…..25 კ 3.1 ኬࠔᇙഢკȐaȑୁຎკȐbȑҥᡏҢཀკ……………………………..........42 კ 4.1 ڰనΟ࣬ϐΚѳᑽკ………………………………………………..……..52 კ 4.2 ௗفीᆉკ………………………………………………………….……52 კ 4.3 (a)਼ϯᗋচϸᔈԄ(b)ᖓጢϐ਼ϯᗋচᄊ.......................................................54 კ 4.4 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ!(M1 ᖓጢ).....................................57 კ 4.5 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ!(M2 ᖓጢ)……………..………...57 კ 4.6 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (M3 ᖓጢ)………..……..……….58 კ 4.7 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (M4 ᖓጢ)…………..…………...58 კ 4.8 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (M5 ᖓጢ)…………..…………...59 კ 4.9 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M1 ᖓጢ)……………..………...59 კ 4.10 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M2 ᖓጢ)…………..…………...60 კ 4.11 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M3 ᖓጢ)……………..………...60ʳ კ 4.12 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M4 ᖓጢ)…………..…………...61ʳ კ 4.13 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M5 ᖓጢ)………….....…………61ʳ კ 4.14 poly(CMS-co-DVB)ᖓጢϐ TGA კ…………………………….…………..62 კ 4.15 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q1 ᖓጢ)…………..…………63 კ 4.16 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q2 ᖓጢ)………..……………63 კ 4.17 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q3 ᖓጢ)………..……………64 VII კ 4.18 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q4 ᖓጢ)………..……………64 კ 4.19 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q5 ᖓጢ)………..……………65 კ 4.20 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q1 ᖓጢ)…………..…………65 კ 4.21 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q2 ᖓጢ)…………..…………66ʳ კ 4.22 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q3 ᖓጢ)…………..…………66 კ 4.23 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q4 ᖓጢ)……………..………67 კ 4.24 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q5 ᖓጢ)………………..……67 კ 4.25 M1 ᖓጢϷ Q1 ᖓጢϐ IR Ӏკ………………………………………….....68 კ 4.26 M2 ᖓጢϷ Q2 ᖓጢϐ IR Ӏკ………………………………………….....68 კ 4.27 M3 ᖓጢϷ Q3 ᖓጢϐ IR Ӏკ………………………………………….....69 კ 4.28 M4 ᖓጢϷ Q4 ᖓጢϐ IR Ӏკ………………………………………..…...69 კ 4.29 M5 ᖓጢϷ Q5 ᖓጢϐ IR Ӏკ……………………………………..……...70 კ 4.30 ЎύѤΌ୷ữᡶ ޑIR Ӏკ………………………………………..…..70 კ 4.31 q-poly(CMS-co-DVB)ᖓጢϐ TGA კ……………………………..………..71 კ 4.32 ਼ϯᗋচᏊ ܭpoly(CMS-co-DVB)ᖓጢޑௗفᡂϯ…………..……..72 კ 4.33!!ѐᚆηН( pH=7 ) ܭpoly(CMS-co-DVB)ᖓጢޑௗف..........................73 კ 4.34 ѐᚆηН( pH=7 ) ܭq-poly(CMS-co-DVB)ᖓጢޑௗف.......................74 კ 4.35 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ! !!!!!!!!(Q1 ᖓጢ)………………………………………………………………..…...75! კ 4.36 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ! !!!!!!!!(Q2 ᖓጢ)………………………………………………………………….....76! კ 4.37 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ! !!!!!!!!(Q3 ᖓጢ)………………………………………………………………….....77 კ 4.38 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ (Q1 ᖓጢ~Q3 ᖓጢ)…………………………………………………………..78 კ 4.39 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑనᅀଯࡋᡂϯკ (Q4 ᖓጢ)…………………………………………………………..………...79 კ 4.40 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑనᅀଯࡋᡂϯკ (Q5 ᖓጢ)……………………………………………………………..……...80 VIII კ 4.41 ਼ϯᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢǴځଯࡋᡂϯࣁh/h0=0.2 ਔ ܌ᐕϐਔ໔(Q4 ᖓጢ)………………………………………………….…81 კ 4.42 ਼ϯᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢǴځଯࡋᡂϯࣁh/h0=0.2 ਔ ܌ᐕϐਔ໔(Q5 ᖓጢ)…………………………………………………….82 კ 4.43 ਼ϯᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢǴځଯࡋᡂϯࣁh/h0=0.2 ਔ ܌ᐕϐਔ໔(Q4 ᖓጢϷ Q5 ᖓጢ)………………………………………...83 კ 4.44 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϐௗف (M3 ᖓጢ)……………………………………….…………………………...84! კ 4.45 όӕᐚࡋޑဟᑗНྋన ܭq-poly(CMS-co-DVB)ᖓጢϐௗف (Q3 ᖓጢ)…………………………………………..………………………...85! კ 4.46 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-! co-DVB)ᖓጢϐௗفᡂϯ(M1 ᖓጢϷ Q1 ᖓጢ)……………………....86! კ 4.47 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-! co-DVB)ᖓጢϐௗفᡂϯ(M2 ᖓጢϷ Q2 ᖓጢ)………………………87! კ 4.48 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-! co-DVB)ᖓጢϐௗفᡂϯ(M3 ᖓጢϷ Q3 ᖓጢ)……………………....88! კ 4.49 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-! co-DVB)ᖓጢϐௗفᡂϯ(M4 ᖓጢϷ Q4 ᖓጢ)……………………....89! კ 4.50 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-! co-DVB)ᖓጢϐௗفᡂϯ(M5 ᖓጢϷ Q5 ᖓጢ)……………………....90! კ 4.51 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-! co-DVB)ᖓጢϐௗفᡂϯ…………………………………………..…91! ! IX ! !!ಃക ᆣፕ ! ᖓጢޑϩᚆೌמӧϯπౢύǴёаᔈҔࡐܭӭൂϡᏹբǴӵӧᇙำύჹނ ፦ޑᐚᕭǵϩᚆϷપϯǴԶᖓጢϩᚆೌמԖڗжϩᚆᇙำޑᖿ༈ǶӢࣁӧ ࣪ૈྍޑਔжǴวϩᚆᇙำӵᇃᚖǵ֎ԏǵڗǴሡाҔεໆૈྍǴ ԶᖓጢϩᚆڀೌמഢԖ࣪ૈྍޑᓬᗺǴ܌аԋࣁπೌמߐޑଯࣽממ ೌǶჹܭᖓጢޑׯࣁزࣴ፦ᖓጢೌמǴᖓጢҁيёаࢂጏஏࠠࢂ܈ӭϾࠠǴ ёаճҔׯ፦ׯٰೌמᡂᖓጢޑࢂ܈܄ቚуᖓጢҁيόڀԖ܄ޑ፦Ǵ٬ᖓጢڀഢ ځдޑфૈ܄ǶڀԖфૈޑ܄ଯϩηᖓጢёวࣁඵችࠠᖓጢǴѬᒿڬᎁᕉნ ޑᡂϯԶׯᡂᖓጢࠠᄊѐᔈཥޑᕉნǶ൩ӵΓᜪҜጥޑЛಒϾᒿѦࣚྕࡋ ޑᡂϯԶፓЛಒϾޑελǴѦࣚᕉნեྕਔǴЛಒϾᕭλ෧ϿΓᡏໆޑණ ѨǹѦࣚᕉნଯྕਔ߾ϸϐǶӧᖓጢׯ፦ೌמБय़ǴБࣁݤΎᅿǺ!1.ᄞӝ!2.ϯ Ꮲௗ݄!3.Ҭᖄ!4.ϕऀᆛၡӅᆫ 5.ߎឦᡶᜪబу!6.ଯϩηܫጕௗ݄!7/ႝዀׯ ፦ǴԶׯ፦ၸࡕޑᖓጢځᔈҔࣁ׳܄ቶݱǴࣁ׳Γᜪ܌٬ҔǶ! !!!!ӧ໘ࢤޑျ္ޗǴΓᜪӞݨޑᑨΞϿၮǴ܌аԖࡐӭЎܴੰפ ߐǴځύനதޑـЎܴੰϐࣁᑗֿੰǶᑡᑗֿੰᗨฅόىठԝǴՠࢂ܌Їวޑ ٳวੱΔӵύ॥ǵЈՈᆅ੯ੰǵ᠌ੰᡂ...ǴࠅӜӈ୯ΓΜεԝΫЬӢǶࣁΑ གྷޑғࢲϷ଼நޑғڮǴѳதᔈ၀ӳՈᑗޑᔠǴЀځᑗֿੰޣჹܭՈᑗޑ ࢂ׳ڋόё܈લǶ܌аᑗֿੰޑᙴᕍഢςԋࣁϞШࣚӚ୯य़ᖏޑख़ाፐᚒǴ ࡺวᅿᛙ܄ۓଯޑဟᑗᐚࡋགෳᏔࢂғϯࣚ࣬ख़ຎޑፐᚒǶ܌аҁࣴزճ ҔϯᏢᇨว࣬ϩᚆᇙഢӭϾ܄ᖓጢǴ٠ஒׯځ፦ࣁڀԖ਼ϯᗋচϐфૈ܄ᖓጢǶ׆ ఈׯ፦ࡕޑᖓጢஒёᔈҔܭঅႬႝཱུǴ٬ႝηܭႝཱུ߄य़Չ਼ϯᗋচϸᔈаճ ஒႝηሀ๏ႝཱུԋૻဦǶԶঅႬࡕޑႝཱུځႝηሀߔΚफ़եǵᡫ௵ࡋගଯǴ ܌аёวࣁႝϯᏢԄဟᑗᐚࡋགෳᏔǶӢဟᑗНྋనܭሇનϯΠёՉ਼ ϯᗋচϸᔈǴ٬ႝηሀԿႝཱུ߄य़ԶԋૻဦǴᙖҗૻဦޑம১ёаԶளޕ ဟᑗНྋనޑᐚࡋଯեǶ! !!!!ҁࣴزа 4-ෛҘ୷शΌࣁൂᡏǵΒΌशࣁҬᖄᏊ ک2,2-ଽේᚈ౦୷㶮ࣁ ଆۈᏊǴӆуΕόӕ֖ໆޑᕉρ₧բྋᏊǴᇙഢҬᖄଯϩηᖓጢǶஒଯϩηᖓጢ 1 ׯک፦ᏊѭёᎇㄽữаϯᏢௗ݄ݤՉׯ፦ϸᔈǶҁჴᡍճҔႝηඔᡉ༾᜔ᢀ ჸᖓጢࠠᄊǴ٠ྋᏊ֖ໆޑӭჲჹܭᖓጢ߄य़ࠠᄊϷϾሜ่ᄬޑቹៜǶԜѦǴ ճҔόӕᐚࡋޑᗋচᏊ(H2S2O3)ǵ਼ϯᏊ(H2O2)ǵဟᑗНྋనϷѐᚆηН(pH=7) ჹᖓጢௗفჴᡍǴ٠Кၨׯ፦ࡕᖓጢޑௗفৡ౦ǶӢࣁׯ፦Ꮚѭёᎇㄽ ữڀԖ਼ϯᗋচϐ܄Ǵ܌аႣයׯ፦ࡕޑᖓጢΨڀԖԜ܄Ƕჹ਼ܭϯᗋচᏊ Ԗᒧ܄Ϸᡫ௵ޑ܄ଯϩηᖓጢǴӧ҂ٰёวࣁඵችࠠ٠ᔈҔܭғ܈ނϯᏢ གෳᏔǶ ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! 2 ಃΒക চϷЎӣ៝ ! 2.1!ᖓጢϐᙁϟ! ᖓጢȐmembraneȑࢂଯϩηϯᏢπനԐޑуπౢࠔϐǴ߈൳ΜԃٰǴ ᒿҡݨϯπک༟уπޑวǴ༟ᖓጢޑғౢǵᔈҔΨᕇளΑࡐεޑว Ǵ٠ӧ༟уπύ՞ᏵΑख़ाޑӦՏǶᖓጢޑԖଯϩηǵߎឦǵഏౠ ǴځύΞаଯϩηКၨܰᇙഢǴԶ่ځᄬΨКၨᙦǴӢԜǴᔈҔޑ ጄൎ࣬ቶᗡǴӵǺхးǵႝηǵࡌᑐǵ୯ٛǵҬ೯ၮᒡ҇کғҔࠔӚБय़ว චख़ाբҔǶ ᖓጢࢂࡰаଯϩη༟ࣁচᇙԋޑጢނރǴΓॺಞᄍࡋࠆעӧ 250͔m аΠޑᆀࣁጢǴࠆࡋӧ 250͔m аޑᆀࣁТǶՠጢکТϐ໔٠คᝄࣚጕǴ ЀࢂځόӕਔǴӵ 70~80͔m ࠆޑฯᆫෛΌጢၨฯǴԶ 300͔m ࠆޑեஏ ࡋᆫΌጢࠅ٠όฯǴӢԜǴӧКၨᖓޑݩΠǴόܰΨؒԖѸाᝄჄϩᖓጢک ТǶ ᖓጢȐmembraneȑࣁᅿࣚय़ȐinterfaceȑǴѬࢂҔٰ႖໒࣬ٿЪڀԖᒧ܄ ࣚޑज़[1]ǴёکڋፓӚᅿނ፦ޑ೯ၸᆶऀೲǴԶၲ܌ډሡϐપϯǵᐚᕭǵ ϩᚆ[2]܈ЍଛޑҞޑǴԜБԄ܌ሡϐԋҁၨځдБԄϩᚆࣁեǶதޑـᖓጢࠠᄊ ԖጏஏࠠǵӭϾࠠǵᗭಈࠠߚکჹᆀࠠǶԶᖓጢ่ޑᄬ߯ࡰځϯᏢಔԋǵ༾ ࠠ܈ᄊಔᙃکϾࢰࠠᄊǶ٩ځ༾ᢀำࡋёஒϾࢰࠠᄊϩࣁ֡፦܄Ȑhomogeneousȑ ᆶߚჹᆀ܄Ȑasymmetricȑ Ƕ֡፦܄ᖓጢࢂࡰ่ځᄬᆶϾࢰϩթڀठ܄Ƕӧႝηᡉ ༾᜔ΠǴԖϾࢰޣǴځϾࢰελऊౣ࣬ӕǹคϾࢰޣǴ߾ࣁጏஏ܄ȐdenseȑᖓጢǴ аԾҗᡏᑈᢀᗺٰ࣮Ǵ่ځᄬૈϢλϩη೯ၸǶԶߚჹᆀ܄ᖓጢࢂࡰϾࢰελϩ թόठǴٯޑࠠڂηࢂҗጏஏޑҜቫȐskin layerȑᆶӭϾ୷ޑ܄፦Ȑporousȑ܌ ಔԋǴځύቫȐtop layerȑࣁ࣬ᖓϐҜቫǴԶΠቫȐsub layerȑࣁӭϾ୷ޑ܄፦Ƕ ԶӭϾ୷ޑ܄፦Ξёϩࣁੇᆟ่ރᄬȐsponge structureȑᆶЋࡰ่ࠠᄬȐfinger structureȑ[3]Ƕ 3 2.1.1 ᖓጢϐ่ᄬᆶ܄፦ ᖓጢ่ޑᄬǴ٩ᖓጢᡏᄬϷϾሜࡋёаϩࣁϖεᜪӵΠǺ (1) ༾ϾሜᖓጢȐmicroporous membraneȑ Ǻᖓጢϣ֖ԖεໆϾࢰǴځϾሜጄൎ 10nm ɴ10ȝmǴԜᅿࠠԄޑᖓጢЬा٬ҔܭӚᅿޑϩᚆำׇύǶ (2) ֡፦ጢȐhomogeneous membraneȑ Ǻ֡፦ጢ೯தࢂࡰጏஏคϾሜᖓጢǴځϩᚆᐒ ᄬΏճҔᘉණБԄǶ (3) ߚჹᆀጢȐasymmetric membraneȑǺځᖓጢ่ᄬЬाࢂҗቫࠆऊ 0.1ɴ2ȝm ޑ ҜቫϷऊ 100ɴ200ȝm ࠆޑӭϾሜЍኖቫ܌ಔԋǴதҔܭаᓸΚৡࣁ០Κޑϩ ᚆำׇǶ (4) ᚆηҬඤጢȐion exchange membraneȑ Ǻࢂᅿଯᑩዎޑ܄ᖓጢǴځ༾Ͼ่ᄬύ ڀԖ҅ႝॄ܈ႝǴаѦуႝౢғႝՏৡբࣁ០ΚǴճҔᖓጢϣڀ܌ ԖޑႝᚆηǴ႖๊ྋనύ࣬ӕႝނޑ፦Ǵ֎Їόӕႝޑᚆη٠٬ځ ೯ၸᖓጢǴаԜচၲډϩᚆޑਏ݀Ƕ (5) คᐒᖓጢȐinorganic membraneȑ ǺڀԖᓬ౦לޑϯ܄ϷӼ܄ۓǴځტڮၨߏᐒ ఓமࡋଯǴՠᇙำόܰǶ 2.1.2 ᖓጢϐᇙഢ! ᖓጢޑᇙഢБݤεठёаϩࣁΠӈ൳ᅿǺ 1. ᅙௗݤȐsinteringȑ: ҔܭલЮྋᏊྋှϐଯϩηǴڀځᡏޑБࣁݤ ஒۓελᗭಈޑણ҃ՉᓸᕭǴฅࡕуԿځᅙᗺߕ߈ࡋྕޑǴᗭಈ໒ۈ Ӣࣁᅙᑼ೬ϯਔǴᗭಈ໔ࣚޑय़ϕ࣬ೱௗǴԜਔᗭಈ໔ϐޜሜԋ༾λޑ ϾࢰǶ 2. ՜ݤȐstretchingȑ: ೭ᅿБࢂݤஒҽ่ϯޑᆫӝނᔒᓸ٠ݮࠟޔ ܭᔒᓸޑБӛ՜Ǵ٬่ୱѳՉܭᔒᓸБӛǶӧᔈΚբҔΠǴё٬ጢय़ઇ ԋ٤λϾࢰǴԶளډӭϾ่ᄬǶ 3. ॉၞᇑݤڅϯȐtrack-etchingȑ:ځБࢂݤ٬ጢ܈ᖓТௗܭޔࠟڙᖓጢޑଯૈಈ ηᒟǴԶ٬ளӧᖓጢύ੮ΠጕऀၸޑॉၞǴॉၞϐଯϩηӢ֎ ԏૈໆԶѺᘐԋϩηໆၨλޑλϩηǴฅࡕஒԜᖓጢΕᇑڅኲύǴճҔྋ Ꮚ٬λϩηྋрǴԶளڀډԖઞϾ৩ϩѲ֡Ϭޑ༝ࢊϾࢰᖓጢǶ 4 4. ྋрݤȐleachingȑǺӃஒٿᅿаނ፦షӝᇙԋᖓጢǴӆճҔྋᏊஒځύᅿ ނ፦ྋрǶ 5. ࣬ᙯඤݤȐphase inversionȑ:܌ᒏ࣬ᙯඤࢂݤ٬ଯϩηҗྋనύ؇ᐘрٰԋࣁ ೱុ࣬ޑᏉጤȐgelȑǴԜᏉጤଳࡕջࣁᖓጢǶ ځύ࣬ᙯඤݤΞёϩࣁΠӈϤᅿБݤǺ (A) ϯᏢᇨว࣬ϩᚆݤȐchemically induced phase separationȑ[4-7] CIPS ΨעѬᆀϯᏢհࠅࢂ܈ᆫӝᇨว࣬ϩᚆȐpolymerization induced phase separationȑϷϸᔈᇨว࣬ϩᚆȐreaction-induced phase separationȑ ǶճҔଯϩη ӧᆫӝޑၸำύǴӢࣁԋҬᖄᆛ่ރᄬޑଯϩηᆶྋᏊྋှࡋό٫Ǵ٬চҁ ᆶൂᡏԋ֡࣬ޑྋᏊрǴΨ൩ࢂӧϯᏢϸᔈၸำύଯϩηᆶྋᏊЇว࣬ϩ ᚆǴӆаڗǵଳᔿǵᇃวБԄஒྋᏊѐନள܌ډሡϐӭϾ܄ᖓጢǶ ࠠڰ༟ጤёճҔӧځวғฯϯၸำਔǴԶ٬ளΒঁଯϩη࣬࣬ޑϩ ᚆำׇౢғ٠ёځڋϾࢰᄊܭኧঁ༾ԯޑጄൎ[8]Ƕ Precursors Ѐ Solvent One liquid phase Curing and in situ phase separation Drying and post curing Two phase solid-liquid Two phase solid-void კ 2.1 ᇙഢᏱԖѮϾࠠϾࢰޑ܄ڰϐϯᏢᇨว࣬ϩᚆำ[ׇ8] ӧБݤॺךёճҔঁߚϸᔈ܄ЪեϩηໆޑనᡏٰڗжڀԖϸᔈޑ܄ჲ ᆫӝނวғ࣬ᡂϯǴ୷ܭаޑҗǴ܌аॺךѸᒧঁؼྋᏊȐgood solventȑǴ٬ځܰᆶ҂ฯϯޑӃ០࣬ނྋǴӵԜёளډঁև֡࣬ޑషӝ ނǴԶӧฯϯϸᔈޑය໔ǴচҁჹܭӃ០࣬ࢂނྋ܄ӳޑྋᏊᙯᡂԋߚྋᏊ Ȑnon-solventȑԶ໒ۈวғ࣬ޑᡂϯ٠ԋόೱុޑన࣬ǴԜਔӧسύϩձ ࢂҗଯࡋҬᖄڰޑᡏҁ፦ᆶϩණޑనᅀ܌ಔԋޑϕό࣬ྋϐ࣬ᄊǴനࡕёߥ ځҬᖄᆛ่ރᄬܭᐎጤᄊਔаࡋྕڋӧྋᏊݦޑᗺаஒྋᏊѐନǴҗॊ ่݀ޑёౢғঁҗ࣬ϩᚆำ܌ׇԋޑϾࢰ่ᄬǶځၸำӵკ 2.1 ܌ҢǶ 5 (B) ᇨᏤԄ࣬ᙯඤ (ݤThermal induced phase separationǹTIPS ) ୷ځҁБݤΏࢂᙖྕࡋᡂϯǴ٬֡࣬ଯϩηྋనϐྋှࡋफ़եǴ࣬ڋϩᚆ ՉࣁޑౢғǴߦ٬ଯϩη؈ᐘԶԋᏉጤȐgelȑǴനࡕԋቫᖓጢǴӆҗ ڗȐextractionȑǵචวȐevaporationȑ܈հএଳᔿȐfreeze dryingȑБݤǴ аѐନූӸϐྋᏊǴനࡕଳᔿԋጢ[9]ǶӢԜǴᇨᏤԄ࣬ᙯඤࢂݤ᠗ጢࡕڋ ځफ़ྕೲϷྕࡋᡂϯǴፓ࣬ځϩᚆՉࣁǴᙖԜׯᡂόӕᖓጢ่ᄬޑԋǶ (C) ᇃ࣬ᙯඤݤȐPrecipitation from the vapour phaseȑ[10] ԜݤനԐࢂҗ 1918 ԃҗ Zsigmondy ܌ගрǶЬाࢂஒᖓጢߚܭྋᏊޑᇃ ࣬ࢂ܈ྋᏊᆶߚྋᏊషӝޑႫکᇃᓸΠǴᙖҗߚྋᏊޑᇃ࣬բࣁ؈ᐘޑ០ ΚǶԜѦǴߚڋྋᏊӧ࣬ύޑᇃᓸٰ،ߚۓྋᏊᘉණΕྋᏊύޑೲ ࡋǴҗܭᇃӧᖓጢྋనύޑᘉණೲࡋᄌǴ٬ளߚྋᏊӧࣚय़Ԗܴᡉޑᐚࡋఊ ࡋৡǴӧᖓጢύ߾ᖿܭѳǶӢԜӧᖓጢ߄ޑय़εؒԖጏஏޑҜቫԶࢂӭϾ ่ޑᄬǶ (D) ଳԄ࣬ᙯඤ (ݤPrecipitation by solvent evaporation )[11-12] ᙖҗଯϩηᆶචว܄ྋᏊଛᇙԋϐ᠗ጢྋనǴӧࢌޑۓڰЍኖቫȐglass or nonwovenȑǵྕࡋǵݗȐේޜ܈ȑϐΠྋᏊᅌචวǶԿֹӄචวࡕǴ җܭଯϩηྋనϐྋှࡋफ़եǴӢԜวғ࣬ϩᚆԶԋᖓጢ่ᄬǶ (E) ᔸԄ࣬ᙯඤ (ݤWet-phase inversion )[13] ԜݤதҔаπᇙำᇙߚჹᆀ܄ᖓጢǴځᇙБ߯ݤஒଯϩηྋన᠗ጢࡕ ΕᏉᆫᏊȐߚྋᏊȑύǴԜਔྋᏊکᏉᆫᏊ໔ՉᘉණҬඤբҔǴճҔߚྋᏊ ஒ᠗ጢనύϐྋᏊڗрٰǴӕਔᏉᆫᏊΨёΕ᠗ጢనύǴᏤठଯϩηྋှ ࡋफ़եǴ٬᠗ጢనڰϯԋጢǶӵԜ܌ᇙளϐᖓጢ೯தڀԖӭϾ่܄ᄬࠠᄊǴ ԶЪጢ่ᄬڀёᡂ܄Ϸёፓ܄Ƕ (F) ଳ/ᔸԄషӝᇙำ( Dry / Wet process)[14] Ԝᇙำࣁॊঁٿᇙำ่ޑӝǴӃஒ᠗ጢྋనᓉࢤਔ໔ᡣྋᏊචวǴӆܫ ΕᏉᆫᏊύஒྋᏊڗрٰǴᏤठଯϩηྋှࡋफ़եǴ٬᠗ጢనڰϯԋጢǶճ ҔڋъࢤޑྋᏊචวਔ໔ǴᖓጢёаڀԖόӕޑҜቫࠆࡋǶ ! 6 2.1.3 ᖓጢϐׯ፦ җൂ፦ၨόܰᇙഢрԖؼӳނமࡋǴЪଯၸᆶᒧޑ܄ϩᚆᖓ ጢǴӢԜऩૈаٿᅿаϐٰׯ፦ԋፄӝ܄ᖓጢȐcomposite membranesȑஒ ёаࡋׯ๓ԜୢᚒǶᖓጢׯ፦БݤЬाԖǺ 1.ᄞӝȐblendingȑ ᄞӝёаճҔނϐБٰݤషӝǴଛᇙԋᖓጢύٿ֖܌ᅿόӕϐᆫӝނǴځϐ ໔όۓԖϯᏢᗖӸӧǶӧ࣬ύҗӚᅿᆫӝ܌ނಔԋǴᙖҗ٬Ҕϕྋ܄ ȐmiscibilityȑၨଯޑǵуΕϿໆ࣬ޑྋᏊȐcompatibilizerȑǴٰׯ๓ٿᜐࣚ ϐ࣬ϩᚆȐphase separationȑՉࣁǴаၲډၨ٫܄ޑ፦Ƕ 2.ϯᏢௗ݄Ȑchemical graftingȑ ௗ݄ᆫӝБࢂݤӧׯ๓ଯϩη܄፦ύനதҔޑБݤǴௗ݄ջࢂஒόӕൂޑᡏௗ ډଯϩηޑЬǴࢂуΕޑଆۈᏊЇวௗ݄ᆫӝϸᔈǴΞёϩࣁ਼ϯᗋ চௗ݄ǵᚆηௗ݄Ǵՠୁޑௗ݄ᆫӝࡋόεਔǴ۳۳ӧᇙԋᖓጢਔЬ๏ хᙟǴځ܄όܰ߄рٰǶ 3.ҬᖄȐcrosslinkingȑ Ҭᖄ೯த٬ҔޑਔᐒࢂࣁΑᗉխଯϩηܭϩᚆำׇύྋှܭྋనǴࣁࢂ܈ Αफ़եଯϩηϐᑩዎำࡋǴауமᖓጢޑӼ܄ۓϷዴߥϩᚆਏ݀ǴаԜᅿБݤёа рε೯ໆޑᖓጢǴՠाዴߥځҬᖄޑำࡋଯǴց߾ጢࡐܰઇཞǶ 4.ϕऀᆛၡӅᆫȐinterpenetrating copolymerizationȑ ೯தࢂஒൂᡏᆶႣᆫނྋӧଆϐࡕǴӆՉϸᔈԶளǴӢԜόӕޑଯϩη໔ ԖϯᏢᗖ่ޑӸӧǴ࣬ځϕޑ่ޟᆛ่ރᄬǴ٬ᖓጢڀԖၨ٫ޑᐒఓ܄፦Ƕ 5.ߎឦᡶᜪబу ӧၸѐኧΜԃٰճҔߎឦᡶᜪϺуΕᆫӝᡏύٰϩᚆрޜύ਼ޑԖεໆޑ ЎൔᏤǴՠ೭٤ᒱӝނҁيԖӼ܄ۓόޑىୢᚒǴԶԋόӼޑۓচӢࢂ೭٤ߎ ឦᒱӝܰނᆶ਼բҔౢғᚈᡏϯϸᔈȐdimerizationȑǴӢԜऩܭᖓጢύуΕߎឦ ᒱӝނǴ२ӃѸफ़ե਼ϯϸᔈޑᐒϷቚуߎឦᒱӝޑނӼ܄ۓǹӧనᡏϩᚆБ य़ǴబуߎឦᡶᜪܭᎉለᠼᆢᇙጢనύǴёගଯНᅖǴճҔԜబуߎނឦᡶᜪ ٬کځጢౢғᒱӝޑނᢀۺǴёۯ՜ԿځдᇙጢǴӵᆫㄽữǵPVDF Ƕ 7 6.ܫጕௗ݄ ଯϩηҗуଭጕౢғԾҗ୷ǴѝाӧచҹΠǴջёԖਏӦஒൂᡏௗ݄ ډଯϩηǴКଆϯᏢௗٰ݄ளᙁߡǵଳృǴЪϸᔈ֡ϬǴӢԜ߈ԃٰǴӭ ᏢаܫጕЇวᆫӝϸᔈϷൂᡏௗ݄ډଯϩηǴаวрཥޑଯϩηǶ ܫጕྣௗ݄ଯϩηϸᔈǴεठёаϩࣁٿεᜪǺ (A) ӕਔྣݤȐmutual irradiationȑǺൂᡏᆶଯϩηӅӸΠаܫጕྣаЇ วଯϩηௗ݄ϸᔈൂᡏǶ (B) ႣྣݤȐpre-irradiationȑ ǺӃྣЬ݄ଯϩηϯӝނǴӆஒܭځϸᔈ ϐൂᡏύǴԶౢғௗ݄ϸᔈǶ 7.ႝዀׯ፦Ȑplasma modificationȑ ႝዀ܄ࢲޑϷૈໆКଆނ፦ޑᄊᗋଯǴᄊϩη܌ևࣁႝύ๊܄ ጔރᄊǴՠӧமεૈޑໆϷႝύǴёаஒύޑ܄ϩηᐟวԋႝηǵᚆηǵԾҗ ୷ރޑᄊǴᆀϐࣁႝዀރᄊǶЬाޑᔈҔёϩࣁႝዀᆫӝȐplasma polymerizationȑǵ ႝዀᇑڅȐplasma etchingȑϷ߄य़ೀБय़Ƕ ! 2.2 ӭϾ܄ଯϩηϐᇙഢ! ӭϾ܄ଯϩηॺךख़ӧ܄ڰӵՖႣෳ࣬ՉࣁکᇙഢǶԋϾࢰޑଯϩ ηǴх֖൳ᅿБݤǴวݰᏊ[15]Ȑgas blowingȑǵ٢ጤڗӸȐemulsion derivedȑ࣬ک ϩᚆȐphase separationȑǶځύӧϯᏢᇨว࣬ϩᚆȐCIPSȑх֖ϸᔈଯϩηᖿ کނྋᏊǴׯᡂ₲Ȑenthalpyȑ⪖کȐentropyȑёׯᡂسޑԾҗૈȐfree energyȑ Զё࣬ڋϩᚆǶ ่ᄬޑԋϩಔԋவႣکقჴ࣬ՉࣁǴёள୷ډҁࡰޑᏤБଞǴЪૈளډനࡕ ϾࢰࠠޑᄊǶ࣬ٿଯϩηనᡏޑၸำΚᏢޑቹៜǴёளېډҥ܈ӅೱុޑϾ ࢰǶ ӧௗΠٰϟಏޑϩǴॺךஒܴکှញόӕޑБݤѐᇙഢӭϾޑଯϩηکᔠ ளډ༾Ͼࢰࠠڰଯϩηޑёૈ܄Ƕനख़ाѐᇙഢଯϩηวೌמޑݰӵΠ [1,2] Ƕӧόӕޑᇙഢ༾ϾࢰଯϩηೌמޑϐύǴёϩࣁΟᅿၡጕǺಃᅿх֖٬ Ҕᡏࣁࢰޜԋޑύ໔ނǶಃΒᅿࢂа٢ϯనࣁύ໔ނǴԋঅႬӅᆫӝ ނǴϐࡕ౽ѐϩණ࣬ǶಃΟᅿᜪձࢂ٬Ҕ࣬ϩᚆޑၸำύѐౢғޑ࣬ঁٿᄊǴന 8 ࡕౢғӭϾޑᄊǶ 2.2.1 ճҔᡏౢғଯϩηวݰᡏ วݰࢂࡰύ֖ԖεໆϾǴԜ่ᄬޑᓬᗺࣁКख़λǵ፦ໆᇸǴӢԜ၀ ፦ӧεԾฅύΨբࣁ่ᄬǴӵЕǵੇᆟǵβᝆǴ܌ࢂ܈ᒏီޑணಔᙃ ΓπҭቶݱᔈҔǴวݰ٩่ځᄬࠠᄊё߃ϩࣁΒεᜪǺ่ݣݰᄬᆶ ီண่ᄬǴԶݣݰȐวݰȑ่ᄬ٩ځϾࢂցೱ೯ΞёϩΒεᜪǺᐱҥࠠȐclose cellȑ ᆶೱ೯ࠠȐopen cellȑ ǶᐱҥࠠϐϾߥԖֹӄݰޑᏛǴ۶Ԝคϕ࣬ೱ೯ǴԶೱ೯ ࠠϐϾ߾ࣁ۶Ԝϕ࣬ೱ೯Ƕ ӧ༟ጤวݰуπၸำύǴޑݰԋёаϩࣁԋਡȐnucleationȑϷݰԋߏ ȐgrowthȑٿᡯǶ༟ጤύݰޑၲޑىډၸႫکȐsupersaturationȑރᄊਔǴ ԋਡբҔ໒ۈวғǴӃԋӭݰ༾ݰȐbubble cellȑ ǴᏤठ༟ጤύޑᡏᐚࡋ ᅌफ़եǶᡏၸႫکำࡋόىਔǴԋਡբҔջଶЗǴ༟ጤύޑᡏᝩុᙖᘉණբ ҔΕݰύǴݰ໒ۈԋߏǴԶ༟ύޑᡏᐚࡋᝩុफ़եǶډၲཥޑႫکᐚ ࡋࡕǴѳᑽख़ཥࡌҥǴԜࡕݰӝٳբҔȐcoalescenceǴᡏҗλݰᘉණΕ εݰȑ܈༟ҁޑيᔈΚکȐstress relaxationȑԶᝩុԋߏǶԋਡຝȐnucleationȑ ё ϩ ࣁ ֡ ࣬ ԋ ਡ Ȑ homogeneous nucleation ȑ Ϸ ߚ ֡ ࣬ ԋ ਡ Ȑ heterogeneous nucleationȑٿᅿᜪࠠ[16]ǶวݰԋࠠǴ२Ӄᔈӧ༟ጤᅙᡏڰ܈ᡏύԋεໆ֡Ϭಒஏ ݰޑਡǴฅࡕӆᑩԋࣁ܌ाϐݰᡏ่ᄬݰޑᡏǶाޑݰڋᑩၸำǴѸ ΑှݰᑩޑΚߔکΚǴӚቹៜӢન࣬کϕϐ໔ޑᜢ߯ǶቹៜݰԋߏޑӢ નࡐӭǴᘜયଆٰёϩࣁٿεᜪǶ ǵ ឦܭচೕǵࠔᅿǵૈ܄аϷҔໆޑቹៜǴٯӵǺวݰᏊޑᐚࡋǵ ྋှࡋǵᘉණ߯ኧǵᆫӝޑނᗹቸૈ܄Ǵдॺׯᡂ࣬ٿϐ໔ނޑሀૈ܄Ǵٰ ቹៜޑݰԋߏၸำǶ Βǵ ឦܭуπୖኧޑቹៜǴٯӵǺᓸΚǵྕࡋǵਔ໔Ƕ೭٤ୖኧჹݰ ԋߏΚԖமਗ਼ޑቹៜǴᗋёаׯᡂቹៜӢનૈ܄ޑǴٰׯᡂѬॺჹวݰၸำޑ ቹៜ[17]Ƕ ᇙวݰᆫӝނനቶݱ٬ҔسޑǴࢂஒᡏϩණܭঁనᄊޑᆫӝނǴ٠Ъ ᛙۓԋޑวݰᡏǴεӭኧ೭ᜪࠠسޑǴวݰᡏޑԋߏࢂӧسᗋؒၲᛙރۓᄊ 9 ਔǴቚуޑݰελǶҗϩණᡏޑำׇǴ܌ᇙрޑวݰᡏх֖Α൳ᅿᜪࠠǺ Ȑ1ȑʳ ༟܄วݰᡏǺஒӳޑ༟܄༟ጤуྋှࡕǴᏤΕ٠ϩණᡏǴհࠅ ࡑځᛙࡕۓǴջԋวݰᡏǶ Ȑ2ȑʳ ܄ڰวݰᡏǺϸᔈނҗϸᔈౢғᡏǴԜਔঁسᗋࢂనᄊǴࡑዕ ԋᛙࡕۓǴջԋวݰᡏǶ วݰᡏྍٰޑԖӳ൳ᅿǴх֖Ǻ 1ǵҗᠳ٬ޜషΕύǶ 2ǵճҔ ଯᓸஒᡏǴӵCO2ǴྋှܭύǴӆ෧ᓸࢂ܈уញܫрᡏǶ 3ǵ٬Ҕեݦ ᗺޑనᡏǴӆ෧ᓸࢂ܈у٬ځԋᡏǶ 4ǵճҔϸᔈౢғᡏǴӵisocyanate ϸ ᔈԋcarbodiimide ܌ౢғޑCO2Ƕ ٬ҔวݰᏊȐBlowing AgentsȑౢғᆫӝޑวݰᡏǴቶݱӦ٬Ҕӧ๊ጔǵ๊ک ࠾းޑǶวݰᡏϣޑϾࢰࢂҗܭᡏᑩౢғޑǴᡏӧషӝᡏౢғݰ ϐᐒᄬԖٿᅿБԄǴϩձࣁނϷϯᏢБݤǶ (1) ނวݰᏊȐPhysical blowing agentsȑ ނวݰᏊࢂեݦᗺܰචวޑనᡏǴ೭٤నᡏх֖િެᅹణᜪǴӵեݦᗺ ᎇǵ⾸ǵ✉ǵޱ३ᅹణᜪǵഛϯᅹణᜪǴӵ CFC-11 ܈CFC-143Ƕঁӳނޑ วݰᏊ಄ӝ൳చҹǺ Ȝ1ȝѸૈ֡ϬషӝྋှܭϸᔈྋనύǴЪόૈቹៜϸᔈྋనϣӚঁಔԋނޑ ϷϯᏢ܄፦Ƕ Ȝ2ȝதྕਔǴाԖեᇃᓸǴӧᡏރᄊਔǴڀഢᛙ܄ۓǶ Ȝ3ȝόڀԖᆭᇑ܄ǵܰᐯ܄ǵࢥ܄ǵૌښǴаϷჹᕉߥค্Ƕ Ȝ4ȝሽեǴܰڗளǶ FreonȐchlorofluorocarbons, CFCsȑࢂനቶݱ٬ҔܭPU วسݰޑᅿނว ݰᏊǴ٠ЪΨёаᔈҔӧځдวسݰύǴӵFreon 11 کFreon 113 ٬ҔܭPolystyrene วݰǴFreon 114 کFreon ٬ҔܭPolystyrene ϷPolyethylene ว[ݰ18]Ƕ җ ܭFreon ڀԖόёᐯ܄ǵեࢥ܄ǵեᘉණ߯ኧǵեᏤ߯ኧǴ܌аεໆ٬ ҔܭπǴޔԿวѬઇᚯεύޑૌ਼ቫࡕǴωЗ٬ҔǶҞςวрё ૈڗж Freon ޑϯӝ ނHCFCsȐ֖ణ ޑCFCsȑǶ (2) ϯᏢวݰᏊȐchemical blowing agentsȑ ϯᏢวݰᏊԖঁٿ٬ҔޑᓬᗺǴಃǴܰܭᏤΕวݰಔԋύǴӢԜܰܭуπǹ 10 ಃΒǴӢࣁᓯӸܰǴЪሽКނวݰᏊեࡐӭǶϯᏢวݰᏊᒧሡा൳ঁచ ҹǺ Ȝ1ȝϩှྕࡋሡᆶଯϩηޑᅙᗺϷฯϯྕࡋ࣬߈Ƕ Ȝ2ȝᡏញܫೲࡋѸሡזೲǴЪܰܭҔྕࡋǵᓸΚڋǶ Ȝ3ȝᡏϷځϩှϐࡕޑౢނሡόڀԖᆭᇑ܄ǵܰᐯ܄ǵࢥ܄ǵૌښǴаϷჹ ᕉߥค্Ƕ Ȝ4ȝϩှޑᡏሡૈ֡ϬషӝܭϸᔈނಔԋύǶϯᏢวݰᏊύǴCO2 ࢂനख़ा ЪᐕўനΦޑᅿǴѬࢂҗNCO/H2OǵCOOH ϸᔈౢғǴࢂᇙวݰᡏ όёલϿޑวݰᏊᡏǶՠӧᇙ୲ฯวݰᡏਔǴаCO2 ࣁЬाวݰᏊԖ ൳ঁୢᚒሡाլܺǴӵ႖๊ਏ݀Πफ़ǵԋࠔЁκόӼۓǵૄϯکҗଯܫϸ ᔈЇଆޑԾวᐯᐨǶబуނวݰᏊǴჹׯ๓೭٤લᗺࢂڀԖਏ݀ޑǶ 2.2.2 ٢ϯԶౢғଯϩηวݰᡏ! ٢ϯȐemulsionȑ[19]ೌמΨૈගٮଯϩηวݰǶ٩ᏵϣکѦ࣬ޑКࣚکٯ य़ࢲ܄ᏊǴёԋጤ፦ಈηǵ༝ࢊࠠǵᖓТځ܈ރд่ᄬǶ೭ኬԾךಔးسी ཥ่ޑᄬǴ௨ӈӧϩηำࡋޑӝ׳ଯޑᔈҔǶӧ೭ౣΠǴܰචวޑన ᡏ܈ᆫӝނ፦ᄬԋϣ࣬ޑǴԶѦ࣬ޑҗᆫӝൂޑᡏǴӵԜӧᆫӝࡕளډ୲ڰ ୷ޑ፦ǶӧճҔаᇃวǵϩှࢂ܈аӝޑྋᏊѐڗԶ౽ѐϣࡕ࣬ޑǴҥջ ளډวݰᡏǶٯӵǴϣ࣬ޑᡏᑈϩຬၸനଯхးஏࡋጄൎޑȐ74%ȑ Ǵϣ࣬ό ߏߥϩ໒Ǵ่݀ౢғ࣬ϕೱௗޑӭय़ᡏϾǶRuckensteinځکӕ٣ᔈҔ೭ᐚᕭ٢ ϯᏊޑ৩ѐӝԋଯϕऀޑ܄ϾࢰଯϩηǴೱុ࣬ޑᡏᑈϩૈᡂԋ 1%ኬեǶ ฅԶ೭ኬޑӭϾ܄ೱុ࣬ѸᆫӝǴዴߥᖓጢޑᐒఓᛙ[܄ۓ20]Ƕ ٢ϯԶౢғଯϩηวݰᡏҗᐚᕭ٢ϯޑБݤǴԶᏱԖଯϕऀޑ܄ǴӵԜග ٮஏࡋၟ 0.02g/cm3ኬեǴӢΚᏢᛙسޑۓԄӧ͔mጄൎϣǶ೭চϢ ӝԋԖᐒ܈คᐒޑઞελϩޑวݰᡏǴගٮቨቶᔈҔޑጄൎǶന߈೭ೌמς ᔈҔӧՈᆅݙᏊsiloxaneݣݰǴځ٢ރనճҔຬᖏࣚࢬᡏБݤǴёᗉխϾࢰॹ༥ [21] Ƕ ᆶଯϕऀޑϾࢰ࣬КǴ࠾ഈϾࢰΨૈளډҗࣁ٢ϯᆫӝǴଷ٬ଆۈϩණӛޑ ᡏᑈϩեܭ30%Ƕന߈೭ೱុ࣬ޑᆫӝԶࡕ౽ѐϩණӛనᅀǴԋӭϾ༟܄Ǵ 11 ӵPSǵPMMAǶ༾٢ϯϸᔈڼࣁೌמԯ༾ણᇙ܌٬ҔޑБݤϐǴ၀Б܌ݤගٮ ޑϸᔈᕉნǴज़่ڋϸᔈӧλܭ༾ԯޑ༾झϣՉǴ܌аౢࠔڀԖؼӳޑᗭಈ֡ Ϭࡋᆶϩණ܄ǴԶځલᗺࣁౢၨեǴচӢࣁనᡏύڼԯ༾ણ֖ໆڙज़ܭ༾झ܌՞ నᡏКٯǹЪӢ٬Ҕޑ٢ϯᏊቹៜౢࠔޑપࡋǴӕਔΨ௨ܫόܰೀϐ֖٢ϯ ᏊቲНǶԶ೭ٿᆫӝБԄόૈගٮനࡕޑϾࢰࠠᄊӧኧঁ͔m໔Ǵ༾٢ϯόૈύ ᘐڋǴЪ೯தځϾࢰጄൎӧ10~100nmǹ٢ϯᆫӝΨ՟Яόૈගٮӧ͔mጄൎ࠾ޑ ഈࠠϾࢰǶவԾךಔးϐtailor-made block copolymers ёளڼډԯጄൎϐ࠾ഈࠠϾ ࢰǴՠځ܄፦όᛙۓǴЪځϾࢰελёҗSAXSکTEMໆෳǶ೭mesoporous่ᄬ ޑԖեஏࡋکեࣚႝதኧǴӵԜૈගٮӧࣁႝηޑᔈҔǶ 2.2.3!ճҔ࣬ϩᚆᇙഢӭϾ܄! ྕࡋڋӧ࣬ϩᚆޑၸำύёளډӭϾଯϩηǶӭϾPSวݰᡏځஏࡋեܭ 0.2g/cm3 Ǵࢂ PS-cyclohexane سޑύҗ࣬ϩᚆ܌ளޑډǴسځ࣬ޑკࣁ UCSTޑՉࣁ[22-23]ǶଯܭᖏࣚྋనྕࡋϐǴ cyclohexane کpolystyrene۶ԜϕྋǶ ᒿհࠅӧ binodal ܈spinodal ޑጕΠǴ߄Ң࣬ϩᚆޑ໒ۈǴӵԜౢғࠠޑ࣬ٿ ᄊǶࠠڋᄊόՠሡाঁ၁ಒ࣬ޑკǴԶЪᗋሡाόӕ࣬ϩᚆᐒޑڋΚᏢک ΚᏢǶ٩ᏵྕࡋᡂϯޑೲǴ࣬ϩᚆ໒ۈҗN.G.Ȑԋਡғߏȑࢂ܈S.D.Ȑϩ ȑǴ่݀ౢғόӕࠠޑᄊǶӧ࣬ϩᚆၸࡕǴᇃวྋᏊёளډӭϾࠠᄊǴځϾ ࢰελӧ 1ȝmԿ 100ȝmϐ໔Ƕեᡏᑈϩޑଯϩη࣬ᏤठϕऀޑϾࢰ่ᄬǴ೭ঁ ೌמѝϢᇙഢࠆࡋλ ܭ1mmޑጢǴёࣁᖓጢǶа࣬ᙯඤᇙഢϕऀϾࢰޑଯϩη ᖓጢςԖΟΜ൳ԃΑǶ೭࣬ᙯඤᖓጢ२Ӄ٬ҔӧੇНޑѐᡶǶϐࡕځճҔӧҡݨ ޑځдӭᡂޑᔈҔǶӧ೭࣬ᙯඤၸำޑБݤǴଯϩηᆶྋᏊషӝނΕߚ ྋᏊޑԣύǶΕߚډྋᏊԣύǴྋᏊޑҬඤکӕਔวғྕࡋᡂϯԶЇଆ࣬ϩ ᚆޑวғǶᏃᆅߚதεπޑ٬ҔکᔮਏǴՠࡋӦΑှှញ่ᄬޑғߏک ፕޑܴǴӧࠔ፦ࢂ࣬ډڙፕޑǶόၸ่ᄬวޑᇙำୖኧࢂֹӄΑ ှǴӵᖓጢࠠޑᄊૈவႽੇᆟ่ޑރᄬډЋࡰ่ࠠޑᄬǶ җϯᏢᇨว࣬ϩᚆౢғޑϾࢰ٬ҔӧՅቫϩБݤύǶFre`chetׯ೭מ ೌԶᇙഢளډPSύޜλౚ [24] Ƕӧ೭ჴᡍύϣ࣬ޑషӝ֖ނԖϸᔈ܄styreneک divinylbenzeneൂᡏߚکϸᔈ܄ྋᏊǶӧᆫӝࡕǴёྋޑᆫӝྋᏊ౽рǴ੮ΠϾ৩ 12 ελࣁ 100~500nm໔ޑѮεϾࢰޑԖϾλ੧ǶӧӃޑύᡉҢǴؒԖೌמёள ډઞ͔mጄൎϩթޑϾࢰǶฅԶǴаΠॺךаཥᑉೌמȸϯᏢᇨว࣬ϩᚆȹǴ ځёளډѮεϾࢰޑ܄ڰǶ 2.3!ଯϩη࣬!܄ ଯϩηࣁΑӢᔈӚᅿόӕޑሡǴόᘐޑ໒วᆶࣴزǹԶӝԋᅿཥޑ ଯϩηǴ೯தሡाၨܳޑԋҁǹӢԜଯϩηᄞӝԋࣁᅿख़ाׯޑ፦БԄǶ ࣬ޑଯϩηᄞӝس೯த่ӝኧঁόӕଯϩηނޑϷϯᏢ܄፦Զԋࣁঁཥ ޑଯϩηǶӢࣁ࣬ޑଯϩηᄞӝسǴ܄ځ፦֖ԖচӃᄞӝଯϩη܄ޑ ፦ǴԶׯ๓ځύଯϩηޑલᗺ٠ቚуќ܄፦ޑᓬᗺǴٯӵᐒఓ܄፦ǵԋҁǵ ૈ܄ᆶӭኬϯǴ࣬ϸޑǴऩࣁό࣬سǴځᄞӝࡕঁձрচӃଯϩη܄ޑ ፦ǴԶౢғ࣬ϩᚆޑǶԶషӝ࣬ޑނѳᑽՉࣁࢂҗషӝԾҗૈȐfree energyȑ ܌ЍଛǴ ̴Gmixɨ̴HmixɡT̴Smix ځύ̴GmixࣁషӝԾҗૈȐGibbs free energy of mixingȑǴ ̴Hmixࣁషӝ₲ȐEnthalpy of mixingȑǴ ̴Smixࣁషӝ⪖ȐEntropy of mixingȑǶ ऩाၲډӧҺՖಔԋΠࣁό֡Ϭ࣬ǴᏤठౢғ࣬ϩᚆǴѸᅈىаΠޑచҹǺ ̴Gmix t 0 § w 2 'Gmix · ¨ ¸ ɦ0 2 I w i © ¹T . P ځύ͝iࣁӚঁಔԋޑᡏᑈϩǶ Զቹៜଯϩη໔ϕྋޑӢનӭǴӵྋᏊ[25]ǵྕࡋ[26]ǵϩηໆ[27]ǵϩηϯᏢ่ ᄬ[28]ǵϩη໔բҔΚ[29-30]… Ǵ٬ளଯϩηҗᄞӝၸำԶև࣬ރᄊჴឦό ܰǶฅԶǴᄞӝسύǴऩϩη໔Ӣਸ୷ૈ۔ԶӸӧբҔΚǴٯӵϩη໔ణᗖ [29-30] ǵᚆη-ଽཱུǵଽཱུ-ଽཱུǵႝηᙯ౽ǴܰᏤठ࣬ᄞӝسޑԋǶ࣬ ܄ᗨฅόࢂᄞӝᡏܭᔈҔਔ܌ሡڀഢޑచҹǴՠࠅёа٬ଯϩηᄞӝᡏ܄ޑ፦ܭ ीࣁ׳БߡᆶܰǴ܌а࣬܄தࢂᢀჸཥଯϩηᄞӝᡏޑ໒ۈǴԶᢀჸ่ځ ᄬ܄፦Ƕ 13 2.4 ଯϩηྋనΚᏢ! ଯϩηᄞӝ܌ނᒥൻޑΚᏢᆶځдނ፦٠ؒԖόӕǴՠԖ٤Չࣁࠅόܰӧ λϩηύᢀჸډǶଯϩηᄞӝނύǴΚᏢ࣬ޑ(܄miscibility)ࢂനЬाࣴޑ زፐᚒǶଯϩη໔࣬ޑࢂ܄،ܭۓషӝਔԾҗૈύ₲(enthalpy)ᆶ⪖(entropy)ޑ ѳᑽǶλϩη⪖ޑၨεǴ೯தࣁ࣬سǴฅԶଯϩη⪖ޑ൳Яࣁ႟Ǵ܌аࢂҗ ₲ٰ،ࢂۓց࣬Ƕ ԶவΚᏢᢀᗺё࣬עϩᚆ࣮ԋࢂسύԾҗૈׯޑᡂ܌ԿǴԵቾપଯϩη ᆶપྋᏊӧࡋྕۓϷᓸΚΠషӝԶԋྋనޑำׇǶӧԜྋှำׇύǴӓѲγԾ җૈȐGibbs free energyȑޑᡂϯ ǻG ёҗȐ2.1ȑԄ߄ҢࣁǺ ǻGɨǻHɡTǻS Ȑ2.1ȑ ځύ ǻH ᆶ ǻS ϩձྍԾܭྋှำׇύϩη໔բҔΚᆶ่ᄬᄊׯޑᡂ܌ԋ₲ޑ Ȑenthalpyȑᡂϯᆶ⪖ȐentropyȑᡂϯǶ ჹܭඔॊঁ࣬ϩᚆำׇǴځၸำ҅ӳёᙖҗԾҗૈԔጕރޑӧӚᅿόӕϐ Πٰ߄Ң[31]Ǵӵკ 2.2 ܌ҢǶ კ 2.2!షӝԾҗૈࣁᡏᑈϩϐڄኧკ[31] ӧԵቾٿԋϩسӧёϕྋݩރޑΠǴӢࣁԜషӝำࣁׇԾวၸำǴ܌аӧ ঁಔԋسύԾҗૈࣁॄॶǴԜᅿࣁჹᔈډკ 2.2 ύ ޑline aǴ࣬ϸޑǴऩٿ ԋϩӧֹӄόϕྋޑΠǴӧΚᏢᢀᗺΠځԾҗૈࣁ҅ॶǴԶ܌ჹᔈࣁޑკ 2.2 ύ ޑline cǴԶ࣬ჹޑঁسύวғ࣬ϩᚆջࢂவϕྋډόϕྋޑᙯඤၸำǴӧኧ Ꮲ߾ཀښԾҗૈڄኧวғԔޑᡂϯǴӧკ 2.2 ύ ޑline bǴځԾҗૈڄኧё ԔጕඔᛤԋڀԖཱུঁٿλॶǵঁཱུεॶঁٿکϸԔᗺޑ܄ǴԜϸԔᗺޑΒ໘Ꮴ ኧࣁ႟ǴԜำׇӧΚᏢᆀࣁϩȐspinodal decompositionȑ Ǵჹܭပٿܭϸ 14 Ԕᗺ໔ޑಔԋǴځԾҗૈჹଯϩηᡏᑈϩޑΒ໘Ꮴኧλܭ႟ǴԾҗૈӧԜ໔ϐ ܌аቚуǴԖٿᅿচӢǺ൩ଯϩη/ଯϩηسԶقǴӧࡡྕΠӢࣁଯϩηᆫԶ ٬ளࡋᡂλȐǻSɦ0, ǻG ϲȑ ǹ൩ଯϩη/ྋᏊسԶقǴӢࣁଯϩηᆶྋᏊϐ ໔ޑҬϕբҔᡂλԶ٬ள ǻH ᡂεǴԋӧԜ໔চҁև֡࣬ޑషӝނϩԋٿ ٰ࣬फ़եԾҗૈǴ٠ᡣځၲཱུډλॶǶ ӧॺךԵቾঁଯϩη/ྋᏊΒԋϩسǴ٠ᡣځಔԋပٿܭϸԔᗺ໔Ǵ߾ྋ ᏊϩηᆶଯϩηϩηஒᙖҗᐚࡋఊࡋԶϩձᘉණԿྋᏊ࣬ᆶଯϩη࣬ύǴ೭ᅿ ࣬ϩᚆᐒڋջࢂ܌ᒏ ޑup-hill diffusionǴԶЪԜᅿᐒڋஒᏤठԾว࣬ޑ܄ϩᚆǴ ܌аԜᐒڋΨᆀࣁϩǴҗԜᅿᐒڋஒِೲޑΕϩޑୱǴԶЪ όाҺՖࢲϯૈǶ ӧკ 2.2 ύ ޑline b ύԾҗૈԔጕޑᗺΨё٬ϐᅈىΚᏢܭѳᑽޑచҹǴ ӢԜόፕࢂଯϩηᗋࢂྋᏊԋҽӧ࣬ٿȐ˧˨کȑύޑϯᏢ༈ૈȐchemical potentialsȑ ࣬ǴჹܭԜΒԋϩسύӧኧᏢёаȐ2.2ȑԄ߄ҢࣁǺ P ,pol P pol , P sol P sol Ȑ2.2ȑ ၸკٰᢀჸܭၲډΚᏢѳᑽٿޑᗺǴନΑځϯ༈࣬ӕѦǴԶЪΨӅӕӸ ӧܭӕచ҅ϪጕǴќБय़Ǵ೭Βᗺёගٮଯϩη࣬Ȑ˧ȑᆶྋᏊ࣬Ȑ˨ȑ ޑಔԋӅӸܭΚᏢ࣬ѳᑽϐύǴԶஒ೭٤ᗺೱௗଆٰ൩ᆀࣁӅӸԔጕȐcoexistence curveȑ܈㛇ጕȐbinodal lineȑ Ƕ ! 2.5 Flory-Huggins theory Ԗ٤ୖኧቹៜسޑɆSکɆHԶׯᡂԾҗૈǴӵ࣬ϩᚆޑวғǶҗଯϩηکྋ Ꮚಔԋޑషӝ⪖ёаঁձीᆉǴаFlory[32]کHuggins[33]ޑηኳࠠȐlattice modelȑ ࣁଆᗺǶѬଷ٬ঁྋᏊϩη՞Ᏽঁηޜ໔ǴനλൂՏޑᡏᑈຎࣁୖԵᡏᑈǴ ӵԜѮεϩη܌՞ᏵޑᡏᑈࣁVPol = ͞·VSolǴ͞ࣁኧǴVPolж߄ঁଯϩηޑᡏ ᑈǴVSolࣁঁྋᏊϩηޑᡏᑈǶ٤ଷࢂѸޑǴჹܭѐीᆉёૈթޑኧໆǶ ӢԜǴଷޜঁۓՏόࢂྋᏊ՞Ᏽ൩Ѯεϩη܌՞ᏵǶவीᏢޑीᆉǴଯϩ η२Ӄ༤кӧη္ǴԶྋᏊϩηܫӧഭΠޑη္ӧֹԋ༤кၸำࡕǶ ӢࣁྋᏊϩηߚதλǴӵԜVPolѸۓεܭVSolǶଯϩηྋᏊسаϯᏢᇨว࣬ϩᚆ 15 ȐCIPSȑೌמѐᇙഢѮεϾࢰ܄ڰᐋિᅈى೭ӚଷǶԜѦǴ܌Ԗଯϩηޑϩη ଷۓԖ࣬ӕޑελǴکᎃѮεޑթᔈ၀όૈԖᐚࡋৡӧηύǶԜԄࣁ 'S R^nPol ln I Pol nSol ln I Sol ` Ȑ2.3ȑ nPolࣁଯϩηޑವԸኧǴnSolࣁྋᏊޑವԸኧǴ I PolࣁଯϩηޑᡏᑈϩǴ I SolࣁྋᏊ ޑᡏᑈϩǴRࣁᡏᘉණ߯ኧǶଯϩηکྋᏊޑᡏᑈϩёۓကࣁǺ I Pol n Pol VPol ǹ VT I Sol nSol VSol VT Ȑ2.4ȑ VpolࣁଯϩηޑವԸᡏᑈǴVsolࣁྋᏊޑವԸᡏᑈǴV Tж߄ӄޑᡏᑈёۓကࣁǺ V T n Pol VPol n Sol VSol Ȑ2.5ȑ ନΑीᆉషӝԾҗ⪖ޑᡂϯǴFlory а֎ЇΚୖኧȐ͞ȑ ǴѐीᆉଯϩηکྋᏊ ϩη໔֎ޑЇΚǴё߄ҢࣁǺ 'H R T F n Pol I Pol [33] Ȑ2.6ȑ ่ӝॊ₲Ȑenthalpyȑᡂϯᆶ⪖ȐentropyȑᡂϯᏤΕFlory-Huggins[33]БำԄё߄ ҢࣁǺ 'G R T nPol ln I Pol nSol ln I Sol F nSol I Pol Ȑ2.7ȑ ! 2.6 ࣬ϩᚆၸำޑԄڮکӜ ࣬ϩᚆݤ೯தаόӕޑᘋБԄǴᇨวسౢғΚᏢϐόᛙރۓᄊǴ٬ଯϩ ηన࣬ϩᚆԋଯϩη࣬Ȑpolymer-rich phaseȑᆶଯϩη೦࣬Ȑpolymer-poor phaseȑ Ƕதـଯϩη࣬ϩᚆޑБԄԖׯᡂȐaȑྕࡋȐbȑᓸΚȐcȑಔԋȐёѦ уߚྋᏊ܈аྋᏊޑචว౽ନȑٰᇨว࣬ϩᚆǶ Զ Florry-Huggins БำԄёϢख़ࡌཷा࣬ޑკٰှញ࣬ϩᚆޑՉࣁǶਥᏵ F-H ࡋྕޕǵ֎ЇΚୖኧȐ͞ȑϷྋᏊکଯϩηޑᡏᑈϩࢂషӝԾҗૈڄޑኧǶঁ ܈٤ୖኧޑᡂϯ٬ԾҗૈౢғׯᡂǴԶԾҗૈޑԔׯᡂ߾࣬ϩᚆΨ൩วғǶ ٤Ꮴठӧଆ߃࣬ϩᚆၸำёૈ܄ǴЪ٩೭٤ᡂϯ٬ԾҗૈׯᡂǴӵΠӈޑёૈ ܄Ƕ 2.6.1 ྕࡋᇨᏤ࣬ϩᚆȐTIPSȑ 16 ঁёᡂӢનӧF-HБำԄࢂྕࡋǶ࣬ϩᚆޑวғࢂҗྕࡋޑᡂϯԶวғǴ Ѭ೯தᆀࣁTIPSǶ࣬ϩᚆޑวғ࣬کკڗރޑ،ܭӚسۓ֎ޑЇΚୖኧ Ȑ͞ȑ ǴԶ͞٠ߚࢂঁதኧǴځ٩ྕࡋǵಔԋکᓸΚԶۓǶ٤ჴᡍБݤёෳ͞ۓǴ ӵlight or neutron scattering کosmometryӧଯีញޑྋనΠǴࢂ܈а࣬ᡏቫϩ ଯϩηޑᅙᗺໆෳ[34-35]Ƕ ٿᅿ࣬კڗ،֎ܭЇΚୖኧၟྕࡋϸКևጕ܄ᜢǴԜԄࣁǺ͞=a+b/T[36]Ǵځ२ ӃHugginsჴᡍ܌ዴᇡрٰǶ კ 2.3 ύ T1 >T2,UǴྕࡋҗଯྕफ़ԿեྕਔǴ߾ౢғ࣬ϩᚆǴԜᅿຝᆀ ࣁ UCSTǴԶ Tc,U ࣁᖏࣚྋనྕࡋ( Upper Critical Solution Temperature UCST )Ƕё ͞ޕஒᒿྕࡋޑቚуԶ෧ϿǴࣗԿᡂࣁॄॶǴӢԶև UCST ޑ ຝǶკ 2.3 ύ T2,L > T1Ǵঁଯϩηషᄞس೯ന߃ࣁ࣬֡ࢂ܈܄Ϭ࣬ǴࣗԿ ࣁҽ࣬ރᄊਔǴҗᇨᏤ࣬ϩᚆϐၸำԶ٬سᡂԋރ࣬ٿᄊǴԜຝᆀϐ ࣁ LCST Ǵ Զ Tc,L ࣁ Π ᖏ ࣚ ྋ న ྕ ࡋ ( Lower Critical Solution Temperature LCST )Ǵ࣬ځՉࣁখӳ کUCST ϐ࣬Չࣁ࣬ϸǶ࣬ϩᚆЬाёϩࣁٿᅿᐒᄬǺ nucleation and growth (NG) کspinodal decomposition (SD)Ǵޣٿځനεޑৡձӧܭ NG খ໒࣬ޑۈϩᚆୱࢂౚ่ރᄬǴᒿਔ໔ޑቚуԶᡂεǴനࡕঁձ࣬ޑୱ ϕ่࣬ӝӧଆǴԋ׳εޑౚ࣬ރϩᚆୱǶԶ SD ߾ࢂ໒ۈаᙝ่ރᄬӸӧǴ ᒿਔ໔ޑቚуԶϕ࣬ӝٳǴനࡕΨԋ کNG ࣬ӕޑౚ่ރᄬǴӵკ 2.4 ܌ҢǶ კ 2.3 ཷा࣬ޑკ߄ҢUCSTکLCSTՉࣁ[37] 17 კ 2.4 spinodal decomposition (SD)ᐒ[ڋ37] 2.6.2 Binodal Curve Binodal curve ࢂΚᏢޑᛙᄊᆶϟᛙᄊޑᜐࣚǶନΑΚᏢޑीᆉѦǴ೯த ёճҔᜦᗺԔጕ (cloud-point curve, CPC) ჴᡍٰ،ۓԜᜐࣚǶس࣬ٿޑಔԋӧѳ ᑽਔǴԜѳᑽރᄊёҗ binodal ٰඔॊǴӚԋҽޑϯ༈ (chemical potential) ӧ࣬ٿ ύᔈ࣬Ƕϯ༈ۓကࣁǺ سѳᑽރᄊ (binodal curve) ёҗΠӈԄη߄ҢǺ ځύ!Dᆶ!E߄Ңӧѳᑽਔ࣬ٿޑǶࡋྕۓڰT ᆶI2D(I1D= 1 - I2D)ਔǴճҔॊ ѳᑽԄёளᙯϯp ᆶI2E(I1E= 1 - I2E)Ǵջёрᙯϯᆶಔԋ০კύޑ binodal curveǶ! 2.6.3 Spinodal Curve Spinodal curve ࢂΚᏢϟᛙᄊᆶߚᛙᄊୱޑᜐࣚǶسӧԜᜐࣚǴѸ ᅈ'(ىPi / wIj)T, P = 0 ޑԄηǶҗΚᏢޑБݤΨёှрspinodal curveǶӧჴᡍ 18 ύspinodal curve നத٬ҔޑሺᏔࣁPulse Induced Critical Scattering (PICS)[38]Ƕ 2.6.4 Critical Point binodal curve ᆶ spinodal curve ޑҬௗᗺᆀࣁᖏࣚᗺǴ܌аԜᗺࣁϯ༈ჹಔ ԋޑԛ༾ϩᆶΒԛ༾ϩࣣࣁ႟Ƕऩׯ፦Ꮚ֖ޑໆຬၸᖏࣚᗺǴᄞӝᡏ൩ౢғ࣬ ϸᙯޑຝǶ 2.6.5 ϯᏢᇨว࣬ϩᚆȐCIPSȑ ԾҗૈޑᡂϯᏤठ࣬ϩᚆޑวғǴԶុׯᡂᆫӝޑނϩηໆǴёගٮ ǻSޑᡂϯǴёаᏤठ࣬ϩᚆǶӵԜ࣬܄ȐmiscibilityȑޑᡂϯҔܭӧྋᏊύᆫ ӝǴаӝԋ༟܄ଯϩηǴ೭ᜪᆫӝޑଯϩηԖଯϩηໆکόྋ܈؈ᐘԶૈவեϩ ηໆޑౢނϩᚆрٰǶԶӧ܄ڰଯϩηޑฯϯၸำՔᒿቚуϩηኧໆǴωԖ ࣬ϩᚆ໒ۈǴӵԜளډࠠޑ࣬ٿᄊǶ೭ၸำёૈᔈҔӧᇙ୲ޑ܄ڰ܈ ࢂଯϩηϩණనǶӵ݀ሡाख़ࡌ࣬კǴځ൩ᡂԋѸஒ₲ᆶ⪖ׯᡂԋࣁᙯϯޑ ڄኧǶॺך२ӃᡣൂՏᡏᑈޑషӝԾҗ⪖ȐǻSvȑڗж⪖ȐǻSȑ[39,40]Ƕ่ӝԄȐ2.3ȑ ~Ȑ2.5ȑёள 'S V 'S VT I ½ I R ® Pol ln I Pol Sol ln ISol ¾ VSol ¯VPol ¿ Ȑ2.8ȑ ॺךଷ Z Pol VPol V0 ک Z Sol VSol V0 Ȑ2.9ȑ Voж߄Ҕٰࡌ܄ڰᆛރޑ០ޑނವԸᡏᑈǴॺךଷVoၟӧচۈ ηኳԄୖޑԵᡏᑈࢂ࣬ޑǴӧ೭ݩΠǴವԸᡏᑈᆶኧҞѳ֡ϩηໆԖаΠᜢ ߯[40,41] Ǻ Z Pol షӝൂᡏᖿޑނኧҞѳ֡ϩηໆǴ ኧҞѳ֡ϩηໆϩѲୱǴ VPol V0 Mn M n0 Ȑ2.10ȑ ǴࢂᖿൂނᡏޑϩηໆکК܌ٯ،ۓǶ Ǵځᆫᕭӝޑ܄ڰଯϩηǴёҗीᏢޑीᆉ 19 ၟϸᔈำࡋڄޑኧኬޑǶӧޑॺךϸᔈύǴаD.E.R. 331 ࣁᖿکނаDETAࣁฯ ϯᏊࣁٯǴځϩηໆϩѲȐmolecular weight distributionȑёҗΠӈ߄Ңр[39,42] Mn M n0 § 4 · ¨1 q ¸ © 3 ¹ Ȑ2.11ȑ ѝाᆛނރԋޑΚᏢࢂϟܭᖿൂނᡏޑϸᔈֹ܌܄ӄޑڋǴٗ೭ኬ ीᏢޑीᆉࢂԖਥᏵޑǶคज़εޑᆛ่ރᄬ໒ۈԋਔǴΨ൩ࢂᏉጤਔǴ ԶᗹࡋΨ࡚ೲቚуǴ٬ϸᔈΨᄌΠٰǴӢԜԄȐ2.11ȑӧᏉጤᗺϐࢂԖਏޑǶ่ ӝȐ2.9ȑ~Ȑ2.11ȑԄԶளډ 'S V R V0 § 4 · ½ I Sol ln ISol ¾ ®¨1 q ¸ I Pol ln I pol Z Sol ¯© 3 ¹ ¿ Ȑ2.12ȑ ೀFlorry-Hugginsঅ҅ޑБำԄǴх֖ӄᡏᑈޑషӝԾҗ⪖ǴǻSvǴࢂځ ঁᙯϯڄޑኧǶԶ₲Ψёа֎ЇΚୖኧٰ߄Ң[40,43]Ǵ߾ёளǻGv 'G V 'G VT RT V0 § 4 · ½ I ®¨1 q ¸ I Pol ln I Pol Sol ln I Sol F I Pol ISol ¾ Z Sol ¯© 3 ¹ ¿ Ȑ2.13ȑ Ȑ2.13ȑԄǴёаϢࡌᄬрٰ࣬Չࣁֹޑ࣬კکႣෳǶ ճҔ೭БݤѐीᆉǻGvޑԔጕǴکѐှញᐎጤቚᕉ਼ᐋિسޑՉࣁǶӧࣴزѐ ीᆉаᙯϯڄኧޑǻGvԔጕǴᗋѸள֎ЇΚୖኧȐ͞ȑ ǶԖ٤ჴᡍёள͞Ǵ ٯӵӛ࣬ቫȐIGCȑ[44]ࢂ܈ύηණȐneutron scatteringȑ[37]ǶЪ͞ޑᡂӢࣁ ٤ୖኧǴӵಔԋǵྕࡋکᓸΚǶ A. ϯᏢᇨว࣬ϩᚆϐ࣬კ ଷ٬٠όགྷ٬ҔFlory֎ޑЇΚୖኧȐ͞ȑǴॺךёаҔྋှࡋୖኧȐ͌ȑѐள ̴ډHǶѬԖั༾Ӧज़ڋӧीᆉǴՠࠅКၨᙁൂǴѝሡाરکǶਥᏵѬޑ ۓကǴ͌=Ȑ̴Ev/Vȑ0.5Ǵ̴EvࣁವԸᇃวૈȐmolar energy vaporizationȑ ǴVࣁൂ ՏವԸᡏᑈǶ̴EvёҗෳьݤȐcalorimetryȑளǶջ٬͌٠όૈҗჴᡍ܌ளǴ ՠ͌ॶޑΨёҗঁձဂᡏޑଅѐளӧᎃ߈ҺՖԄޑѮεϩηǶਥᏵ HildebrandۺཷޑǴ̴HΨё߄Ңࣁ 'H VT G Pol G Sol I Pol ISol 2 Ȑ2.14ȑ ਥᏵۓကǴ̴HόёૈளॶॄډǶऩૈϕྋȐmiscibilityȑǴ߾ଯϩηޑྋှࡋ ୖኧȐ͌PolȑکྋᏊޑྋှࡋୖኧȐ͌Solȑࢂৡ౦ߚதλޑǶ೭ቶݱӦճҔӧᔠ 20 ຎଯϩηکྋᏊޑϕྋ܄ǶӧCIPSޑБݤǴ໒ޑۈϕྋߚࢂ܄த،ޑ܄ۓǴե ϩηໆޑనᡏѸவঁྋᏊᙯᡂԋঁߚྋᏊӧϸᔈޑၸำύǶӵԜǴ͌ࢂॶޑ ᔅշॺךᒧӝޑྋᏊӧ࣬ϩᚆޑ٬ҔǶ ྋှࡋୖኧЬाཱུ܄Ȑ͌pȑǵణᗖȐ͌hȑکϩණΚȐ͌dȑ܌ЍଛǴаΠࣁ аӛໆ߄ҢǴـკ 2.5ǶྋှࡋୖኧޑБӛࢂ٩ྣځϯᏢ่ᄬǶԶଯϩηྋှࡋୖ )& )& )& ኧȐ G Pol ȑ کྋᏊྋှࡋୖኧȐ G Sol ȑޑৡࣁȐ d ȑё߄Ңࣁ კ 2.5 ྋှࡋୖኧޑӛໆკ߄Ȑqࣁᙯϯȑ[8] d ^G Pol d G dSol G 2 Pol P G PSol G 2 Pol h G hSol ` 2 Ȑ2.15ȑ Զ Hildebrand БำԄёᡂࣁ 'H V 'H VT I pol I Sol d 2 Ȑ2.16ȑ ଷ٬ཱུک܄ణᗖ࣬ޑϕբҔΚё۹ౣǴ߾Ȑ2.16ȑԄёϯᙁࣁȐ2.14ȑԄǶ ӧϸᔈၸำύǴଯϩηޑྋှࡋୖኧόՠׯᡂځБӛԶЪΨׯᡂࡋߏځǴёவ კ 2.5 ёޕǶӧ҂ϸᔈਔȐq=0ȑ Ǵ߾ӛໆ ࣁࡋߏޑd q 0 ࣁᖿޑނྋှࡋୖኧӛ ໆکྋᏊޑྋှࡋୖኧӛໆکޑǴЪࡋߏځΨၨอǶӵԜషӝ̴ޑH ၨλǴ߾ϕྋ ܄ၨӳǶ໒ۈϸᔈࡕǴ߾ d q ࡋߏޑΨᅌቚуǴӵԜԋ̴H ΨཇٰཇεǶ ਥᏵ Hildebrand БำԄёޕǴ̴H ᆶ d q ޑѳБࢂԋКޑٯǶӵԜόՠׯᡂ̴H 21 ԶЪΨׯᡂΑ̴SǴ٠٬ׯځᡂ࣬ϩᚆޑՉࣁǶଷଯϩηޑྋှࡋୖኧวғׯᡂ ᆶᙯϯևጕ܄ᜢ߯Ȑӵკ 2.5ȑǴ߾ d q ё߄Ңࣁ d q z q G Sol unreact z q G Pol react Ȑ2.17ȑ Ȑ2.18ȑ q y unreact y G Pol G Pol Ȑ2.19ȑ ߾ёஒ d q ߄Ңࣁ d q G dunreact q G dreact G dunreact G dSol ½ ° unreact ° q G preact G punreact G pSol ¾ ®G p °G unreact q G react G unreact G Sol ° h h h ¿ ¯ h §a· ¨ ¸ ¨b¸ ¨c¸ © ¹ Ȑ2.20ȑ d ж߄ࣁ dispersiveǴp ࣁ polarǴh ࣁ hydrogen bondingǶ ่ӝȐ2.12ȑǵ Ȑ2.16ȑکȐ2.20ȑԄ߾ёளډаᙯϯࣁڄኧ̴ޑGv 'G v 'G VT RT V0 2 § 4 · ½ I Sol ln I Sol ¾ d q I Pol I Sol ®¨1 q ¸ I Pol ln I Pol Z Sol ¯© 3 ¹ ¿ Ȑ2.21ȑ ϯᏢᇨว࣬ϩᚆ࣬ޑკӵკ 2.6 ܌ҢǴ㛇ጕᆶጕϩձёҗӅӸᗺᆶ ϸԔᗺޑԾҗૈԔጕԶаᙯϯࣁڄኧޑᜢ߯ԄԶள[8,40]Ƕ კ 2.6 ϯᏢᇨว࣬ϩᚆϐ࣬კ[8] ӧаԜ࣬კٰှញࠠڰଯϩηܭฯϯය໔ځಃΒ࣬ޑౢғচӢǴӧฯϯϸ ᔈය໔ځᙯϯࢂុቚуޑǴӧঁֹӄϕྋ҂วғฯϯϸᔈسޑਔǴਥᏵځ 22 ᐚࡋᆶϸᔈೲځᙯϯࣁ႟ǴԶӧԜ໘ࢤسёΕϟᛙȐmetastableȑ܈ ᗺϩԶวғ࣬ϩᚆǴӧϟᛙϣ࣬ޑϩᚆᐒࣁڋԋਡԋߏȐnucleation and growthȑǴ܌ځჹᔈޑջࢂკ2.2ύϸԔᗺᆶཱུλॶϐ໔ޑϩǴӧԜ໔ύҺՖޑ ԋҽਁᕏǴ٬షکԾҗૈϲǴԶ࣬ϩᚆ٬ளᡏԾҗૈΠफ़ډၲཥޑѳᑽ ރᄊǴՠѸӃլܺૈምࡕ࣬ϩᚆωૈՉǶԜૈምջࣁԋਡ܌ϐനλૈໆǴځ ࡕਡझωૈុԋߏǶϸϐǴऩسୱϼௗ߈Ԕጕޑ၉൩วғᗺϩ ǴԜᅿவᛙᄊҗ࣬ᙯඤΕډϟᛙᗋࢂ่ᗺϩ࣬ޑϩᚆᐒڋёа࣮ԋ ࢂϯᏢేϯȐchemical quenchȑǴԜ࣬ϩᚆᐒڋᆀࣁϯᏢᇨว࣬ϩᚆȐchemically induced phase separationǴᙁᆀCIPSȑǶ җϯᏢᇨว࣬ϩᚆᐒڋԶளϐᄊǴځԋਡԋߏ࣬ޑϩᚆᐒڋϐૈໆѳᑽࢂ җᘉεԋཥ߄य़܌ሡૈޑໆᆶԋၨεᡏᑈ܌ቚуૈޑໆ܌ӅӕЍଛޑǴӢԜಃΒ ࣬ஒаᏱԖന٫ޑᡏᑈᆶय़ᑈКރޑрǴջҗԜᐒ܌ڋԋਡࢂևౚރ ޑǶӵӧฯϯϸᔈය໔Ǵسวғ࣬ϩᚆԶΕϟᛙύǴځനಖޑᄊஒډڙҗ ϩණ࣬ޑԋਡکԋߏ࣬ϕᝡݾǴаϷӧុϸᔈԋϩηໆቚуکᗹࡋϲԶफ़ե ਡԋߏೲ܌ڋǶ аϩᐒڋԶளޑᖓጢᄊஒҗӚᅿόӕ࣬ޑᄊԶԋ[8]Ǵӧ߃ය ԋଯϩη࣬ᆶྋᏊ࣬ϕ࣬ೱ่ޑᚈೱុ࣬Ȑco-continuous phaseȑ่ᄬǴฅࡕ ᘐԋౚϩණ࣬Ǵаफ़ե߄य़ૈǴԶϩණ࣬ٿޑஒӧനࡕ࣬ޑϩᚆၸำύ ԋߚ֡ୱރޑǶ B. ϯᏢᇨว࣬ϩᚆᔈҔܭᇙഢӭϾ܄ᖓጢ җॊ࣬ϩᚆၸำޑΚᏢϐϟಏǴॺךёаख़ཥҔკ 2.7(Π।)ٰᇥܴाӵ ՖڋଯϩηᆶྋᏊ໔ޑКٰٯၲԋ܌ॺךाޑᖓጢᄊ[8]Ƕ ӧკ 2.7 ύѬૈගٮঁᇙഢᏱԖϕ࣬ೱௗȐinterconnectedȑ࠾ࢂ܈ഈȐclosedȑ ࠠϾࢰ܄ڰଯϩηᖓጢࡰޑǶٯӵགྷाள࠾ډഈࠠϾࢰᄊޑᖓጢǴ߾ྋᏊޑ ᡏᑈϩѸߥӧၨλރޑᄊǴаᗉխၸӭޑྋᏊౢғೱௗࠠޑϾࢰᄊǴќ Бय़ǴΨё٬࣬ځϩᚆࢂаԋਡԋߏޑБԄՉǴԶᗉխӢຬၸ࣬ᙯඤำࡋளډᗭ ಈޑރଯϩηǴԶྋᏊໆё࣬ᙯඤಔԋज़ڋӧ㛇ጕᆶጕޑᄒᗺೀǴӵკ 2.7 ύ ޑIc ǴԜᗺᆀࣁᖏࣚಔԋ[45]ǶࡺаΠޑϣёϩࣁٿҽᇥܴǺ 23 კ 2.7 ᔈҔϯᏢᇨว࣬ϩᚆݤᇙഢ܄ڰଯϩηᖓጢܭόӕᄊϐ࣬კ[8] 1. سಔԋɦ Ic ǺऩسಔԋࢂೀӧԜ໔ЪྋᏊ֖ໆၨϿਔǴ߾ฯϯϸᔈӧ ၨଯᙯϯਔวғ࣬ϩᚆǴӧԜਡझᗨฅӧଯᗹࡋЪեᘉණ߯ኧύޑᕉნԋǴՠ ࢂӢځਡझԋߏࢂӧଯᙯϯΠՉޑǴ܌аᏤठځԋߏೲቚזǴՠၸࢤ ਔ໔ࡕǴځԋߏೲफ़ࣁ႟ǴځচӢԖঁٿǺ२ӃࣁԋਡޑᐚࡋςၲঁѳᑽॶǴ ࡺ០Κफ़եǴᆙௗࢂᏉጤϯȐgelationȑޑౢғᏤठᗹࡋِೲϲᖿӛคज़εǴ җа܌ளޑډϾࢰࢂևрၨ֡ϬޑЁκϩթȐnarrow size distributionȑ ǶԶ ځԋਡԋߏೲᒿϸᔈၸำᄽϯӵკ 2.8Ȑaȑ܌ҢǶϸϐǴऩسಔԋΨࢂೀܭԜ ໔ՠޑ֖܌ྋᏊၨӭਔǴᗨฅ࣬ϩᚆখวғਔਡझࢂԋߏӧեᗹࡋЪᘉණ߯ኧଯ ޑᕉნύǴՠਡझޑԋࠅࢂӧၨեᙯϯǴ܌а࣬ၨΠӧԜ໘ࢤύԋߏೲᇻ εܭཥਡԋޑೲǴԶЪӧวғጤϯຝǴԋߏޑᐚࡋӢࣁᕓ໔ၲډঁޑ ѳᑽॶԶफ़ࣁ႟ǴՠӧԜӕਔཥਡझࠅᗋӧόᘐԋǴҗа܌ளޑډϾࢰ ևрߚ֡ޑЁκϩթȐbimodal distributionȑǴԶԜᅿԋਡԋߏೲᒿϸᔈၸำ ᄽϯޑკӵკ 2.8Ȑbȑ܌ҢǶ 2. سಔԋɧ Ic ǺऩسಔԋࢂೀӧԜ໔Ǵ߾ஒᏤठ࣬ϩᚆԶԋଯϩηᗭಈ ϩණӧྋన҆ᡏύǴՠࢂ೭٤ᗭಈޑϐಔԋᗋࢂပӧ㛇ጕǴӢԜ೭٤ᗭಈϣ ᗋࢂԖх֖ىԋ࣬ϩᚆޑྋᏊໆǴፏӵԜᜪܭϣԖϾࢰޑᗭಈǴ୯ѦJ. M. J. Freshetزࣴޑი໗ջࢂճҔԜᅿБԄǴᇙഢӭϾޑ܄ଯϩηᗭಈٰڗжՅቫϩ ύᆅࢊ[࣬ۓڰޑ47]Ƕ 24 NΚnucleation rate GΚgrowth rate კ 2.8 ԋਡԋߏೲᒿ࣬ϩᚆၸำᄽϯޑკ[46] ȐaȑଯԋਡೲکեԋߏೲԶౢғϾࢰελև֡܄ǹ ȐbȑեԋਡೲکଯԋߏೲԶౢғϾࢰελևߚ֡܄ ٬ҔၨଯྋᏊޑᐚࡋǴᡣ࣬ϕೱௗޑనᅀޑౢғҗԋਡғߏᐒڋǴёԋϕ࣬ೱ ௗࠠӭϾ܄Ƕࢂ܈٬ҔၨଯޑϸᔈೲҗϩᐒڋǴᡣӧനࡕၸำӝٳ ࣬ϕೱௗԋޑϾࢰԶԋౚޑރᐒૈڋڋǶฅԶόᆅࢂҔϩࢂ܈٬Ҕ ၨଯྋᏊໆԶҗԋਡԋߏ࣬ޑϩᚆᐒڋёᔈҔܭᇙഢঁᏱԖϕ࣬ೱௗࠠϾ ࢰࠠᄊޑᖓጢǶ 2.7 ׯ፦Ꮚޑϟಏ(nicotinamide) ύЎ:ѭёᎇㄽữ ߫Ӝ:ᆢд ڮB3 ձӜ:3-pyridinecarboxamide ǵpyridine 3carboxamide ǵ ྟለϯނ ܄፦:਼ϯᗋচ܄ Ьाфૈ:ᑗֿੰݯᕍکႣٛǵԖ਼לϯǵלวکݹanticarcinogenic ࢲǶNADբ ࣁႝηၩᡏǴёௗکڙਈᜄႝηჹӚᅿӚኬޑሇનϟΕӧૈໆཥഋжᖴǶ + Ьाжᖴౢނ:NAD (nicotinamide adenine dinucleotide)ǴϟΕӧεጄൎғނၸ ำǴхࡴૈໆޑғౢǴિެለᆕӝǴᖌڰᎇکᜪڰᎇǵߞဦᙯᏤࢉکՅᡏޑᆢៈǶ 25 2.7.1 ճҔׯ፦ೌמᇙഢфૈ܄ᖓጢ !!!!ճҔׯ፦ׯٰೌמᡂᖓጢޑࢂ܈܄ቚуᖓጢҁيόڀԖ܄ޑ፦Ǵ٬ᖓጢޑᔈ Ҕጄൎ׳ቶݱǶԶׯ፦ೌמύаϯᏢௗ݄ᆫӝࣁݤനதҔޑБݤǴௗ݄ջࢂஒόӕ ൂޑᡏௗډଯϩηޑЬǴ٬ଯϩηڀԖׯ፦Ꮚޑ܄ǶஒӭϾ܄ᖓጢᆶׯ፦Ꮚ Οભữѭёᎇㄽữ(nicotinamide)ճҔϯᏢௗ݄ݤՉׯ፦ϸᔈǴӢࣁѭёᎇㄽ ữڀԖ਼ϯᗋচϐ܄Ǵ܌аႣයׯ፦ࡕޑᖓጢஒڀԖ਼ϯᗋচϐфૈǶᖓጢӧ਼ ϯᄊޑ໘ࢤਔǴௗ݄ޑᙟᇂϾࢰ෧ϿНޑᅖբҔǴԶӧᗋচᄊޑ໘ࢤǴӢ ࣁᖓጢޑଯϩηளႝηϣᕭǴ෧ϿᙟᇂᖓጢϾࢰޑᐒǴ܌аᖓጢჹܭНޑ ᅖගϲ[48]Ƕ 2.7.2 RedoxӅᆫޑނᔈҔ(nicotinamide)[49] ӧၨԐޑਔයǴεӭኧزࣴޑख़ܭڀႝϯᏢࢲ( ܄ջϩηҁ਼ڀيϯᗋ চނ)܄፦ޑႝϯᏢՉࣁǴ਼ϯᗋচϸᔈၸำ܌ԋޑႝηᙯ౽ǴႝཱུᏤԿ ѦጕၡࡕǴΓॺߡҗ܌ᢀჸளϐႝࢬ܈ႝՏॶٰޕϸᔈՉ܈ݩރϸᔈނᐚࡋǴ ϩޑᆒઓߡ֖ཷځύǶВࡕଞჹғނϩηǴҗܭғނϩη໔தڀԖ౦܄ᜢ߯(ӵ ሇન୷ک፦ǵלᡏלکচ)ǴࣴߡޣزճҔځᜢٰ߯ၲԋගଯᒧޑ܄ҞޑǴӕਔΨ ගଯϩྗޑዴࡋǶႝϯᏢسᙁܰ(simplicity)ޑ܄ǴӕਔڀԖόᒱޑᡫ௵ࡋǴ ӢԜԋࣁঁ㶥٫ޑགෳϡҹᏤᐒ(ڋtransduction)Ǵуғނϩη໔ޑ౦܄ᜢ ߯Ǵ׳ёှ،གෳϡҹதय़ᖏޑᒧ܄ୢᚒǶҞதޑـΟᅿғނϩηགෳϡ ҹǴхࡴǺሇનۓڰϯႝϯᏢགෳᏔ(electrochemical enzyme-immobilized biosensor)ǵ ႝ ϯ Ꮲ Ԅ խ ࣝ ག ෳ Ꮤ (electrochemical immunoassay) ǵ Ϸ ႝ ϯ Ꮲ Ԅ ਡ ለ ག ෳ Ꮤ (electrochemical sensors of nucleic acids)ΟᅿǴҁჴᡍࢂағނᛰࠔnicotinamideׯ ፦ڀԖशΌ่ᄬسӈޑᆫӝނǴ٬ׯځ፦ࡕڀԖᚈ܄܄፦ޑᆫӝނЪԖ਼ϯᗋচ ޑ܄ǶӢԜ܄፦КၨୃӛሇનۓڰϯႝϯᏢགෳᏔǴӧௗΠٰޑϣஒϟಏԜ གෳᏔǶ ሇનۓڰϯႝϯᏢགෳᏔ;! ! ! !ሇનۓڰϯགෳᏔགෳᐒڋЬाࢂճҔܭۓڰགෳႝཱུϐሇન౦܄ϯ ࡑෳނǴ٠ᙖҗགෳϯၸำύ܈ౢғޑႝϯᏢࢲނ܄፦ǴԶளૻډဦǴҞ നத٬Ҕϐচࣁགෳϸᔈၸำύ਼ޑ܌ǵౢғޑၸ਼ϯణǵΒ਼ϯᅹǵ܈ 26 ᚆηǶሇનۓڰϯޑғϯགෳᏔё٩ځགෳᐒޑڋวϩࣁΟঁШжǶಃ Шж;ճҔྋ਼གෳႝཱུǴགෳ਼ϯሇનϯࡑෳނၸำύޑ܌ྋ਼Ǵ໔ ௗளࡑޕෳނᐚࡋǹќᅿ߾ୀෳሇનϯϸᔈޑౢނǴԶளࡑޕෳނᐚࡋǴԜ ౢނѸሡࢂڀႝϯᏢࢲ܄ϐނ፦Ǵதޑـӵၸ਼ϯణǶಃΒШжکಃШжޑৡ౦ ЬाࣁႝηሀޑނуΕǴಃШжύྋ਼܈ౢ֡ނѸሡၸᘉණբҔωૈܢႝཱུ ߄य़ՉϸᔈǴࢂԋեႝࢬਏޑЬाচӢǶಃΒШжᙖҗႝηሀނගଯႝη ሀԿႝཱུ߄य़ޑਏǴӕਔҭёफ़եགෳ܌ሡϐႝՏǴႝηሀނҁڀيԖ਼ϯ ᗋচёޑ܄Ǵٯӵӧঁ਼ϯޑགෳၸำύǴႝηሀނௗԏགෳϸᔈ܌ౢ ғޑႝη٠ԾيᗋচԋᗋচᄊǴ٠ܭႝཱུ߄य़Չ਼ϯϸᔈаճஒႝηሀ๏ႝ ཱུԋૻဦǶќঁᓬᗺࣁႝηሀڀނၨե਼ޑϯᗋচႝՏǴёफ़եঁགෳբ Ҕ܌ሡޑႝՏǴᗉխӢଯႝՏԋځѬυᘋނ፦)ڀႝϯᏢࢲޑ*܄ቹៜǶය ගଯགෳᐒႝηሀޑਏǴଞჹ٤ڀᇶշӢηޑሇનǴ߾уΕᇶշӢηаफ़ե ሇનϯ਼ϯ܈ᗋচϸᔈਔႝηԾሇનሀрߔޑΚǴԜᆀࣁಃΟШжޑሇનགෳ ᏔǴനதޑـᇶշӢηӵNAD+/NADHϷFAD/FADH2Ǵёஒς֖ԖᇶշӢηޑሇન ᇙഢܭۓڰкᅈႝηሀޑނНྋጤଯϩηύǴႝηӧځύᙖҗኧঁё਼ޑϯϷ ᗋচၸำஒႝηሀԿႝཱུǴࣴزԋ݀ᡉҢځႝηޑሀਏᇻଯܭΒШжǴ ӢԜགෳᏔёளၨଯޑᡫ௵ࡋǴՠલᗺ߾ࣁᇙഢၸำၨࣁፄᚇǶ! 27 hexane, cyclohexane DGEBA ࠠᕉ ਼ᐋિ ለ✊ᐋિ CIPS CIPS 28 ٬ځᐒఓ܄፦फ़եǶ బуྋᏊޑቹៜǴวᒿྋᏊቚӭԶ җᘉණᐒڋᇴрଯϩηύǶځύ٠аDMA όؼྋᏊǴӧ࣬ϩᚆࡕǴྋᏊуǴԶ ᗺǵჹൂᡏࢂؼྋᏊϷჹฯϯᆛރଯϩηࢂ ځύྋᏊࣁϩණ࣬ǴЪڀԖեϩηໆǵեݦ ᖓጢǴځϟႝதኧᒿϾሜࡋϐቚуԶᡂλǶ ຓܴεϩޑࠠڰଯϩηճҔ CIPS ӝԋ cyclohexane ᚈ⇌ E ࠠ⋸ εǴЪځελϩթࡌҥӧᅿޑԋਡԋߏᆶ ϾࢰελᒿྋᏊໆ܈ฯϯྕࡋޑቚуԶᡂ ่ࣴ݀ز ฯϯϸᔈޑᝡݾΠǶ cyclohexane CIPS БԄ ଯϩη hexane, ࣬ϩᚆ ྋᏊ or ༟܄ ȐDER-332ȑ ਼ᐋિ DGEBA ࠠᕉ ଯϩηൂᡏ ޑፄӝ ଯਏૈᗹᏊϷӭϾ ๊ᡏ եϟႝᆶ๊ጔک 1999 [50] K. Joachim et al., 1999 [4] K. Joachim et al., 1996 [46] ၸᘠϷቫЍኖނ Ўрೀ J. Kiefer et al., ᔈҔ ๊ጔ๊کᡏǵᖓጢǵ ߄ 2.1 ϯᏢᇨว࣬ϩᚆݤᇙഢӭϾ܄ଯϩηϐЎ߄ ਼ᐋિ DGEBA ࠠᕉ ȐDER-332ȑ cyclohexane CIPS 29 Ԕጕӛ౽Ƕ ଯ߾ᙯϯཇଯǹวᒿྕࡋϲଯǴᜦᗺᙯϯ ᡍளډᜦᗺᙯϯჹಔԋޑԔጕǴᒿྕࡋཇ near-infrared spectroscopyȐNIRȑऀکჴ ׯᡂᄊǶ ՠᄊׯᡂǹԶಔԋׯᡂᜦᗺᙯϯ٠Ψ CIPS ਼ᐋિ water ࣴزวᜦᗺᙯϯ٠όᒿ٢ϯᏊԶׯᡂ ᗺᙯϯޑԔጕǶ ໆෳளډᜦᗺਔ໔Ǵஒ่ঁٿӝளډಔԋჹᜦ CIPSǶ٠ᙖҗDSCளᙯϯϷᙖҗᜦᗺޑ ीᆉளډbinodalϷspinodalԔጕǴ٠ှញ ่ࣴ݀ز DGEBA ࠠᕉ polmers(HBP) ਼ᐋિ CIPS БԄ ଯϩη Hyperbranched ࣬ϩᚆ ྋᏊ or ༟܄ DGEBA ࠠᕉ ଯϩηൂᡏ ᔈҔ Ѝኖނ ᡏǵᖓጢǵၸᘠϷቫ ӭϾ܄ଯϩηǴӵวݰ ጢ ӵӧ༾ႝηޑϟႝᖓ ӭϾ܄܄ڰଯϩηǴ ଯϩηፄӝ ߄ 2.1 ϯᏢᇨว࣬ϩᚆݤᇙഢӭϾ܄ଯϩηϐЎ߄Ȑុȑ 2003 [53] E. Soule et al., 2000 [52] L. Garcia et al., 2000 [51] M. Raffaele et al., Ўрೀ MY720 30 ࠠᄊ ᄊҗsea-islandࠠᄊᙯඤԋࣁSAN-richᗭಈރ బуόӕ֖ໆSANਔǴׯᡂ߄ځय़ࠠ CIPS ᐋિ ܭᆫӝϸᔈύǴబуSAN༟܄ଯϩηǴ ༾ࡋྕޑᡂϯԔጕᏤठᄊׯޑᡂǶ ᄊǴԶPSF/PEIКௗ߈ӧόёྋߕ߈Ǵ ᇸ /PEIКቚуǴځևрᗭಈރόӕࠠޑ ܭᆫӝϸᔈύёӕਔబуPSFکPEIǴᒿޣPSF ่ࣴ݀ز ׯᡂځᏉጤϯ࣒کዟϯޑਔ໔Ǵ่݀Ψว SAN PEI RIPS БԄ ଯϩη PSF ࣬ϩᚆ ྋᏊ or ༟܄ TGDDM ᕉ਼ ȐDER-332ȑ ਼ᐋિ DGEBA ࠠᕉ ଯϩηൂᡏ ᔈҔ ଯϩηፄӝ ่ᄬޑ܄Ƕ Զׯᡂғౢᆫӝޑ ёගٮཥࢰޑჸΚ ߄ 2.1 ϯᏢᇨว࣬ϩᚆݤᇙഢӭϾ܄ଯϩηϐЎ߄Ȑុȑ 2002 [55] J. Lopez et al., al.,2005 [54] MI. giannotti et Ўрೀ polystyrene (sPS) poly(1,2-butyle ne glycol) monobutyl ether ਼ᐋિ ȐDER-330ȑ Dicyclopentad iene (DCPD) CIPS RIPS БԄ ଯϩη syndiotactic ࣬ϩᚆ ྋᏊ or ༟܄ DGEBA ࠠᕉ ଯϩηൂᡏ 31 ࠠᄊޑቹៜǶ ރPDCPDǴ٠ᙖҗϯᏊᅿᜪ֖کໆჹ ёᒧӝޑϾᏊᇙഢڀԖ༾Ͼࢰکᗭಈ Ǵ่݀ځҗีܭញਏᔈکᗹࡋׯᡂ܌ቹៜ եځϸᔈǴᒿޣਔ໔ޑቚуځϸᔈΞቚу ғޑਔ໔ௗ߈ǴԶబуsPSӧଆ߃ޑਔ໔फ़ ჴᡍ่݀ࡰр࣬ϩᚆޑਔ໔کsPS่ϯว ่ࣴ݀ز ᔈҔ ๊๊کጔ ࣬ϩᚆᐒڋ ёׯᡂϸᔈΚᏢک ߄ 2.1 ϯᏢᇨว࣬ϩᚆݤᇙഢӭϾ܄ଯϩηϐЎ߄Ȑុȑ al., 2004 [57] A.D. Martina et 2005 [56] N. Salmon. et al., Ўрೀ 4-ෛҘ୷शΌ ᆶΒशΌ AIBN BPO --- Neutral Red 4-ෛҘ୷शΌ ଆۈᏊ ϸᔈނ --- Tris nicotinamide ׯ፦Ꮚ 32 ᙖҗThermal ImprintingБԄǴᆫӝрӭቫጢ хᙟޑ༾ౚǶ ڀԖؼӳЪե༹ޑpHགᔈᏔǶ Takekoh et al., 2005[60] L. Zhang et al., 1997[59] A.A.Karyakin et al., 2003[58] NAD+کNADHޑѳᑽႝՏޑᜢ߯Ƕ аशΌᖓጢ୷Ǵӧय़Չׯ፦Ǵ٬ځ Ўрೀ ࣴزϣ ߄ 2.2 4-ෛҘ୷शΌϷѭёᎇㄽữ࣬ᜢϐЎ߄ ଆۈᏊ azobis dihydrochloride BPO ϸᔈނ 4-ෛҘ୷शΌ ΕΒशΌΕ˖˔ ᆶशΌ 4-ෛҘ୷शΌ ᆶΒशΌ diethanolamine succinic anhydride --- ׯ፦Ꮚ 33 ᇙഢфૈ܄ಈηԶวࣁ weak cationexchange packingǶჴᡍ่݀weak cationexchange packingКthe silica-based packingsҔጄൎ׳ ቶǵ׳ᛙۓǶ! ಈη܄ޑКၨ ճҔ٢ϯᆫӝݤᇙഢڀԖᅶ܄ಈη٠کคᅶ܄ ࣴزϣ ߄ 2.2 4-ෛҘ୷शΌϷѭёᎇㄽữ࣬ᜢϐЎ߄Ȑុȑ Bolin Gong et al., 2005[62] Reza Faridi-Majidi et al., 2006[61] Ўрೀ --- --- nicotinamide KPS ଆۈᏊ nicotinamide 4-ෛҘ୷शΌ ΕΒशΌ ᆶशΌ ϸᔈނ --- --- Thymine potassium salt ׯ፦Ꮚ Y.Feng et al., 2006[64] K.Takagi et al., 1998[65] NicotinamideໆޑӭჲکΓᡏޑᜢ߯Ϸख़ा܄Ƕ ճҔNADёޑ܄ӧғނ൞ޑᔈҔǶ 34 Michael F. Cunningham et al., 2005[63] Ўрೀ ჹܭthyminefunctionalizedpolystyrene microspheres ࣴزр׳ԖਏޑӝԋБ! Ԅ٠ճҔܭғמࣽނ! ࣴزϣ ߄ 2.2 4-ෛҘ୷शΌϷѭёᎇㄽữ࣬ᜢϐЎ߄Ȑុȑ AIBN BPO ΒशΌᆶशΌ 4-ෛҘ୷शΌ ΕशΒΌ ᆶᕉρ₧ ଆۈᏊ ϸᔈނ ׯ፦ࡕޑ༾ಈёճҔࡷܭᒧӦ፦ύޑख़ߎឦᚆη 1,5,9,13-tetr athiacyclohe xadecane-3, 11-diol 35 ፕ ozone ࢬໆᆶ೯ ozone ޑਔ໔ߏอჹ༾ಈޑቹៜ ࣴزϣ --- ׯ፦Ꮚ ߄ 2.2 4-ෛҘ୷शΌϷѭёᎇㄽữ࣬ᜢϐЎ߄Ȑុȑ C. Kavaklı et al., 2005[67] E. Partouche et al., 2005[66] Ўрೀ ! ಃΟക!ჴᡍБ!ݤ 3.1 ჴᡍᛰࠔ 1. 4-ෛҘ୷शΌ(4-chloromethylstyrene)(CMS) CH2 Molecular Weight=152.62 ભ:၂ᛰભ(90%) ቷ:ACROS ᛰࠔጓဦ:1592-20-7 Cl 2. ΒΌश(divinylbenzene)(DVB) HC HC 3. CH2 Molecular Weight=130.19 bp= 195 °C ભ: ၂ᛰભ~80% ቷ: Fluka ᛰࠔጓဦ:43908 CH2 2,2-ଽේᚈ౦୷㶮(2,2-azobisisobutyronitrile)(AIBN) N CN N CN Molecular Weight=164.21 ભ:၂ᛰભ(99%) ቷ:SHOWA ᛰࠔጓဦ: 0159-2130 36 ᕉρ₧(cyclohexane) 4. Molecular Weight=84.16 bp= 81 °C ભ:HPLC ቷ: MERCK ᛰࠔጓဦ: Art.2827 ѭёᎇㄽữ(nicotinamide) 5. N NH2 O Molecular Weight=122.12 bp= 150-160 °C ભ:၂ᛰભ(98%) ቷ:ACROS ᛰࠔጓဦ:98-92-0 6. Ч✉(acetone) Molecular Weight=58.08 bp= 56 °C ભ:ʳ˛ˣ˟˖ʳʻˌˌˁˈʸʼ ቷ:TEDIA ᛰࠔጓဦ:67-64-1 7. Ҙᎇ(methanol) Molecular Weight=32.04 bp= 64.7 °C ભ: HPLC (99.9%) ቷ: TEDIA ᛰࠔጓဦ:67-56-1 37 8. ౷ж౷ለ໊(Na2S2O3Ƿ5H2O) Molecular Weight=248.19 ભ: ၂ᛰભ(99%) ቷ: SHOWA ᛰࠔጓဦ:1960-2150 9. ᚈ਼Н(H2O2) Molecular Weight=34.01 bp= 114 °C ભ: ၂ᛰભ(35%) ቷ: ACROS ᛰࠔጓဦ:7722-84-1 10. ဟᑗ(alpha-D(+)-Glucose) Molecular Weight=180.15 mp=156-158 °C ભ:၂ᛰભ(99+%) ቷ:ACROS ᛰࠔጓဦ:492-62-6 3.2 ჴᡍሺᏔ 1. ᅲԄႝηᡉ༾᜔(scanning electron microscope)(SEM) ቷ:HITACH ࠠဦ:S-3000H ൂՏ:ѠчࣽמεᏢϯπᓔᆒஏሺᏔ࠻ 2. ख़ໆཞѨϩሺ(Thermo Gravimetric Analsis)(TGA) ቷǺTA ࠠဦǺDu Pont951 ൂՏǺѠчࣽמεᏢϯπᓔ 407 ࠻ 38 3. ഡΚယᙯඤआѦጕӀሺ(fourier transformation infrared spectrophotometer)(FTIR)ʳ ቷ:Perkin Elmer ࠠဦ:Spectrum 2000 ൂՏ: ѠчࣽמεᏢϯπᓔᆒஏሺᏔ࠻ 4. ჴᡏᡉ༾᜔(Micro Scopes) ࠠဦǺMIRAGE ൂՏ: ѠчࣽמεᏢϯπᓔ 401 ࠻ 5. DVឪቹᐒ(Digital Video Camera) ࠠဦǺNV-DE3ǴPanasonic ѠчࣽמεᏢϯπ܌401࠻(းკߕܭᒵA) 6. ႝηኧᏵϺગ ቷǺA and D Co.Ltd.,Japan ࠠဦǺBL210S ൂՏ: ѠчࣽמεᏢϯπᓔ 401 ࠻ 7. ޜᔅ(Vacuum PUMP) ቷ:ܿϡႝᐒ ࠠဦ:BSGV ൂՏ: ѠчࣽמεᏢϯπᓔ 401 ࠻ 8. ޜጃ ቷ:DENG YANG Instruments Co. ࠠဦ:DOV-30 ൂՏ: ѠчࣽמεᏢϯπᓔ 401 ࠻ 39 3.3 ჴᡍࢬำᆶᡯ 3.3.1 ჴᡍࢬำ! 1. Ҭᖄଯϩηᖓጢϐӝԋ ൂᡏ,ଆۈᏊ,ҬᖄᏊ! ! уΕόӕᡏᑈໆޑྋᏊǴషӝ֡Ϭ!! ! ஒషӝ֡Ϭޑྋనᅀ࣒ܭዟТޑ᠗ኳኲύǴ! ӆа࣒ዟᙟᇂځ!! ܫΕጃՉҬᖄϸᔈ ! Ҭᖄଯϩηᖓጢ! аҘᎇϸᙟࢱృኧԛ SEM TGA FTIR 40 ௗف ᅖ! ܄፦! 2. ճҔׯ፦Ꮚׯ፦Ҭᖄଯϩηᖓጢ Ҭᖄଯϩηᖓጢ+ׯ፦Ꮚ аacetoneࣁׯ፦ᏊޑྋᏊǴ ϲྕԿ60ʚǴՉׯ፦ϸᔈ ਼ϯᗋচགෳޑ܄ Ҭᖄଯϩηᖓጢ аacetoneϸᙟࢱృኧԛ SEM TGA FTIR 41 ௗف ᅖ! ܄፦! 3.3.2!ჴᡍᡯ! Ҭᖄଯϩηᖓጢϐӝԋ a.ஒۓڰವԸК ޑٯCMSǵDVBǵAIBN ᆶόӕᡏᑈໆ ޑcyclohexane షӝ֡ ϬǴԶӚኬࠔޑжဦᆶಔԋԋϩӵ߄ 3.1ǹ ߄ 3.1 ኬࠔޑжဦᆶಔԋԋϩ CMSǺDVBǺAIBN CMS ᡏᑈ cyclohexane ᡏᑈ (ವԸኧК) (ml) (ml) ኬࠔжဦ M1 0.8 M2 1.2 48Ǻ1Ǻ21 M3 1 1.6 M4 2 M5 2.4 b.ஒషӝ֡Ϭޑྋనᅀ࣒ܭዟТޑ᠗ኳኲύǴӆа࣒ዟᙟᇂځǹ (b) (a) ᓸӝ ࣒Т! ᠗ኳኲ! ࣒Т! ! 1. షӝ֡Ϭޑྋన! ࣒Т! ! ᠗ኳኲ! ! ࣒Т షӝ֡Ϭޑྋన! კ3.1 ኬࠔᇙഢკȐaȑୁຎკȐbȑҥᡏҢཀკ[68] 42 c.ܫΕ 60ʚޑጃύ 8 λਔǴՉҬᖄϸᔈǹ! d.ӆа 9 λਔϣǴவ 60ʚᄌᄌϲྕԿ 85ʚǹ e.ᆢ 85ʚ ࡋྕޑ4 ঁλਔǴаѐନྋᏊǹ! f.ӝԋϐᖓጢаҘᎇϸᙟమࢱኧԛǹ g.ஒҬᖄଯϩηᖓጢܫΕ 110ʚޜጃύǴଳᔿ 24 λਔǶ 2. ճҔ nicotinamide ׯ፦Ҭᖄଯϩηᖓጢ a.ஒҬᖄଯϩηᖓጢǵnicotinamideΕЧ✉ܭஏ࠾ޑᐨ݆ύǹ b.ܫΕ 60ʚޑጃύ 24 λਔǴՉׯ፦ϸᔈǹ c.ׯ፦ࡕޑҬᖄଯϩηᖓጢճҔЧ✉પϯǹ d.ܫΕ 110ʚޜጃύǴଳᔿ 24 λਔǴׯ፦ࡕޑᖓጢжဦӵ߄ 3.2Ƕ ߄ 3.2 ᖓጢׯ፦ࡕޑжဦ ҂ׯ፦ޑᖓጢ ׯ፦ࡕޑᖓጢ жဦ жဦ M1 ׯ፦ϸᔈ Q1 M2 ׯ፦ϸᔈ Q2 M3 ׯ፦ϸᔈ Q3 M4 ׯ፦ϸᔈ Q4 M5 ׯ፦ϸᔈ Q5 43 3.3.3 ჴᡍϸᔈԄ ճҔ nicotinamide ׯ፦Ҭᖄଯϩηᖓጢϐӝԋ! H H H H C C C C n H H DVB / AIBN / cyclohexane n H CH2 CH2 C C Cl Cl H H H H H H C C C C n H H nicotinamide 60к, in acetone H CH2 N+ Cl- C C H H NH2 O !! 44 3.4 ჴᡍϩ 1.!ඔԄႝηᡉ༾᜔(SEM) ᢀჸҬᖄଯϩηᖓጢׯܭ፦ࡕ߄ޑय़Ϸᄒय़ࠠᄊǶ ኬࠔᇙഢǺעҬᖄଯϩηᖓጢܫΕጃଳᔿѐନНϩǴаᅹጤܭۓڰၩѠ ǴӧޜΠᇃᗓቫߎǴ٬၂ТԋࣁႝᏤᡏǶ 2. ख़ཞѨϩሺ(TGA)!! ෳໆҬᖄଯϩηᖓጢޑှྕࡋǶ ኬࠔೕǺҬᖄଯϩηᖓጢϐኬࠔ 10~15mg ᏹբచҹǺϲྕೲࣁ 10ʚ/mioǴේࢬໆ 40ml/min. ྕࡋጄൎǺ࠻ྕ~700ʚ 3. ഡҥယᙯඤआѦጕӀሺ(FTIR) ෳໆҬᖄଯϩηᖓጢϐ֎ޑ୷ૈ۔ԏǴ٠ёаҗᖓጢׯ፦ࡕϐ C-Cl ܄ঢ়!!! !!!ևޑቚ෧ٰीᆉׯ፦Ƕ! ኬࠔೕǺڰᄊ༝၂Т ᏹբచҹǺᅲጄൎ 400 ~ 4000 ʡ-1Ǵᅲ 8 ԛ ! ! ! ! ! ! ! ! ! ! 45 ! ಃѤക ่݀ᆶፕ 4.1 ྋᏊ֖ໆჹܭҬᖄଯϩηᖓጢϐቹៜ 4.1.1 ྋᏊ֖ໆჹ ܭpoly(CMS-co-DVB)ᖓጢࠠᄊϐቹៜ ҁჴᡍճҔόӕᡏᑈКൂޑٯᡏᆶྋᏊӝԋҬᖄଯϩηᖓጢǴ٠ճҔඔԄ ႝηᡉ༾᜔(SEM)ᢀჸᖓጢ༾ᢀ߄ޑय़Ϸᄒय़ࠠᄊǶஒ܌ᢀჸόӕྋᏊ֖ໆ܌ӝԋ ޑpoly(CMS-co-DVB)ᖓጢځѦᢀ܄Ϸ༾ᢀࠠᄊӵ߄ 4.1ǴԶྋᏊ֖ ໆჹᖓጢࠠᄊޑቹៜǶ ߄ 4.1!poly(CMS-co-DVB)ᖓጢޑѦᢀ܄Ϸ༾ᢀࠠᄊ! ! poly(CMS-co-DVB)ᖓጢжဦ! M1 M2 M3 M4 !!!ᖓጢ! ѦᢀᚑՅ! ܴ!ޑ Յ! ъܴ!ޑ ٢қՅ! қՅ! !!!ᖓጢ! ૄࡋமࡋ! ૄ! ૄ! Ԗ!܄ Ԗ!܄ Ԗ!܄ ! ᖓጢ! ߄य़ࠠᄊ! ! ߄य़ѳ ϩթ٤λ Ͼࢰ კ 4.4 ߄य़ѳ ϩթ٤λ Ͼࢰ კ 4.5 ߄य़ϩթε λǵుభό ޑϾࢰ კ 4.6 ߄य़ϩթࡐ ӭుభό ޑϾࢰ კ 4.7 ϩණӭೀޑ ᗭಈ߄य़ კ 4.8 ! ᖓጢ! ᄒय़ࠠᄊ! ! ጏஏ คϾࢰ კ 4.9 ጏஏ ԖϿϾࢰ კ 4.10 ελόޑ Ͼࢰ კ 4.11 ᗭಈ่ᄬ ۶Ԝ໔Ԗϕ ऀޑϾࢰ კ 4.12 ᗭಈ่ᄬ ۶Ԝ໔ࡐӭ ϕऀޑϾࢰ კ 4.13 !!!қՅ! M5 !!!қՅ! !!!!ൂᡏՉҬᖄϸᔈᡂԋҬᖄଯϩηǴځύྋᏊࢂόୖᆶϸᔈޑǴ܌аଯϩη ֹԋҬᖄϸᔈࡕǴගଯྕࡋаѐନҬᖄଯϩη่ᄬύޑྋᏊǶӧଯϩηᆶྋᏊЇ วڰన࣬ϩᚆၸำύǴྋᏊ֖ໆޑӭჲஒቹៜᖓጢࠠޑᄊǶҁჴᡍวǺӧྋᏊ 46 ֖ໆϿਔǴᖓጢ߄य़ϾࢰࡐϿЪᄒय़ጏஏؒԖϾࢰǹྋᏊ֖ໆၨӭਔǴᖓጢ߄य़ ڀԖుభǵελόޑϾࢰЪᄒय़ԖϕऀϾࢰǴޣٿϐ໔ޑৡ౦ࡐεǶஒճҔ Ўკ 2.7 ٰፕҁჴᡍ܌ᇙഢޑᖓጢࠠᄊǶM1~M3 ᖓጢឦܭྋᏊ֖ໆϿޑᖓጢǴ سځಔԋК֤ٯပӧϟᛙᄊϣǶӧϟᛙᄊϣޑᖓጢࠠᄊΞᒿྋᏊ֖ໆޑӭჲ ԶԖ܌όӕǴྋᏊ֖ໆϿǴᖓጢڀԖελठޑϾࢰǴԶྋᏊ֖ໆӭਔǴ߾ᖓጢ Ԗελό֡ޑϾࢰрǶӧҁჴᡍύ ޑM1 ᖓጢϷ M2 ᖓጢޑϾࢰ൩ࢂឦܭε λၨठޑǴԶ M3 ᖓጢӢࣁྋᏊ֖ໆၨӭǴ܌аځϾࢰ߾ࢂελό֡ǶќѦޑ M4 ᖓጢϷ M5 ᖓጢسځಔԋК֤ٯပӧᖏࣚಔԋޑѓᜐ(سಔԋɧ Ic )Ǵឦܭ ᗭಈᖓጢǴҗკ 4.12 Ϸკ 4.13 ёаᢀჸрᗭಈ่ᄬǶҗჴᡍ่݀ёаᘜયǺᖓጢ ߄य़ࢂ܈ᄒय़ϣቫࠠޑᄊǴᒿྋᏊ֖ໆԖ܌ᡂϯǴځϾࢰЁκᒿబуྋᏊ ֖ޑໆևрൂϩѲ(Ͼࢰελ֡)ډᚈϩѲ(Ͼࢰελό)ޑᖿ༈ǶӢࣁόӕޑ ༾ᢀݩԶԋόኬޑѮᢀ߄ǶྋᏊ֖ໆϿਔǴᖓጢϣϾࢰࡐϿ܌аӀጕ ܰऀǴᖓጢևъӀǹྋᏊ֖ໆӭਔǴᖓጢϣϾࢰࡐӭԋӀጕޑϸ ԶևрқՅޑѦᢀǶԶᖓጢૄࡋமࡋБय़ǴวᒿྋᏊ֖ໆຫӭԶᖓጢຫԖ ܄ǴځচӢکҬᖄஏࡋԖᜢ߯ǶӢࣁྋᏊ֖ໆϿǴ߾ൂᡏӧϸᔈޑషӝྋన ύϐᐚࡋଯǴ܌а۶Ԝ໔วғҬᖄϸᔈޑᐒӭǴҬᖄஏࡋଯǴࡺᖓጢ่ᄬࢂጏ ஏޑǶ࣬ჹޑǴྋᏊ֖ໆၨӭਔǴ߾ൂᡏӧϸᔈޑషӝྋనύϐᐚࡋ൩ၨ եǴ܌а۶Ԝ໔วғҬᖄϸᔈޑᐒफ़եǴҬᖄஏࡋᡂեǴࡺᖓጢ่ᄬࢂၨόጏ ஏޑǶᢀჸᖓጢޑᄒय़ࠠᄊёᕇளှញǴа M1 ᖓጢࣁٯǴځྋᏊ֖ໆനϿǴᄒय़ კ(კ 4.9)วᖓጢ่ᄬࢂጏஏޑǴ܌аᖓጢޑமࡋࡐଯǹԶ M5 ᖓጢځྋᏊ֖ໆ നӭǴᄒय़კ(კ 4.13)วᖓጢࢂҗࡐӭᗭಈ࣬ϕௗೱԶԋޑǴԶᗭಈ۶Ԝޑௗ य़ᑈϿǴ܌а่ᄬණǴࡺᖓጢޑமࡋၨեǶᇙഢଯϩηᖓጢਔǴྋᏊ֖ໆନ ΑቹៜᖓጢޑҬᖄஏࡋѦǴΨԖёૈྋᏊܭଯϩη่ᄬύόܰ౽ନֹӄԶԋࣁ ᖓጢޑё༟ᏊǴԶ೭ё༟ᏊΨஒࢂቹៜᖓጢૄࡋᆶޑ܄ӢનϐǶӧჴᡍύޑ M4 ᖓጢϷ M5 ᖓጢӢࣁྋᏊ֖ໆၨӭǴԖёૈ҂ѐନֹӄޑྋᏊᡂࣁଯϩηᖓጢ ޑё༟ᏊǴ܌а M4 ᖓጢϷ M5 ᖓጢڙё༟ᏊޑቹៜǴࡺ܄ᓬځܭдᖓጢǶ ! ! ! 47 4.1.2 ྋᏊ֖ໆჹ ܭpoly(CMS-co-DVB)ᖓጢ܄፦ϐቹៜ! !!!!ճҔTGAϩpoly(CMS-co-DVB)ᖓጢޑ܄፦Ƕკ 4.14 ࣁϖಔόӕᖓጢ (M1)~(M5)ޑTGA᠄კǶკ 4.14 ύёวԖࢤٿှǴಃࢤှෳ ࢂCH2C1 ϩޑᘐᗖǴಃΒࢤှෳࢂशᕉ่ޑᄬǶ߄ 4.2 ࣁϖಔᖓጢޑ ख़ϩኧᏵǶҗჴᡍวǺϖಔᖓጢޑ܄፦Ԗঁᖿ༈Ǵځᖿ༈ࣁM1 ᖓጢԿ M5 ᖓጢ ځ5%ख़ໆཞѨྕࡋǵനεှྕࡋϷchar yeildԖᅌᡂλǶᢀჸϖಔ ᖓጢൂޑᡏǵҬᖄᏊکଆۈᏊޑವԸКࢂٯኬޑǴѝԖྋᏊ֖ໆόӕǴԶྋᏊ ֖ໆନΑቹៜᖓጢ߄ޑय़ࠠᄊϷϾሜ่ᄬѦǴΨቹៜଯϩηޑҬᖄำࡋǶӧϸ ᔈྋనύǴྋᏊຫӭ߾ൂᡏᐚࡋຫեǴൂᡏ࿘ናᐒ෧Ͽ߾Ҭᖄࡋ൩फ़եǹ࣬ ჹޑǴྋᏊຫϿ߾ൂᡏᐚࡋຫଯǴൂᡏ࿘ናᐒගϲ߾Ҭᖄࡋ൩ϲǶଯϩη ᖓጢޑҬᖄࡋଯեቹៜҁيϐ܄፦ǴҬᖄࡋଯޑᖓጢӢࣁϩη่ᄬࢂၨڰآǴ ܌аाઇᚯځϩη่ᄬࢂၨ֚ᜤޑǴሡाၨଯࡋྕޑǶ܌аҬᖄࡋଯޑᖓጢ ځ5% ख़ໆཞѨྕࡋǵനεှࢂࡋྕޑଯޑǴЪӧࡋྕޑۓڰΠځchar yeildࢂӭޑǶ ࣬ჹޑǴҬᖄࡋեޑᖓጢ߾ϸϐǶҁჴᡍύM1 ᖓጢԿM5 ᖓጢࣁྋᏊ֖ໆҗჲԿ ӭǴෳM1 ᖓጢޑҬᖄஏࡋനଯǴM5 ᖓጢޑҬᖄஏࡋനեǴ܌а܄፦Ӣࣁ ҬᖄࡋޑόӕԶԖόኬ߄ޑǶ ߄ 4.2!poly(CMS-co-DVB)ᖓጢख़ϩኧᏵ poly(CMS-co-DVB) 5%ख़ໆཞѨ! നεှ! char yeild ᖓጢжဦ ྕࡋ(к) ྕࡋ(к) (wt%) M1 369 449 32.52 M2 324 449 26.53 M3 311 442 22.20 M4 308 444 23.12 M5 328 437 22.10 48 4.2 ճҔѭёᎇㄽữׯ፦ poly(CMS-co-DVB)ᖓጢ! 4.2.1 ᢀჸ poly(CMS-co-DVB)ᖓጢׯ፦ࡕޑ܄Ϸࠠᄊ! ஒ poly(CMS-co-DVB)ᖓጢܭݰЧ✉ύǴబуѭёᎇㄽữׯ፦ᏊՉׯ፦ ϸᔈǶӢࣁ poly(CMS-co-DVB)ᖓጢόྋܭЧ✉ǴԶׯ፦Ꮚѭёᎇㄽữёྋܭ Ч✉ύǴ܌аྋܭЧ✉ύׯޑ፦Ꮚёаܭᖓጢ߄Չׯ፦ϸᔈǶϸᔈྕࡋࣁ 60! ʚǴၸ 24 λਔׯ፦ǴวᖓጢޑѦᢀᚑՅςԖܴᡉᡂϯǶׯ፦ࡕޑᖓጢճҔ ඔԄႝηᡉ༾᜔(SEM)ᢀჸࠠځᄊׯک፦ࢂցԖᡂϯǶஒ q-poly(CMS-co-DVB) ᖓጢޑѦᢀ܄Ϸ༾ᢀࠠᄊӵ߄ 4.3Ƕ! ! ߄ 4.3!!q-poly(CMS-co-DVB)ᖓጢޑѦᢀ܄Ϸ༾ᢀࠠᄊ! ! q-poly(CMS-co-DVB)ᖓጢжဦ! Q1 ! ! ᖓጢ! ѦᢀᚑՅ! Q2 ! ܴ!ޑ ፃՅ! ! ᗺӀ! ޑՅ! ! ! ૄ! ! ! ᖓጢ! ߄य़ࠠᄊ! ! !!!ᖓጢ! ᄒय़ࠠᄊ! ! ! ᖓጢ! ૄࡋமࡋ! ! Q3 ! Q4 ! Q5 ! ણጥՅ! ! ણጥՅ! ! ણጥՅ! ! ! ૄ! ! ! Ԗ!܄ ! ! Ԗ!܄ ! !!! Ԗ!܄ ! ߄य़ѳ ϩթ٤λ Ͼࢰ კ 4.15 ߄य़ѳ ϩթ٤λ Ͼࢰ კ 4.16 ߄य़ϩթε λǵుభό ޑϾࢰ კ 4.17 ߄य़ϩթࡐ ӭుభό ޑϾࢰ კ 4.18 ϩණӭೀޑ ᗭಈ߄य़ კ 4.19 ጏஏ คϾࢰ კ 4.20 ጏஏ ԖϿϾࢰ კ 4.21 ελόޑ Ͼࢰ კ 4.22 ᗭಈ่ᄬ ᗭಈ่ᄬ ۶Ԝ໔Ԗϕ ۶Ԝ໔ࡐӭ ऀޑϾࢰ ϕऀޑϾࢰ კ 4.23 კ 4.24 ! Кၨ߄ 4.1 Ϸ߄ 4.3Ǵᢀჸ poly(CMS-co-DVB)ᖓጢׯ፦ࡕޑᡂϯǴว(1) 49 ᖓጢѦᢀᚑՅԖܴᡉׯᡂǴׯ፦ࡕޑᖓጢᚑՅКׯ፦ୃుǶ(2)วׯ፦ࡕޑ ᖓጢ߄ځय़ࠠᄊԖ٤༾ׯᡂǴ߄ځय़ޑϾࢰԖᡂλᖿ༈Ǵа M2 ᖓጢ(კ 4.5)Ϸ Q2 ᖓጢ(კ 4.16)ࣁനܴᡉٯޑηǶᖓጢׯ፦ࡕ߄ޑय़ࠠᄊόӕǴځচӢࣁׯ፦Ꮚௗ ݄ܭᖓጢԶᙟᇂᖓጢচӃޑϾࢰǴԋᖓጢ߄य़ޑϾࢰᡂλǶ(3)ᖓጢޑᄒय़ࠠ ᄊׯܭ፦ࡕ٠คׯᡂǶӢࣁׯ፦ϸᔈεҽวғ߄ܭय़Ǵ٠όቹៜډϣ่ ᄬǴ܌аᄒय़ࠠᄊ҂ڙቹៜǶ 4.2.2 ѭёᎇㄽữჹ ܭpoly(CMS-co-DVB)ᖓጢׯޑ፦! q-poly(CMS-co-DVB)่ޑᄬ᠘ۓ ճҔ IR Չ่ᄬ᠘ۓᆶׯ፦ޑᆉǶӢࣁ IR ࢂճҔၸϩη֎ԏआѦӀ ᒟբҔЇଆਁکᙯૈ໘ޑᎂ౽܌ౢғޑआѦጕ֎ԏӀǴٰ᠘ۓϯӝ ނǴεӭҔޑ୷ૈ۔ܭ᠘ۓǴ܌а IR ёճҔٰղ่ۓᄬ୷ૈ۔ޑǶ! კ 4.25~კ 4.29 ࣁϖಔόӕྋᏊ֖ໆޑpoly(CMS-co-DVB)ᖓጢׯܭ፦ࡕϐ IRკǴᢀჸׯ፦ࡕ֎ԏঢ়ޑᡂϯǴܴׯ፦ϸᔈࢂցԋфǶவЎკ 4.30 ள ޕC-N+-R3ޑቻঢ়֎ԏߏݢӧ 1000~1050cm-1໔Ƕҗკ 4.25~კ 4.29 วׯ፦ࡕ ޑᖓጢӧ ߏݢ1030cm-1ѰѓрΑ֎ԏঢ়Ǵෳࢂq-poly(CMS-co-DVB)ᖓጢޑ ѤભữᡶC-N+-R3ϐቻঢ়ǶନΑճҔѤભữᡶC-N+-R3ቻঢ়ղࢂۓցׯ፦ԋф ѦǴΨёճҔځд֎ԏঢ়ٰܴׯ፦ϸᔈࢂցԋфǽ(1) வკ 4.25~კ 4.29 ύёа วǴׯ፦ࡕ-CH2Cl֎ԏঢ়(1265cm-1)ᆶC-Cl֎ԏঢ়(675cm-1)ჹܭशᕉ֎ԏঢ় (702cm-1)ޑय़ᑈКٯԖᡂλǴёаᇥܴ 4-ෛҘ୷शΌ(CMS)ޑෛᚆηׯ፦ Ꮚڗж٠߄ҢԖׯ፦ԋфǶ(2) җܭq-poly(CMS-co-DVB)ᖓጢޑѤભữᡶԖόᒱ ֎ޑН܄ǴёӧӀܴᡉว ࣁߏݢ3395cm-1ޑOHቻ֎ԏঢ়ᡂεǶ(3) வׯ ፦ࡕޑკύёа࣮ډӧ 1686cm-1Ԗࡐம֎ޑԏঢ়ǴԜࣁnicotinamideޑC=O ቻ֎ԏঢ়Ǵ׳ёаᇥܴׯ፦ࡕޑᖓጢڀԖnicotinamide่ޑᄬǴܴԖׯ፦ԋфǶ җॊᇥܴёаܴׯ፦ϸᔈࢂԋфޑǶ q-poly(CMS-co-DVB)ׯޑ፦ ճҔIRკǴशᕉޑჹᔈቻ֎ԏঢ়(702cm-1)ϷC-Clޑჹᔈቻ֎ԏঢ় (675cm-1)ޑጕΠۓໆय़ᑈǴаΠӈϦԄीᆉׯځ፦Ǻ 50 A2 ( 675) conversion(%) 1 A2( 702 ) A1( 675) ຏǺA1=ׯ፦ A1( 702 ) A2=ׯ፦ࡕ җӈБำԄύёаᆉр nicotinamide ჹ ܭpoly(CMS-co-DVB)ᖓጢׯޑ፦Ǵӵ ߄ 4.4Ƕ ߄ 4.4 q-poly(CMS-co-DVB)ᖓጢׯޑ፦ q-poly(CMS-co-DVB)ᖓጢжဦ! ׯ፦ Q1 21% Q2 22% Q3 24% Q4 31% Q5 28% ҁჴᡍࢂճҔྋܭЧ✉ύޑѭёᎇㄽữՉᖓጢׯ፦ǴԶׯ፦ϸᔈЬाว ғܭᖓጢ߄य़ǴԿܭᖓጢϣׯޑ፦ǴӢϾࢰޜ໔Ϸᘉණୢᚒޑቹៜ܌аځϣ ׯ፦ډڙज़ڋǶჴᡍύճҔ FTIR ՉჴᡍϩਔǴځኬࠔᇙഢࣁڗλ༧ޑᖓጢ ᆶ KBr Ѻᒭԋڰᄊ༝၂ТǴ܌аׯځ፦ж߄ࣁᖓጢᡏׯޑ፦Զߚᖓጢ߄ य़ׯޑ፦Ƕࡺᖓጢ߄य़ׯޑ፦К܌ᆉׯޑ፦ٰޑଯǶ! ! 4.2.3 Кၨ poly(CMS-co-DVB)ᖓጢׯ፦ࡕޑ܄፦! !!!!ճҔ TGA ϩ q-poly(CMS-co-DVB)ᖓጢޑ܄፦Ǵ٠ᆶ poly(CMS-co-DVB) ᖓጢޑ܄፦࣬ϕКၨǶკ 4.31 ࣁϖಔόӕᖓጢ(Q1)~(Q5) ޑTGA ᠄კǶКၨ კ 4.31 Ϸკ 4.14 ёวǺׯ፦ࡕޑᖓጢԖΟࢤှǴᆶׯ፦ޑΒࢤ ှԖ܌όӕǶׯ፦ࡕޑᖓጢӧ 260ʚѰѓӭΑࢤှǴෳࢂׯ፦ѐޑ ѤભữᡶϐှǴҗԜຝёаᇥܴׯ፦ϸᔈࢂԋфޑǶ 51 4.3 ਼ϯᗋচᏊჹܭᖓጢޑௗف !!!!ڰᡏ߄य़֎ߕቫᡏǴऩనᡏགྷाӧ߄ځय़ᘉǴѸӃஒ֎ߕϐ ᡏ௨໒ǴԜຝջࣁዎᔸǶԶڰᡏ߄य़ǵᡏϷనᅀΟ࣬ၲΚѳᑽਔǴᆀనڰ ௗय़(͐ف֨ޑკ 4.1)ࣁԜనᡏჹڰᡏޑௗفǶ! ! Ӱ კ 4.1 ڰనΟ࣬ϐΚѳᑽკ! ! җܭҁჴᡍ܌ᇙഢϐᖓጢࣁӭϾ܄ᖓጢǴనᅀᅀܭᖓጢ߄य़ਔǴనᅀᅖ ΕϾࢰύǴԶቹៜௗفϐໆෳǴ܌аճҔᏤϦԄीᆉௗ!فǴϦԄӵΠǺ! ͐ɨ180-2tan-1Ȑb/2aȑ [ԜϦԄҗ༝ࠠనᅀᆉǴa ࣁనᅀഗᗺᆶࣚय़ϐຯᚆǴb ࣁనᅀᆶࣚय़ௗߏࡋ] ! a ! ! ! b კ 4.2 ௗفीᆉკ !!!!ჴᡍύճҔόӕᐚࡋ਼ޑϯᏊ(H2O2)ǵᗋচᏊ(Na2S2O3)ǵဟᑗНྋనکѐᚆ ηН(pH=7)ෳ၂poly(CMS-co-DVB)ᖓጢکq-poly(CMS-co-DVB)ᖓጢϐௗفǶᢀ ჸᖓጢޑௗفελǴёаΑှᖓጢ߄ޑय़܄፦Ǵӵᖓጢ߄य़ޑಉᕫࡋǵ ᖓጢޑᒃНϷ౧Нׯک܄፦ࡕޑᖓጢࢂցڀԖ਼ϯᗋচϐ܄፦Ƕ! 4.3.1 ਼ϯᗋচᏊ ܭpoly(CMS-co-DVB)ᖓጢϐௗف !!!!ճҔόӕᐚࡋ਼ޑϯᏊ(H2O2)ǵᗋচᏊ(Na2S2O3)کѐᚆηН(pH=7)ჹܭϖಔ poly(CMS-co-DVB)ᖓጢௗفໆෳǴஒໆෳ่݀аკ 4.32(όӕᐚࡋ਼ޑϯᗋচ Ꮚჹܭᖓጢޑௗفᡂϯ)Ϸკ 4.33(ѐᚆηНჹܭᖓጢޑௗ߄)فҢǴ٠ஔ 52 فኧᏵߕܭᒵBύǶჴᡍวǺ(1)όӕᐚࡋ਼ޑϯᗋচᏊჹܭ҂ׯ፦ᖓጢޑௗ فࣁ 90±Ѱѓ(ନM5 ᖓጢѦ)Ǵ٠ؒԖӢᐚࡋόӕԶԖೕ߾܄ᡂϯǶፕԜ ຝࢂӢpoly(CMS-co-DVB)ᖓጢ҂ׯ፦Ǵࢂ౧Н܄ЪόڀԖ਼ϯᗋচϐ܄፦Ǵ ܌аௗفόӢ਼ϯᗋচᏊᐚࡋόӕԶԖ܌ᡂϯǶ(2)Кၨϖಔᖓጢௗفჴ ᡍǴM5 ᖓጢޑௗفКځдѤಔᖓጢௗفୃεǴෳځচӢࣁௗفελ ڙᖓጢ߄य़ࠠᄊԶቹៜǶ ᢀჸΠߘࡕޑጪယ߄य़ΔᕴࢂૈߥଳᔿЪᄾߘޑ੧ߡעယय़ޑ ԪლوǶ೭ᅿ౧Н܄ᆶԾךዅృޑຝǴᆀࣁጪਏᔈ(Lotus effect)Ƕӧႝηᡉ ༾᜔Πᢀჸጪယ߄य़Ǵ߄य़ڀԖ༾ԯભǵڼԯભँޑଆ߄ҜಒझǴ೭ኬ߄य़ޑ ಒ༾่ᄬǴ٬Нᆶယय़ޑௗय़ᑈ׳λԶௗفᡂεǴ܌аጪယёаڀԖࡐ ӳޑ౧Н܄ǶҗҁჴᡍᢀჸM1 ᖓጢ߄ޑय़ࠠᄊ(კ 4.4)ѳԶM5 ᖓጢ߄ޑय़ࠠᄊ (კ 4.8)ࣁӭೀౚރᗭಈޑόѳ߄य़Ǵనᅀᅀܭόѳ߄ޑय़ਔǴวғጪ ਏᔈǴ܌аM5 ᖓጢޑௗفКځдѤಔٰޑεǶ! ! 4.3.2 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢϐௗف ճҔόӕᐚࡋ਼ޑϯᏊ(H2O2)ǵᗋচᏊ(Na2S2O3)کѐᚆηН(pH=7)ჹܭϖಔ q-poly(CMS-co-DVB)ᖓጢௗفໆෳǴ٠ஒک่݀ځpoly(CMS-co-DVB)ᖓጢޑ ௗفჴᡍКၨǶკ 4.33 Ϸკ 4.34 ϩձࣁѐᚆηНჹܭpoly(CMS-co-DVB)ᖓጢ Ϸq-poly(CMS-co-DVB)ᖓጢޑௗفკǴ٠ஒځௗفࣁ߄ 4.5Ƕҗ߄วǺ ׯ፦ࡕޑᖓጢǴѐᚆηНჹځܭௗفК҂ׯ፦ᖓጢλǶځচӢࣁׯ፦ࡕޑ ᖓጢڀԖѤભữᡶ(୷ૈ۔C-N+-R3)ǴԶѤભữᡶࣁ୷ૈ۔ᒃН୷იǴ܌аׯ፦ࡕ ޑᖓጢڀԖؼӳޑᒃН܄፦ǴࡺځௗفᡂλǶ ߄ 4.5!ѐᚆηНჹܭᖓጢޑௗف poly(CMS-co-DVB)ᖓጢжဦ ѐᚆηНჹܭᖓጢϐௗف M1 M2 M3 M4 M5 88° 89° 94° 93° 126° q-poly(CMS-co-DVB)ᖓጢжဦ ѐᚆηНჹܭᖓጢϐௗف Q1 Q2 Q3 Q4 Q5 59° 59° 52° 46° 40° 53 ! კ 4.35~კ 4.37 ࣁόӕᐚࡋ਼ޑϯᗋচᏊکѐᚆηНܭQ1ǵQ2 ϷQ3 Οಔᖓ ጢޑௗفᡂϯ(კ 4.38 ࣁკ 4.35~კ 4.37 ϐ᠄კ)Ǵკ 4.39 Ϸკ 4.40 ࣁόӕᐚࡋ ਼ޑϯᗋচᏊکѐᚆηНܭQ4 ϷQ5 ᖓጢޑనᅀଯࡋᡂϯკǴკ 4.41 Ϸკ 4.42 ࣁ όӕᐚࡋ਼ޑϯᗋচᏊکѐᚆηНనᅀଯࡋᡂϯࣁh/h0=0.2 ਔܭQ4 ϷQ5 ᖓጢ܌ ᐕޑਔ໔(კ 4.43 ࣁკ 4.41~კ 4.42 ϐ᠄კ*ǶჴᡍวǺ(1)όӕᐚࡋ਼ޑϯᏊ ჹܭq-poly(CMS-co-DVB)ᖓጢޑௗفቹៜ٠όܴᡉǶ(2)ᗋচᏊܭq-poly (CMS-co-DVB)ᖓጢޑௗفᒿᗋচᏊᐚࡋຫεځௗفຫλǶ(3)Q4 ᖓጢϷ Q5 ᖓጢޑᒃН܄٫ǴనᅀܭᖓጢޑᅖೲࡋཱུזǴ܌аճҔనᅀޑଯࡋᡂϯკᢀ ჸځᖿ༈Ƕҗаຝёаෳᖓጢׯޑ፦ϸᔈࢂԋфޑǴӢࣁׯ፦ԋфޑᖓጢ ڀԖѤભữᡶ୷ૈ۔ޑǴ٬ׯ፦ࡕޑᖓጢڀԖᒃН܄Ϸ਼ϯᗋচϐ܄Ƕ !!!!ׯ፦ࡕޑᖓጢڀԖკ 4.3 ύޑѤભữᡶ่ᄬǴᗋচᏊ(Na2S2O3)ᅀܭq-poly (CMS-co-DVB)ᖓጢਔǴᖓጢ҅ႝޑѤભữᡶ୷ૈ۔ᗋচԶளډႝηǶᙟ ᇂܭᖓጢϾࢰޑଯϩηӢࣁளႝηևႝύ܌܄аϣᕭǴϩη۶Ԝ໔ޑ ௨ѾΚᡂ১Ǵ٬ளᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢܰܭᅖǴࡺځௗ࣬ف ၨ਼ܭϯᏊکѐᚆηНܭᖓጢޑௗޑٰفλǶ (a) (b) კ 4.3!(a)਼ϯᗋচϸᔈԄ[58](b)ᖓጢϐ਼ϯᗋচᄊ[48] ! ԶᗋচᏊޑᐚࡋΨቹៜᖓጢޑௗفελǴӵଯᐚࡋޑᗋচᏊڀԖၨம 54 ޑᗋচфૈǴԋၨӭޑଯϩηࢤᗋচǴຫӭଯϩηࢤᗋচ߾ᗋচᏊޑᅖ ൩ຫคߔᛖǴ܌аځௗفၨλǶԿܭόӕᐚࡋ਼ޑϯᏊ(H2O2)ჹܭϖಔ q-poly(CMS-co-DVB)ᖓጢޑௗفቹៜ٠όᡉǴځচӢࣁׯ፦ࡕޑᖓጢև਼ϯ ᄊ൩ӵკ 4.3(b)ύǴ٠ό਼ڙϯᏊቹៜǴ܌аόӕᐚࡋ਼ޑϯᏊܭᖓጢޑௗ فৡ౦όεǶҗკ 4.39 Ϸკ 4.40 ޑనᅀଯࡋᡂϯკǵკ 4.41 Ϸკ 4.42 ޑనᅀᅖ ਔ໔ǴวǺ(1)నᅀᅀܭᖓጢޑ໒(ۈࣾϣ)ǴаᗋচᏊޑ௹നεǴԶ ࣾࡕǴᗋচᏊޑ௹਼کϯᏊϷѐᚆηНޑ௹ৡόӭǶ(2)ׯ፦ࡕޑᖓጢჹܭᗋ চᏊᅖೲനזǴԶ਼ϯᏊനᄌǶ(3)όӕᐚࡋޑᗋচᏊჹׯܭ፦ࡕᖓጢޑᅖ ೲ߾όӕǴаଯᐚࡋ(2M)ᗋচᏊޑᅖೲനזǶ(4)਼ϯᏊჹׯܭ፦ࡕᖓጢޑ ᅖೲόӢࣁ਼ϯᏊᐚࡋׯޑᡂԶԖ܌όӕǴՠࢂ਼ϯᏊКଆᗋচᏊϷѐᚆ ηНǴځᅖೲࣁനᄌǶ ᗋচᏊᅀׯܭ፦ࡕޑᖓጢǴᖓጢޑଯϩηࢤӢࣁளႝηϣᕭǴ٬ளᗋ চᏊёаזೲᅖΕᖓጢϣǴࡺᅖೲଯǹ਼ϯᏊᅀځܭǴᖓጢޑଯϩη և਼ϯᄊǴଯϩηࢤᙟᇂᖓጢϾࢰǴՠࢂׯ፦ࡕޑᖓጢΞڀᒃН୷Ǵࡺ ਼ϯᏊޑᅖೲၨեǶԶᗋচᏊޑᐚࡋቹៜׯ፦ࡕᖓጢޑᅖೲǴӢࣁଯ ᐚࡋᗋচᏊ٬ᖓጢ҅ႝޑଯϩηεໆᗋচǴԋ۶Ԝ໔ޑ௨ѾΚᡂλǴ ܌аଯᐚࡋᗋচᏊځᅖКၨזೲǶԿ਼ܭϯᏊᐚࡋჹׯܭ፦ࡕᖓጢޑቹៜό εǴځচӢࣁׯ፦ࡕᖓጢࢂ਼ϯᄊǴ਼ϯᏊჹځቹៜόεǴ܌аᖓጢޑௗف ελόᒿ਼ϯᏊᐚࡋޑόӕԶԖׯ܌ᡂǶ 4.3.3 ဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly (CMS-co-DVB)ᖓጢϐௗفКၨ ճҔόӕᐚࡋޑဟᑗНྋనکѐᚆηН(pH=7)ჹ poly(CMS- co-DVB)ᖓጢ Ϸ q-poly(CMS-co-DVB)ᖓጢௗفໆෳǴஒໆෳ่݀аკ 4.44~კ 4.51 ߄ҢǶ җკ 4.44 Ϸკ 4.45 ёаܴᡉ࣮рဟᑗНྋనჹׯܭ፦ࡕޑᖓጢКׯ፦ޑᖓጢ ؼڀ׳ӳޑዎᔸਏ݀ǶӢࣁဟᑗНྋనׯک፦ࡕᖓጢޑѤભữᡶ୷ૈ۔ว ғ਼ϯᗋচϐϸᔈǴ٬ᖓጢ҅ႝϐଯϩηࢤӢளႝηԶϣᕭǴࢤ໔۶Ԝ ޑϕѾΚᡂλǴ܌аဟᑗНྋనёаၨคߔᛖޑᅖΕᖓጢǴڀԖၨӳޑዎᔸ ǴࡺௗفλǶԶ҂ׯ፦ޑᖓጢǴόڀԖᒃНޑ܄Ѥભữᡶ୷ૈ۔Ǵ܌аჹ 55 ܭНྋనޑዎᔸࣁݩৡǴࡺௗୃفεǶ ҂ׯ፦ᖓጢޑௗفελڙဟᑗНྋనᐚࡋޑቹៜǴځচӢෳکဟᑗ НྋనޑϣᆫΚԖᜢǶӢࣁ҂ׯ፦ᖓጢࣁ౧Н܄ЪόڀԖ਼ϯᗋচϐфૈǴ܌а ဟᑗНྋనܭ҂ׯ፦ᖓጢޑዎᔸࢂݩόགྷޑǴԶଯᐚࡋޑဟᑗНྋనӢ ࣁၨᗹ܌аځϣᆫΚεǴࡺӧ҂ׯ፦ᖓጢޑௗفεǹեᐚࡋޑဟᑗНྋ నӢࣁၨόᗹځϣᆫΚλǴࡺӧ҂ׯ፦ᖓጢޑௗ࣬فჹၨλǶ ԶဟᑗޑᐚࡋΨቹៜׯ፦ࡕᖓጢޑௗفελǴଯᐚࡋޑဟᑗНྋ నڀԖၨமޑᗋচфૈǴ܌аᖓጢ҅ႝޑϩηᗋচޑำࡋଯǴϕѾΚᡂ ১Ǵ܌аଯᐚࡋޑဟᑗНྋనׯܭ፦ࡕᖓጢޑௗف൩ၨλǶ࣬ჹޑǴե ᐚࡋဟᑗНྋనޑᗋচфૈၨ১Ǵ܌аჹׯܭ፦ࡕޑᖓጢዎᔸݩৡ٤Ǵࡺ ௗفКၨεᗺǶᗨฅဟᑗᐚࡋቹៜׯ፦ࡕᖓጢޑௗفελǴՠࢂک ᗋচᏊ࣬Кၨޑ၉ǴځቹៜΚၨόᡉǶа Q1 ᖓጢٯηٰКၨǴკ 4.35 ࣁᗋচᏊᐚࡋჹ ܭQ1 ᖓጢޑௗفᡂϯǴკ 4.46 ࣁဟᑗᐚࡋჹ ܭQ1 ᖓጢޑௗ فᡂϯǴҗٿკКၨёวǺᗋচᏊᐚࡋჹׯܭ፦ࡕᖓጢޑௗفᡂϯၨεǴ Զဟᑗᐚࡋჹׯܭ፦ࡕޑௗفᡂϯ࣬ჹКၨόᡉǶෳࣁဟᑗНྋనޑ ᗋচૈΚၨৡ܌ᏤठǶ ! ! ! ! ! ! ! ! ! ! ! ! ! 56 ʳ ʳ კ 4.4 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ!(M1 ᖓጢ) კ 4.5 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ!(M2 ᖓጢ) 57 კ 4.6 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (M3 ᖓጢ) კ 4.7 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (M4 ᖓጢ) 58 კ 4.8 poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (M5 ᖓጢ) კ 4.9 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M1 ᖓጢ) 59 კ 4.10 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M2 ᖓጢ) კ 4.11 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M3 ᖓጢ) 60 კ 4.12 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M4 ᖓጢ) კ 4.13 poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (M5 ᖓጢ) 61 110 ––– – – ––––– · –––– ––––– – ––––––– M1 M2 M3 M4 M5 90 Weight (%) 70 50 30 10 0 100 200 300 400 500 Temperature (°C) კ 4.14 poly(CMS-co-DVB)ᖓጢϐ TGA კ 62 600 700 Universal V4.2E TA Instruments კ 4.15 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q1 ᖓጢ) კ 4.16 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q2 ᖓጢ) 63 კ 4.17 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q3 ᖓጢ) კ 4.18 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q4 ᖓጢ) 64 კ 4.19 q-poly(CMS-co-DVB)ᖓጢ߄य़ϐ SEM კ (Q5 ᖓጢ) კ 4.20 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q1 ᖓጢ) 65 კ 4.21 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q2 ᖓጢ) კ 4.22 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q3 ᖓጢ) 66 კ 4.23 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q4 ᖓጢʼ კ 4.24 q-poly(CMS-co-DVB)ᖓጢᄒय़ϐ SEM კ (Q5 ᖓጢʼ 67 poly(CMS-co-DVB) 1018.08 706.84 1263.56 671.78 q-poly(CMS-co-DVB) %T 1031.23 1265.75 709.04 1018.08 673.97 3389.01 1686.57 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0 cm-1 კ 4.25 M1 ᖓጢϷ Q1 ᖓጢϐ IR Ӏკ poly(CMS-co-DVB) 1018.08 706.84 1263.56 671.78 q-poly(CMS-co-DVB) %T 1029.04 1263.56 1018.08 706.84 673.97 3389.01 1686.57 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 cm-1 კ 4.26 M2 ᖓጢϷ Q2 ᖓጢϐ IR Ӏკ 68 1000 800 600 400.0 poly(CMS-co-DVB) 1018.08 706.84 676.16 1263.56 q-poly(CMS-co-DVB) %T 1029.04 1265.75 709.04 1018.08 673.97 3410.98 1690.95 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0 cm-1 კ 4.27 M3 ᖓጢϷ Q3 ᖓጢϐ IR Ӏკ poly(CMS-co-DVB) 1018.08 706.84 1263.56 673.97 q-poly(CMS-co-DVB) 1031.23 %T 1265.75 1018.08 709.04 673.97 3397.80 1690.95 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 cm-1 კ 4.28 M4 ᖓጢϷ Q4 ᖓጢϐ IR Ӏკ 69 1000 800 600 400.0 poly(CMS-co-DVB) 1018.08 709.04 1263.56 673.97 q-poly(CMS-co-DVB) 1029.04 %T 1265.75 1018.08 709.04 673.97 3406.59 1688.76 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 cm-1 კ 4.29 M5 ᖓጢϷ Q5 ᖓጢϐ IR Ӏკ კ 4.30 ЎύѤΌ୷ữᡶ ޑIR Ӏკ (ЇҔ The Aldrich Library of Infrared Spectra,pouchert,second edition) 70 400.0 110 ––– – – –––– ––––– · ––––––– ––– ––– Q2 Q1 Q5 Q3 Q4 90 Weight (%) 70 50 30 10 0 100 200 300 400 500 Temperature (°C) კ 4.31 q-poly(CMS-co-DVB)ᖓጢϐ TGA კ 71 600 700 Universal V4.2E TA Instruments M M M M M 140 5 1 2 3 4 contact angle( ) 120 100 80 60 2 1.6 1.2 0.8 0.4 conc. of Na 2 S2 O 3(M) 0 0.4 0.8 1.2 1.6 conc. of H 2 O2 (M) კ 4.32!਼ϯᗋচᏊ ܭpoly(CMS-co-DVB)ᖓጢޑௗفᡂϯ! (ԜკϐኧᏵܭಃ 100 ।ߕᒵ B) 72 2 M1 ᖓጢ M2 ᖓጢ M3 ᖓጢ M4 ᖓጢ M5 ᖓጢ ! კ 4.33!ѐᚆηН( pH=7 ) ܭpoly(CMS-co-DVB)ᖓጢޑௗ!ف 73 Q1 ᖓጢ Q2 ᖓጢ Q3 ᖓጢ Q4 ᖓጢ Q5 ᖓጢ ! კ 4.34!ѐᚆηН( pH=7 ) ܭq-poly(CMS-co-DVB)ᖓጢޑௗ!ف ! ! ! ! 74 ! ! ! ! ! ! ! 80 contact angle( ) 60 40 20 2 1.6 1.2 0.8 0.4 0 conc. of Na2 S2 O 3(M) 0.4 0.8 1.2 1.6 2 conc. of H 2O 2(M) ! კ 4.35 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ(Q1 ᖓጢ)! (ԜკϐኧᏵܭಃ 101 ।ߕᒵ C) ! ! ! ! ! ! 75 ! ! ! ! ! ! ! ! 80 contact angle( ) 60 40 20 2 1.6 1.2 0.8 0.4 0 conc. of Na 2 S2 O 3(M) 0.4 0.8 1.2 1.6 2 conc. of H 2O 2(M) ! კ 4.36 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ(Q2 ᖓጢ)! (ԜკϐኧᏵܭಃ 101 ।ߕᒵ C) ! ! ! ! ! ! 76 ! ! ! ! ! ! ! ! 80 contact angle( ) 60 40 20 2 1.6 1.2 0.8 0.4 0 conc. of Na 2 S2 O 3(M) 0.4 0.8 1.2 1.6 2 conc. of H 2O 2(M) ! კ 4.37 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ(Q3 ᖓጢ)! (ԜკϐኧᏵܭಃ 101 ।ߕᒵ C) ! ! ! ! ! ! 77 ! ! ! ! ! ! Q1 Q2 Q3 80 contact angle( ) 60 40 20 2 1.6 1 .2 0.8 0.4 conc. of Na 2 S2 O 3(M) 0 0.4 0.8 1.2 1.6 conc. of H 2 O 2 (M) ! კ 4.38 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑௗفᡂϯ! (Q1 ᖓጢ~Q3 ᖓጢ)(ԜკϐኧᏵܭಃ 101 ।ߕᒵ C)! ! ! ! ! 78 2 ! ! ! ! ! Q4 1M H 2 O 2 2M H 2 O 2 0.5M H 2 O 2 H 2 O (pH=7) 0.5M Na 2S 2O 3 1M Na 2S 2O 3 2M Na 2S 2O 3 0.8 h/h0 0.6 0.4 0.2 0 0 1 2 3 tim e(sec) 4 ! ! კ 4.39 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑనᅀଯࡋᡂϯკ)Q4 ᖓጢ*! (h0߄Ңਔ໔ࣁ႟ਔޑనᅀଯࡋ)(ԜკϐኧᏵܭಃ 102 ।ߕᒵD) ! ! 79 ! ! ! ! Q5 1M H 2 O 2 2M H2 O 2 0.5M H 2 O 2 H 2O (pH=7) 0.5M Na 2S2 O 3 1M Na 2S2 O 3 2M Na 2S2 O 3 0.8 h/h0 0.6 0.4 0.2 0 0 1 2 3 4 time(sec) ! ! კ 4.40 ਼ϯᗋচᏊ ܭq-poly(CMS-co-DVB)ᖓጢޑనᅀଯࡋᡂϯკ)Q5 ᖓጢ)! (h0߄Ңਔ໔ࣁ႟ਔޑనᅀଯࡋ)(ԜკϐኧᏵܭಃ 103 ।ߕᒵE) ! 80 ! ! ! ! ! ! 3.5 3 2 t h/h 0 = 0. 2 (sec) 2.5 1.5 1 0.5 2 1.6 1.2 0.8 0.4 conc. of Na 2S 2O 3 (M ) 0 0.4 0.8 1.2 1.6 2 conc. of H 2 O 2 (M) კ 4.41 ਼ϯᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢǴځଯࡋᡂϯࣁh/h0=0.2 ਔ܌ ᐕϐਔ໔(Q4 ᖓጢ)(h0߄Ңਔ໔ࣁ႟ਔޑనᅀଯࡋ) (ԜკϐኧᏵܭಃ 104 ।ߕᒵ F) 81 3.5 3 2 t h/ h0 =0.2 (sec) 2.5 1.5 1 0.5 2 1.6 1.2 0.8 0.4 conc. of Na2 S2 O 3(M) 0 0.4 0.8 1.2 1.6 2 conc. of H 2 O 2(M) კ 4.42 ਼ϯᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢǴځଯࡋᡂϯࣁh/h0=0.2 ਔ܌ ᐕϐਔ໔(Q5 ᖓጢ)(h0߄Ңਔ໔ࣁ႟ਔޑనᅀଯࡋ) (ԜკϐኧᏵܭಃ 104 ।ߕᒵ F) ! ! 82 ! ! ! ! ! ! Q4 Q5 3.5 3 t h/ ho =0.2 (sec) 2.5 2 1.5 1 0.5 2 1.6 1.2 0.8 0.4 conc. of Na 2S 2O 3 (M) 0 0.4 0.8 1.2 1.6 2 co nc. of H 2 O 2 (M) კ 4.43 ਼ϯᗋচᏊܭq-poly(CMS-co-DVB)ᖓጢǴځଯࡋᡂϯࣁh/h0=0.2 ਔ܌ ᐕϐਔ໔(Q4 ᖓጢϷQ5 ᖓጢ)(h0߄Ңਔ໔ࣁ႟ਔޑనᅀଯࡋ) (ԜკϐኧᏵܭಃ 104 ।ߕᒵ F) 83 ! H2O(aq)ܭM3 ᖓጢ ! ! ! 0.1 M glucose(aq)ܭM3 ᖓጢ ! ! !! 0.5 M glucose(aq)ܭM3 ᖓጢ ! ᖓ ! ! 1 M glucose(aq)ܭM3 ᖓጢ !! ! ! კ 4.44 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϐௗف 84 (M3 ᖓጢ) ! H2O(aq)ܭQ3 ᖓጢ !! ! ! 0.1 M glucose(aq)ܭQ3 ᖓጢ!! ! ! 0.5 M glucose(aq)ܭQ3 ᖓጢ !! ᖓ ! ! 1 M glucose(aq)ܭQ3 ᖓጢ !! ! ! კ 4.45 όӕᐚࡋޑဟᑗНྋన ܭq-poly(CMS-co-DVB)ᖓጢϐௗف 85 (Q3 ᖓጢ) ! 140 M1 Q1 120 cont act angle( ) 100 80 60 40 20 0 0.2 0.4 0.6 0.8 conc. of glucose(M) ! კ 4.46 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly! (CMS-co-DVB)ᖓጢϐௗفᡂϯ(M1 ᖓጢϷ Q1 ᖓጢ)! (ԜკϐኧᏵܭಃ 104 ।ߕᒵ G) ! ! ! ! 86 1 ! ! ! ! ! ! ! ! ! 140 M2 Q2 120 contact angle( ) 100 80 60 40 20 0 0.2 0.4 0.6 0.8 conc. of glucose(M) კ 4.47 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly! (CMS-co-DVB)ᖓጢϐௗفᡂϯ(M2 ᖓጢϷ Q2 ᖓጢ)! (ԜკϐኧᏵܭಃ 105 ।ߕᒵ H) 87 1 140 M3 Q3 120 contact angle( ) 100 80 60 40 20 0 0.2 0.4 0.6 0.8 conc. of glucose(M) ! კ 4.48 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly! (CMS-co-DVB)ᖓጢϐௗفᡂϯ(M3 ᖓጢϷ Q3 ᖓጢ)! (ԜკϐኧᏵܭಃ 105 ।ߕᒵ I) ! ! ! ! 88 1 ! ! ! ! ! ! ! M4 Q4 140 120 contact angle( ) 100 80 60 40 20 0 0.2 0.4 0.6 0.8 conc. of glucose(M) კ 4.49 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly! (CMS-co-DVB)ᖓጢϐௗفᡂϯ(M4 ᖓጢϷ Q4 ᖓጢ) (ԜკϐኧᏵܭಃ 106 ।ߕᒵ J) ! 89 1 M5 Q5 140 120 contact angle( ) 100 80 60 40 20 0 0.2 0.4 0.6 0.8 conc. of glucose(M) კ 4.50 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly! (CMS-co-DVB)ᖓጢϐௗفᡂϯ(M5 ᖓጢϷ Q5 ᖓጢ)! (ԜკϐኧᏵܭಃ 106 ।ߕᒵ K) 90 1 M5 M3 M4 M1 M2 Q1 Q2 Q3 Q4 Q5 140 120 contact angle( ) 100 80 60 40 20 0 0.2 0.4 0.6 0.8 conc. of glucose(M) კ 4.51 όӕᐚࡋޑဟᑗНྋన ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-co-DVB)ᖓጢϐௗفᡂϯ (ԜკϐኧᏵܭಃ 104~106 ।ߕᒵ G~K) 91 1 ಃϖക ่ፕ! (1) ᇙഢଯϩηᖓጢਔǴൂᡏکྋᏊޑКٯቹៜ poly(CMS-co-DVB)ᖓጢ߄ޑ य़ࠠᄊϷϾሜ่ᄬǶྋᏊ֖ໆϿਔǴᖓጢ߄य़ᄊࢂѳЪڀԖϾࢰǴᖓ ጢ่ᄬࢂጏஏޑǹྋᏊ֖ໆᡂӭਔǴᖓጢ߄य़ࠠᄊࢂόѳЪڀԖుభǵ ελόޑϾࢰǴᖓጢ่ᄬࢂၨණޑǴឦܭᗭಈ่ᄬǶ! ! (2) ᇙഢଯϩηᖓጢਔǴྋᏊ֖ໆӭჲቹៜ poly(CMS-co-DVB)ᖓጢޑҬᖄ ࡋǶྋᏊ֖ໆຫϿ߾ଯϩηᖓጢҬᖄࡋຫଯǴځှ܌ሡाࡋྕޑ ࢂၨଯޑǶ࣬ჹޑǴྋᏊ֖ໆӭਔ߾ϸϐǶ! ! (3) ճҔڀԖ਼ϯᗋচфૈޑ܄ѭёᎇㄽữࣁׯ፦ᏊǴаϯᏢௗ݄ׯݤ፦ poly(CMS-co-DVB)ᖓጢǴׯ፦ࡕޑq-poly(CMS-co-DVB)ᖓጢӢڀԖᒃН ୷იޑѤભữᡶ(୷ૈ۔C-N+-R3)ԶவচӃޑ౧Н܄፦ᡂࣁᒃН܄ᖓጢǶ! ! (4) ᗋচᏊNa2S2O3ჹq-poly(CMS-co-DVB)ᖓጢޑௗفελϷᅖǴӢᗋ চᏊᐚࡋޑόӕԶԖ܌ቹៜǶեᐚࡋޑᗋচᏊჹܭᖓጢޑௗࢂفၨε ޑǵᅖࢂၨᄌޑǴԶଯᐚࡋޑᗋচᏊჹܭᖓጢޑௗ࣬فჹࢂၨλޑǵ ᅖࢂၨޑזǶচӢࣁᗋচᏊޑᐚࡋቹៜᖓጢଯϩηࢤᗋচޑ ำࡋǴຫӭଯϩηࢤᗋচԶևႝύ܄ਔǴ߾ଯϩη໔൩ຫค௨Ѿ ΚԶϣᕭǴ܌аᗋচᏊܭᖓጢޑௗف൩ຫλǵᅖೲ൩ຫזǶ! ! (5) Ⴃයჹ਼ܭϯᗋচᏊڀԖᒧ܄ǵᡫ௵ޑ܄ଯϩηᖓጢёаวࣁඵችࠠ ٠ᔈҔܭғ܈ނϯᏢགෳᏔǶ! 92 ୖԵЎ [1] M. Mulder, “Basic principles of membrane technology,” 2nd ed., Kluwer Academic Publishers, Boston (1996). [2] R. W. Baker, E. L. Cussler, W. Eykamp, W. J. Koros, R. L. Riley, and H. Strathmann, “Membrane separation systems,” Noyes Data Corporation, Park Ridge, New Jersey (1991). [3] T. H. Young, J. Y. Lai, W. M. You, and L. P. Cheng, “Equilibrium phase behavior of the membrane forming water-DMSO-EVAL copolymer system,” Journal of Membrane Science, Vol.128, pp.55-65 (1997). [4] J. Kiefer, J. L. Hedrick, and J. G. Hilborn, “Macroporous thermosets by chemically induced phase separation,” Advances in Polymer Science, Vol.147, pp.163-247 (1999). [5] A. Della Martina, J. G. Hilborn, A. 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(1993). 98 ߕᒵ! (A) నᅀቹႽϐးϐҢཀკ H D A E C F B G AǺӀྍ BǺё༾ፓѳᆵ CǺᇙഢϐSample DǺ నᅀ EǺDV ቹႽᘏڗ FǺႝတഢ GǺӀᏢѳᆵ HǺ༾ໆݙଞ฿ 99 (B) όӕᐚࡋޑᗋচᏊ(Na2S2O3)ǵ਼ϯᏊ(H2O2)ϷѐᚆηНH2O(pH=7)ჹܭ !!!!poly(CMS-co-DVB)ᖓጢޑௗ(فᇤৡࣁ²1.2±)(ᏹբྕࡋǺ30.5ʚ)! ! poly(CMS-co-DVB)ᖓጢжဦ M1 M2 M3 M4 M5 2M Na2S2O3 90° 89° 95° 88° 118° 1M Na2S2O3 87° 91° 95° 98° 116° 0.5M Na2S2O3 91° 92° 90° 93° 92° 0.1M Na2S2O3 86° 95° 97° 87° 94° 0.05M Na2S2O3 91° 88° 91° 95° 126° H2O (pH=7) 88° 89° 94° 93° 126° 0.05M H2O2 85° 95° 89° 84° 95° 0.1M H2O2 88° 93° 88° 93° 95° 0.5M H2O2 86° 93° 97° 108° 121° 1M H2O2 55° 89° 98° 99° 120° 2M H2O2 89° 89° 95° 96° 94° Ԝ߄ࣁკ 4.32 ϐኧᏵ 100 (C) όӕᐚࡋޑᗋচᏊ(Na2S2O3)ǵ਼ϯᏊ(H2O2)ϷѐᚆηНH2O (pH=7)ჹܭ q-poly(CMS-co-DVB)ᖓጢޑௗ(فᇤৡࣁ²3±)(ᏹբྕࡋǺ30.0ʚ)! ! q-poly(CMS-co-DVB)ᖓጢжဦ Q1 Q2 Q3 2M Na2S2O3 31° 32° 25° 1M Na2S2O3 34° 33° 25° 0.5M Na2S2O3 40° 33° 33° 0.1M Na2S2O3 42° 43° 35° 0.05M Na2S2O3 58° 55° 43° 59° 59° 52° H2O (pH=7) 0.05M H2O2 65° 68° 63° 0.1M H2O2 59° 70° 71° 0.5M H2O2 69° 61° 69° 1M H2O2 70° 71° 60° 2M H2O2 63° 67° 66° Ԝ߄ࣁკ 4.35 ~კ 4.37 ϐኧᏵ 101 (D) όӕᐚࡋޑᗋচᏊ(Na2S2O3)ǵ਼ϯᏊ(H2O2)ϷѐᚆηНH2O (pH=7)ჹܭ q-poly(CMS-co-DVB)ᖓጢޑనᅀଯࡋᡂϯ(Q4 ᖓጢ)(ᏹբྕࡋǺ30.0ʚ)! ! h/ho time(sec) h/ho h/ho h/ho h/ho h/ho h/ho 2M Na2S2O3 1M Na2S2O3 0.5M Na2S2O3 H2O (pH=7) 0.5M H2O2 1M H2O2 2M H2O2 0.3 0.56ʳ 0.64ʳ 0.7ʳ 0.79ʳ 0.8ʳ 0.83ʳ 0.85ʳ 0.6 0.32ʳ 0.55ʳ 0.59ʳ 0.66ʳ 0.77ʳ 0.8ʳ 0.81ʳ 0.9 0.21ʳ 0.43ʳ 0.48ʳ 0.55ʳ 0.75ʳ 0.77ʳ 0.77ʳ 1.2 0.11ʳ 0.33ʳ 0.35ʳ 0.43ʳ 0.69ʳ 0.76ʳ 0.7ʳ 1.5 0.05ʳ 0.2ʳ 0.25ʳ 0.35ʳ 0.6ʳ 0.7ʳ 0.61ʳ 1.8 0.02ʳ 0.11ʳ 0.17ʳ 0.24ʳ 0.53ʳ 0.63ʳ 0.52ʳ 2.1 0ʳ 0.09ʳ 0.1ʳ 0.18ʳ 0.41ʳ 0.54ʳ 0.46ʳ 2.4 0ʳ 0.03ʳ 0.04ʳ 0.1ʳ 0.3ʳ 0.44ʳ 0.39ʳ 2.7 0ʳ 0ʳ 0ʳ 0.04ʳ 0.21ʳ 0.3ʳ 0.29ʳ 3.0 0ʳ 0ʳ 0ʳ 0ʳ 0.13ʳ 0.19ʳ 0.2ʳ 3.3 0ʳ 0ʳ 0ʳ 0ʳ 0.09ʳ 0.09ʳ 0.11ʳ 3.6 0ʳ 0ʳ 0ʳ 0ʳ 0.03ʳ 0.02ʳ 0.02ʳ 3.9 0ʳ 0ʳ 0ʳ 0ʳ 0ʳ 0ʳ 0ʳ Ԝ߄ࣁკ 4.39 ϐኧᏵ (ho߄Ңਔ໔ࣁ႟ਔޑనᅀଯࡋ) 102 (E)!όӕᐚࡋޑᗋচᏊ(Na2S2O3)ǵ਼ϯᏊ(H2O2)ϷѐᚆηНH2O (pH=7)ჹܭ q-poly(CMS-co-DVB)ᖓጢޑనᅀଯࡋᡂϯ(Q5 ᖓጢ)(ᏹբྕࡋǺ30.0ʚ)! ! h/ho time(sec) h/ho h/ho h/ho h/ho h/ho h/ho 2M Na2S2O3 1M Na2S2O3 0.5M Na2S2O3 H2O (pH=7) 0.5M H2O2 1M H2O2 2M H2O2 0.3 0.56ʳ 0.64ʳ 0.7ʳ 0.79ʳ 0.8ʳ 0.83ʳ 0.85ʳ 0.6 0.32ʳ 0.55ʳ 0.59ʳ 0.66ʳ 0.77ʳ 0.8ʳ 0.81ʳ 0.9 0.21ʳ 0.43ʳ 0.48ʳ 0.55ʳ 0.75ʳ 0.77ʳ 0.77ʳ 1.2 0.11ʳ 0.33ʳ 0.35ʳ 0.43ʳ 0.69ʳ 0.76ʳ 0.7ʳ 1.5 0.05ʳ 0.2ʳ 0.25ʳ 0.35ʳ 0.6ʳ 0.7ʳ 0.61ʳ 1.8 0.02ʳ 0.11ʳ 0.17ʳ 0.24ʳ 0.53ʳ 0.63ʳ 0.52ʳ 2.1 0ʳ 0.09ʳ 0.1ʳ 0.18ʳ 0.41ʳ 0.54ʳ 0.46ʳ 2.4 0ʳ 0.03ʳ 0.04ʳ 0.1ʳ 0.3ʳ 0.44ʳ 0.39ʳ 2.7 0ʳ 0ʳ 0ʳ 0.04ʳ 0.21ʳ 0.3ʳ 0.29ʳ 3.0 0ʳ 0ʳ 0ʳ 0ʳ 0.13ʳ 0.19ʳ 0.2ʳ 3.3 0ʳ 0ʳ 0ʳ 0ʳ 0.09ʳ 0.09ʳ 0.11ʳ 3.6 0ʳ 0ʳ 0ʳ 0ʳ 0.03ʳ 0.02ʳ 0.02ʳ 3.9 0ʳ 0ʳ 0ʳ 0ʳ 0ʳ 0ʳ 0ʳ Ԝ߄ࣁკ 4.40 ϐኧᏵ (ho߄Ңਔ໔ࣁ႟ਔޑనᅀଯࡋ) ! 103 (F)!όӕᐚࡋޑᗋচᏊ(Na2S2O3)ǵ਼ϯᏊ(H2O2)ϷѐᚆηНH2O (pH=7)ϐనᅀଯ ࡋᡂϯࣁh/h0=0.2 ਔܭQ4 ϷQ5 ᖓጢ܌ᐕޑਔ໔(ᏹբྕࡋǺ30.0ʚ)! q-poly(CMS-co-DVB)ᖓጢжဦ Q 4 (sec) Q 5 (sec) 2M Na2S2O3 1 0.9 1M Na2S2O3 1.5 1.5 0.5M Na2S2O3 1.7 1.6 H2O (pH=7) 2 2 0.5M H2O2 2.8 2.7 1M H2O2 2.9 3.3 2M H2O2 3 3 Ԝ߄ࣁკ 4.41 Ϸკ 4.42 ϐኧᏵ (G) όӕᐚࡋޑဟᑗНྋనჹ ܭpoly(CMS-co-DVB)ᖓጢ q-poly(CMS-co-DVB) ᖓጢޑௗ(فᇤৡࣁ± 2.2°)(ᏹբྕࡋǺ27.5ʚ)! H2O (pH=7) poly(CMS-co-DVB) ᖓጢжဦ q-poly(CMS-co-DVB) ᖓጢжဦ M1 Q1 90° 56° 0.1M glucose 89° 49° 0.5M glucose 93° 42° 1M glucose 96° 38° Ԝ߄ࣁკ 4.46 ϐኧᏵ 104 (H) όӕᐚࡋޑဟᑗНྋనჹ ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-co-DVB) ᖓጢޑௗ(فᇤৡࣁ± 2.2°)(ᏹբྕࡋǺ27.5ʚ)! H2O (pH=7) poly(CMS-co-DVB) ᖓጢжဦ q-poly(CMS-co-DVB) ᖓጢжဦ M2 Q2 85° 55° 0.1M glucose 87° 47° 0.5M glucose 87° 40° 1M glucose 95° 38° Ԝ߄ࣁკ 4.47 ϐኧᏵ (I)!όӕᐚࡋޑဟᑗНྋనჹ ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-co-DVB) ᖓጢޑௗ(فᇤৡࣁ± 2.6°)(ᏹբྕࡋǺ27.5ʚ)! H2O (pH=7) poly(CMS-co-DVB) ᖓጢжဦ q-poly(CMS-co-DVB) ᖓጢжဦ M3 Q3 91° 53° 0.1M glucose 94° 45° 0.5M glucose 99° 36° 1M glucose 93° 31° Ԝ߄ࣁკ 4.48 ϐኧᏵ 105 (J) όӕᐚࡋޑဟᑗНྋనჹ ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-co-DVB) ᖓጢޑௗ(فᇤৡࣁ± 2.5°)(ᏹբྕࡋǺ27.5ʚ)! H2O (pH=7) poly(CMS-co-DVB) ᖓጢжဦ q-poly(CMS-co-DVB) ᖓጢжဦ M4 Q4 90° 45° 0.1M glucose 91° 33° 0.5M glucose 96° 27° 1M glucose 98° 27° Ԝ߄ࣁკ 4.49 ϐኧᏵ (K)!όӕᐚࡋޑဟᑗНྋనჹ ܭpoly(CMS-co-DVB)ᖓጢϷ q-poly(CMS-co-DVB) ᖓጢޑௗ(فᇤৡࣁ± 2.5°)(ᏹբྕࡋǺ27.5ʚ)! H2O (pH=7) poly(CMS-co-DVB) ᖓጢжဦ q-poly(CMS-co-DVB) ᖓጢжဦ M5 Q5 123° 41° 0.1M glucose 121° 34° 0.5M glucose 134° 27° 1M glucose 134° 28° Ԝ߄ࣁკ 4.50 ϐኧᏵ 106
