Shiao-Wei Kuo,* 1 Chih-Feng Huang, 1 Chu-Hua Lu, 1 Ho-May Lin, 1 Kwang-Un Jeong, 2 Feng-Chih Chang 1

Transcription

1 2006 DI: /mp Full Ppr Summry: A sris of PCL--PVPh dilok opolymrs wr prprd throuh omintions of rin-opnin nd tom-trnsfr rdil polymriztions of -prolton nd 4-toxystyrn, nd susqunt sltiv hydrolysis of th tyl prottiv roup. This PCL--PVPh dilok opolymr shows sinl lss trnsition tmprtur ovr th ntir omposition rn, inditin tht this opolymr is l to form misil morphous phs du to th formtion of intrmolulr hydron ondin twn th hydroxyl of PVPh nd th ronyl of PCL. In ddition, DSC nlyss lso inditd tht th PCL--PVPh dilok opolymrs hv hihr lss trnsition tmprturs thn thir orrspondin PCL/PVPh lnds. FT-IR ws usd to study th hydron-ondin intrtion twn th PVPh hydroxyl roup nd th PCL ronyl roup t vrious ompositions. FT-IR sptr in th m 1 for PCL--PVPh opolymrs with vrious PVPh ontnts. Synthss nd Spifi Intrtions of Poly(-prolton)-lok-poly(vinyl phnol) Copolymrs tind vi Comintion of Rin-pnin nd Atom-Trnsfr Rdil Polymriztions Shio-Wi Kuo,* 1 Chih-Fn Hun, 1 Chu-Hu Lu, 1 Ho-My Lin, 1 Kwn-Un Jon, 2 Fn-Chih Chn 1 1 Institut of Applid Chmistry, Ntionl Chio Tun Univrsity, Hsin Chu, Tiwn Fx: þ ; E-mil: kuosw@mil.ntu.du.tw 2 Dprtmnt of Polymr Sin, Th Univrsity of Akron, hio, USA Rivd: My 22, 2006; Rvisd: Auust 25, 2006; Aptd: Auust 28, 2006; DI: /mp Kywords: tom trnsfr rdil polymriztion; lok opolymrs; hydron ondin; rin-opnin polymriztion Mromol. Chm. Phys. 2006, 207, ß 2006 WILEY-VCH Vrl GmH & Co. KGA, Winhim

2 Synthss nd Spifi Intrtions of Poly(-prolton)-lok-poly(vinyl phnol) Copolymrs tind Introdution Th study of nw livin/ontrolld polymriztions hs n on of th most intrstin topis in polymr hmistry for mny yrs. Tody, mny livin systms r known to nompss polymriztion mhnisms suh s nioni, tioni, rdil, rin-opnin nd oordintiv. [1,2] Controlld polymriztions hv providd nw mtrils with pris ontrol ovr th mromolulr prmtrs, in prtiulr, molulr wiht, polydisprsity, rhittur, nd omposition. Amon thm, ontrolld rdil polymriztions hv rivd rt dl of ttntion ovr th lst fw yrs us vrious monomrs, inludin funtionl ons, n rdilly polymrizd. Controlld or livin fr rdil polymriztion hs svrl forms inludin tom-trnsfr rdil polymriztion (ATRP), [3 6] rvrsil ddition-frmnttion hin trnsfr (RAFT), [7] nd nitroxid-mditd polymriztion (NMP), [8 11] whih hv n hvily invstitd to produ polymrs with ontrolld nd oftn novl rhittur. Amon ths ontrolld systms, ATRP is proly th most vrstil providin vrity of djustl options suh s vrid hoi of monomrs, tlysts, solvnts, nd rtion tmprturs. [12 15] Similrly, th livin rin-opnin polymriztion of ltons hs lso rivd intnsiv ttntion ldin to th disovry of diffrnt livin/ontrolld systms. Th dsir to ontrol polymr proprtis throuh th synthss of lok opolymrs nd omplx mromolulr rhitturs is ontinuin thm throuhout polymr hmistry. Misil inry polymr lnds with stron intrtion hv lso ttrtd rt intrst in polymr sin. [16 18] Bsd on th rystllizility of th onstitunts, inry rystllin polymr lnds n torizd into rystllin/ morphous nd rystllin/rystllin systms. [19,20] Crystllin/morphous inry polymr lnds r mor widly studid us of thir simplr rystllin phs rltiv to rystllin/rystllin ons. [21 25] A ommonly mployd omponnt in most rystllin misil lnds is polystr, suh s poly(-prolton) (PCL). PCL is hihly rystllin polymr misil with svrl morphous polymrs throuh spifi intrtions tht wr disussd in Estmond s rviw. [26] In our prvious studis, [27 30] w lso studid th PCL lndin with vrious morphous hydron ond-dontin polymrs, suh s poly(vinyl phnol) (PVPh), phnoli rsin, nd phnoxy rsin. Howvr, to th st of our knowld, th rystllin-morphous dilok opolymr throuh hydron ondin intrtion hs nvr n rportd. PVPh is n intrstin monomr with rin-sustitutd styrn drivtivs tht hs n rportd to form misil lnds with svrl polymrs ontinin ssil protonptor or proton-donor roups, suh s rylt, str, thr, pyridin, nd hydroxyl roups throuh th formtion of hydron ond intrtions. [30 34] Aordin to th litrtur, [35 37] most of th immisil lok opolymrs with slf-rulr morpholois hv primrily mrd from th invstition of dilok opolymrs with mrophs or mirophs sprtion s funtion of omposition, tmprtur, nd intrtion prmtr. Howvr, w intnd to synthsiz th misil poly(prolton)-lok-poly(vinyl phnol) (PCL--PVPh) lok opolymrs y omintion of rin-opnin nd ATRPs to ompr with th orrspondin PCL/PVPh lnds whih r known s misil in th morphous rion du to stron hydron ondin twn th PCL ronyl nd th PVPh hydroxyl roups. [30,38] To th st of our knowld, lok opolymrs of PVPh with iodrdl polymrs PCL hv not n rportd so fr. [39 43] In this ppr, w first om up with strty to omin two dissimilr hmistris in squn to prpr sris of lok opolymrs, poly(-prolton)-lokpoly(4-toxystyrn) (PCL--PAS), nd thn onvrt to PCL--PVPh lok opolymrs throuh s-tlyzd hydrolysis. Th hmil strutur, molulr wiht, vrition of lss trnsition hvior, nd spifi intrtion in ths lok opolymrs r hrtrizd nd invstitd y usin 1 H NMR, l prmtion hromtorphy (GPC), DSC, nd FT-IR sptrosopy nlyss. Exprimntl Prt Mtrils 4-Atoxystyrn (AS) ws purifid y olumn hromtorphy nd th -prolton (-CL) ws distilld from lium hydrid for us. Followin purifition, ll monomrs wr stord in frzr. All solvnts wr distilld prior to us. Trithylmin ws stirrd ovr mnsium sulft nd filtrd prior to us. Coppr(I) romid (CuBr) ws stirrd in lil ti id ovrniht, filtrd, nd thn rinsd with solut thnol undr lnkt of ron nd drid undr vuum t 60 8C ovrniht. Amrlit IR-120 (H form) tion xhn rsin, N,N,N 0,N 00,N 00 -pntmthyldithylntrimin (PMDETA) (99% Aros), nzyl lohol (99% Aros), stnnous otot [Sn(ot) 2 ] (99% Aldrih), 2-romopropionyl romid (99% TCI), nd 4,4 0 -dinonyl-2,2 0 -dipyridyl (dnbipy) wr usd s rivd (97% Aldrih). Produr for Rin-pnin Polymriztion Th polymriztion of -CL ws inititd with nzyl lohol y usin tlyti mount of Sn(ot) 2. Th polymriztion ws rrid out in th mlt t 120 8C (20 h). Th polymr ws thn dissolvd in ttrhydrofurn (THF) nd pripittd from old mthnol nd purifid y rptin its pripittion thr tims from MH. Th rsultin polymr ws filtrd nd drid ovrniht t 40 8C undr vuum to otin whit powdr. Prprtion of Mroinititor Undr ron, 2-romoisoutyryl romid (5.37 ml, 43.4 mmol) ws ddd dropwis to stirrin mixtur of PCL-H

3 2008 S.-W. Kuo, C.-F. Hun, C.-H. Lu, H.-M. Lin, K.-U. Jon, F.-C. Chn H ε -CL, Bulk 120 C, Sn(ot) 2 H m PCL-H TEA/Tolun 0 C, BPB m Br PCL-Br CuBr/PMDETA,110 C Atoxystyrn, Bulk m n PCL--PAS RT, dioxn, N 2 H 4 Sltiv hydrolysis m n PCL--PVPh H Shm 1. Th synthti routs of PCL--PVPh y omintions of rin-opnin nd tom trnsfr rdil polymriztions. (17.3 mmol) nd trithylmin (6.02 ml, 42.8 mmol) in 50 ml of tolun in n i th for 1 h. Aftr omplt ddition of th id romid, th rtion ws stirrd t room tmprtur for 24 h. Th rtion mixtur ws wshd with wtr (3 150 ml) nd thn drid with MS 4. Aftr filtrtion, th mixtur ws pripittd with tn-fold mthnol for purifition. Th rsultin polymr ws filtrd nd drid ovrniht t 40 8C undr vuum to otin whit powdr. Gnrl Produr for Synthsis of PCL--PAS Blok Copolymrs Blok opolymrs r sily prprd y ATRP of AS nd PCL-Br in th prsn of CuBr/PMDETA s tlyst systm. In typil xprimnt, 100-mL round-ottom flsk ws hrd with pproprit mounts of CuBr, mroinititor. 2 ws rmovd y rptd vuum-nitron yls. Tl 1. Summry of th rin-opnin polymriztion of PCL-H. Smpls CL ) BA ) Yild M n;th ) M n;gpc % M n;nmr PDI PCL PCL PCL PCL ) CL: -prolton, BA: nzyl lohol. ) Rf. [58] : M PCL ¼ M 1:073 PS.

4 Synthss nd Spifi Intrtions of Poly(-prolton)-lok-poly(vinyl phnol) Copolymrs tind d f x Br i d+f (B) PCL-Br i d f x-1 d f h H d+f (A) PCL-H h Chmil Shift (ppm) Fiur 1. 1 H NMR sptr of (A) PCL-H nd (B) PCL-Br. n filld with N 2, doxyntd toxystyrn nd lind wr ddd nd th solution ws stirrd for 30 min t room tmprtur to promot th formtion of th Cu omplx. All prosss wr undrtkn in N 2 -filld dry ox. Th polymriztion ws thn prformd in n oil th t n pproprit tmprtur. Th rtion mixtur immditly m drkrn nd mor visous s it prorssd. Aftr spifi tim, th mixtur ws oold nd dilutd with fiv-fold THF nd stirrd with Amrlit IR-120 (H form) tion-xhn rsin (3 5 ) for min to rmov th tlyst. Th mixtur ws thn pssd throuh n lumin olumn nd pripittd into MH. Th produt ws dissolvd in THF nd purifid y thr tims rptd pripittions from MH nd thr. Th rsultin PCL--PAS lok opolymr ws filtrd nd drid ovrniht t 50 8C undr vuum to otin whit powdr. PCL--PVPh ws prprd from th sltiv hydrolysis of th PCL--PAS. Rmovl of th tyl prottin roups from th AS polymrs ws rrid out in 1,4-dioxn y trtin it with hydrzin hydrt t room tmprtur. Typilly, lok opolymr PCL--PAS (7.2 mmol of AS) ws ddd in flsk nd soluilizd with 1,4-dioxn (30 ml). Thn, hydrzin hydrt (3 ml) ws ddd vi syrin nd th rtio of hydrzin hydrt to 1,4-dioxn ws 1:9 y volum. Th rtion ws llowd to prod t room tmprtur undr nitron for pproximtly 10 h. Th solution ws onntrtd y vportion of th solvnt nd wshd with dion- Intnsity (.u.) PCL52--PAS48 M n =15000 /mol PDI = 1.48 pur PCL M n =9400 /mol PDI = 1.19 Sltiv Hydrolysis Elution Volum (ml) Fiur 2. GPC trs of PCL-H nd PCL--PAS opolymr.

5 2010 S.-W. Kuo, C.-F. Hun, C.-H. Lu, H.-M. Lin, K.-U. Jon, F.-C. Chn izd wtr svrl tims, followd y dryin in vuum ovn t room tmprtur for 2 d. Msurmnts 1 H NMR nd 13 C NMR sptr wr rordd in CDCl 3 on Brukr AM 500 (500 MHz) sptromtr nd th solvnt sinl ws usd s n intrnl stndrd. Molulr wihts nd molulr wiht distriutions wr dtrmind y siz xlusion hromtorphy (SEC) usin Wtrs 510 HPLC quippd with 410 Diffrntil Rfrtomtr, UV dttor, nd thr Ultrstyrl olumns (100, 500, nd 10 3 Å) onntd in sris. Th THF ws usd s n lunt t flow rt of 0.4 ml min 1. Th molulr wiht lirtion urv ws otind usin polystyrn stndrds. FT-IR msurmnt ws md usin Niolt Avtr 320 FT-IR Sptromtr, 32 sns t rsolution of 1 m 1 wr olltd with NCl disk. Th THF solution-ontinin th smpl ws st onto NCl disk nd thn drid t 50 8C. Th smpl hmr ws purd with nitron in ordr to mintin th film drynss. Thrml nlysis ws rrid out on DSC instrumnt from DuPont (modl 910 DSC-9000 ontrollr) with sn rt of 20 8C min 1 nd tmprtur rn of C in nitron tmosphr. Approximtly 5 10 m of smpl ws wihd nd sld in n luminum pn. Th smpl ws thn quikly oold to room tmprtur from th first sn nd thn snnd twn 100 nd 200 8C t sn rt of 20 8C min 1. Th lss trnsition tmprtur is tkn s th midpoint of th ht pity trnsition twn th uppr nd lowr points of dvition from th xtrpoltd lss nd liquid lins. Rsults nd Disussion Synthss of PCL-Bsd Blok Copolymrs Th strty for th synthsis of PCL sd lok opolymrs ws modifid from Mtyjszwski [41] nd is outlind in Shm 1. Th rin-opnin polymriztion of -CL, inititd y nzyl lohol usin Sn(ot) 2 s tlyst, produd PCL ontinin on hydroxyl hin nd. d f m h i Br n d+f+i o +h () PCL--PVPh p H p o d f m h i n Br j k d+f+i +h () PCL--PAS j k Chmil Shift (ppm) Fiur 3. 1 H NMR sptr () for hydrolysis, PCL--PAS, nd () ftr hydrolysis, PCL--PVPh.

6 Synthss nd Spifi Intrtions of Poly(-prolton)-lok-poly(vinyl phnol) Copolymrs tind PCL-PVPh PCL-PAS pur PCL () PCL61--PVPh Wvnumr () PCL52--PAS48 () pur PCL Wvnumr (m -1 ) Fiur 4. IR sptr of () pur PCL, () PCL--PAS, nd () PCL--PVPh t room tmprtur rnin from 600 to m 1. Th rin-opnin polymriztion of -CL is summrizd in Tl 1, inditin th low polydisprsity (<1.2) of this sris of PCL-H homopolymrs. Th hydroxyl hin nd ws modifid to form n -hlostr, PCL-Br, n fftiv inititor for ATRP. Th mroinititor PCL-Br ws thn mployd s th inititin spis for th ATRP of AS in th prsn of CuBr/PMDETA omplx to produ PCL--PAS dilok opolymrs. Evntully, PCL--PAS dilok opolymrs wr onvrtd into PCL--PVPh dilok opolymrs y sltiv hydrolyss. Aordin to th litrtur, [44 46] numr of mthods hv n mployd to onvrt th AS polymr into th orrspondin polymr ontinin phnoli roup. It is diffiult to prod with th hydrolysis of PAS to PVPh in th prsn Tl 2. Chrtriztions of PCL--X (X ¼ PAS or PVPh) opolymrs prprd y rin-opnin nd tom trnsfr rdil polymriztions. Copolymr ) M n;pcl ) M n;x ) Totl M n ) Totl M n X ) ) M w =M n PCL48--PAS PCL52--PAS PCL58--PAS PCL77--PAS PCL57--PVPh PCL61--PVPh PCL67--PVPh PCL83--PVPh ) tind from 1 H NMR msurmnt. ) tind from GPC nlysis. wt.-%

7 2012 S.-W. Kuo, C.-F. Hun, C.-H. Lu, H.-M. Lin, K.-U. Jon, F.-C. Chn of PCL du to its unstl hvior inst hydrolysis onditions. To ddrss this prolm, sltiv hydrolysis twn PAS nd PCL is nssry to produ dsirl dilok opolymr y rtin with hydrzin hydrt. An optiml hydrolysis ondition ws hosn to onvrt th PCL--PAS into PCL--PVPh dilok opolymrs (s Exprimntl Prt). Fiur 1 illustrts 1 H NMR of PCL-H homopolymr nd PCL-Br mroinititor, showin th mthyl roup (i hydron) of th 2-romopropionyl romid unit in th PCL-Br. This rsult indits tht th PCL-Br mroinititor ws indd synthsizd sussfully. Th GPC tr of th PCL--PAS lok opolymr ws otind ftr ATRP s shown in Fiur 2. Blok opolymrs prprd from th PCL mroinititor rsultd in produts with nrrow polydisprsity nd hih symmtry, with monomodl GPC trs. Th sn of th PCL mroinititor pk supports th formtion of PCL--PAS dilok opolymrs. Complt limintion of th prottiv roups nd th nrtion of th phnoli hydroxyl roups wr dmonstrtd y 1 H NMR sptrosopy. Fiur 3 shows typil 1 H NMR sptr of th dilok opolymr rordd for (ottom) nd ftr (top) dprottion. A hmil shift t 2.2 ppm orrsponds to th tyl roup of th PCL--PAS opolymr (in DMS-d 6 ). Ths pks orrspondin to th tyl roup dispprd ssntilly from th sptrum of th hydrolyzd lok opolymr, nd only th polymr kon protons ppr in th hmil shift rion of 1 2 ppm. In ddition, pk (8.0 ppm) orrspondin to th proton of th hydroxyl roup pprs ftr hydrolysis rtion. Althouh this dilok opolymr systm hs not n invstitd prviously, ATRP of th prottd 4-vinyl phnol monomr [47 49] nd th rin-opnin polymriztion of prolton monomr [50] hv n doumntd. To otin PVPh lok, it is nssry to prott th hydroxyl roup prior to polymriztion to void th trmintion of th livin hin nd. Vrious prottin roups, inludin tyl, [47] trt-utyl thr, [51] nd trtutyldimthylsilyl [52] roups, hv n usd for hydroxyl roup prottion durin polymriztion. As mntiond ov, th tyl roup ws dlirtly hosn s prottiv roup in this study us it ws xptd to mor sltiv nd rdily rmovd from th prnt opolymr without hydrolyzin th str roups. [53] Th FT-IR sptr of pur PCL, PCL--PAS, nd PCL--PVPh r shown in Fiur 4. Th hrtristi ronyl strthin of th PCL--PAS is split into two nds, du to sorption y PCL nd PAS t nd m 1, rsptivly. Th sorption t m 1 pur PVPh PCL57--PVPh43 Ht Flow (Endo, ) PCL61--PVPh39 PCL67--PVPh33 PCL83--PVPh17 pur PCL PCL 67--PVPh 33 PCL83- -PVPh17 pur PCL Tmprtur ( o C) Tmprtur ( o C) Fiur 5. DSC trs of PCL--PVPh opolymrs with vrious PVPh ontnts.

8 Synthss nd Spifi Intrtions of Poly(-prolton)-lok-poly(vinyl phnol) Copolymrs tind orrspondin to th tyl roup of th PCL--PAS dispprd ssntilly nd it shiftd to m 1 orrspondin to th hydron ondd ronyl roup twn th ronyl roup of PCL nd th hydroxyl roup of PVPh ftr hydrolysis. Th rod pk t m 1 in Fiur 4() lso indits th prsn of th hydroxyl roups. Th molulr wiht frtion of th PCL--PVPh lok opolymr ws msurd y 1 H NMR sptrosopy nd GPC, y nlyzin th rltiv sinl intnsitis of th protons of th PCL nd PVPh smnts. Th lultion ws prformd y omprin th sinls of th romti protons of th PVPh smnt ( ppm) nd th sinl of th mthyln roups of th PCL smnt (3.6 ppm). Tl 2 lists ths lultd molulr wiht frtions nd th totl molulr wihts dtrmind y GPC; th numr n sid th dsriptor PCL--PAS nd PCL--PVPh rflts th molulr wiht prnt. Tl 1 nd 2 dmonstrt ommon prolm in GPC msurmnt du to th us of PS s th stndrd, whih hs dissimilr solution hvior in th rsultin polymrs (hr, PCL nd PCL-sd lok opolymrs). W liv tht thr is systmti dvition in msurin th vlus of M n nd M w in our GPC systm, whrs th polydisprsity vlus providd us rltiv molulr wiht distriution t th st of mroinititor nd lok opolymr prprtions. Ltr, our quntittiv rprsnttion of hin lnth ws sd on th 1 H NMR msurmnts for th rsultin polymrs. Thrml Anlyss Fiur 5 shows DSC thrmorms for PVPh, PCL, nd PCL--PVPh opolymrs, inditin tht th T of th pur PVPh is 120 8C (M n ¼ mol 1 ), nd th mltin tmprtur of th pur PCL is 60 8C. Th T of PVPh shifts to lowr tmprtur s th PCL ontnt in th dilok opolymr is inrsd. Mnwhil, th mltin tmprtur of th PCL omponnt in th opolymr drsd with inrs in th PVPh ontnt. A mltin dprssion is hrtristi of th misil dilok opolymr in th mltin stt. Althouh th immisil dilok opolymr lso hs similr phnomn, [54] w liv tht this is hrtristi of misil dilok opolymrs sin ll PCL--PVPh opolymrs show only on sinl lss trnsition tmprtur (T ) with n ovrll lnd omposition. A sinl T stronly susts tht ths two omponnts r fully misil dilok opolymrs in th morphous phs. Th dpndn of T on th omposition of th misil PCL--PVPh is shown in Fiur 6. vr th yrs, numr of qutions hv n proposd to prdit th vrition of th lss trnsition tmprtur Kwi qution: K=1, q=0 nd Linr Rul for PCL-PVPh Dilok Copolymr T ( o C) Asorn (.u.) pur PVPh PCL57--PVPh43 PCL61--PVPh Kwi qution: K=1, q=-85 sd on PCL/PVPh Blnd Systm PCL67--PVPh33 PCL83--PVPh PVPh Wiht Frtion Fiur 6. Plots of T vrsus omposition sd on (&) xprimntl dt nd Kwi qution Wvnumr (m -1 ) Fiur 7. FT-IR sptr in th m 1 rion for PCL--PVPh opolymrs with vrious PVPh ontnts.

9 2014 S.-W. Kuo, C.-F. Hun, C.-H. Lu, H.-M. Lin, K.-U. Jon, F.-C. Chn of misil lnd s funtion of omposition. Th most populr qution is th Kwi qution: [55] T ¼ W 1T 1 þ kw 2 T 2 W 1 þ kw 2 þ qw 1 W 2 (1) whr W 1 nd W 2 r omponnt wiht frtions of th opolymr, T 1 nd T 2 rprsnt th orrspondin lss trnsition tmprturs, nd k nd q r fittin onstnts. Th prmtr q orrsponds to th strnth of th spifi intrtion in opolymr or polymr lnd. Th Kwi qution n pply to polymr lnds with spifi intrtion, suh s hydron ondin in polymr lnd, nd opolymr systm. In this study, w us th Kwi qution from inry lnd in ordr to prdit th misil dilok opolymr. k ¼ 1 nd q ¼ 0 r otind from th nonlinr lst squrs st fit vlus, whih is similr to th linr rul. Comprd with th prvious PCL/PVPh lnd (k ¼ 1, q ¼ 85), th diffrn in q osrvd twn th two systms n intrprtd s it indits tht th strnth of th spifi intrtions within th PCL-- PVPh dilok opolymrs is rtr thn th orrspondin PCL/PVPh lnds, whih is onsistnt with our prvious studis. [33,56] diffrn (Dn) twn th hydron ondin hydroxyl sorption nd fr hydroxyl sorption. [57] This osrvtion rvls tht th vr strnth of th hydron ond twn th PVPh hydroxyl nd th PCL ronyl in th lnd systm (Dn ¼ 95 m 1 ) is wkr thn tht of th slf-ssoitd hydroxyl of th PVPh (Dn ¼ 175 m 1 ), whih is rsponsil for th osrvd ntiv q vlu in th Kwi qution in this lnd systm. Howvr, in PCL--PVPh dilok opolymr systm, Dn m 1 twn th hydroxyl nd ronyl roups is los to th hydroxyl-hydroxyl, nd thus rsults in q ¼ 0in th Kwi qution. Fiur 8 shows th infrrd sptr of th ronyl strthin t room tmprtur rnin from to m 1 for PCL--PVPh opolymrs. Th ronyl strthin for th pur PCL is split into two nds, sorption y morphous nd rystllin onformtions t nd m 1, rsptivly. Anothr ontriution t pproximtly m 1 is ssind to th PCL ronyl roup, nd hydron ondd to th PVPh hydroxyl roup. Ths sorptions n wll fittd in th Gussin funtion s shown in Fiur 8. Th frtion of th hydron ondd ronyl roup of PCL n FT-IR Anlyss Infrrd sptrosopy hs provn to powrful tool for invstitin spifi intrtions twn polymrs nd th mhnism of intrpolymr misiility throuh th formtion of hydron onds oth qulittivly nd quntittivly. Svrl rions within th infrrd sptr of PCL--PVPh opolymrs r inflund y hydron-ondin intrtion. Fiur 7 shows th infrrd sptr in th m 1 of pur PVPh, nd vrious PCL--PVPh opolymrs msurd t room tmprtur. Th pur PVPh polymr is omposd of two omponnts in this sptrum; vry rod nd ntrd t m 1 is ttriutd to th wid distriution of th hydron ondd hydroxyl roups, whil rltivly nrrow nd t m 1 is usd y th fr hydroxyl roup. Fiur 7 indits tht th intnsity of fr hydroxyl roup (3 525 m 1 ) drss rdully with th inrs in PCL ontnt. Howvr, th rod hydron ondd hydroxyl nd of th PVPh dos not shift sinifintly t round to m 1. Comprd with th PCL/PVPh lnd systm, [30] th rod hydron ondd hydroxyl nd of th PCL--PVPh shifts into hihr frquny rion with inrsin PCL ontnt t m 1. This shift is du to th swith from th hydroxyl-hydroxyl ond to th hydroxylronyl ond, inditin th xistn of n hydron ondin intrtion twn th PCL ronyl roup nd th hydroxyl roup of PVPh. Th vr strnth of th intrmolulr intrtion n otind y th frquny Asorn (.u.) PCL57--PVPh43 PCL61--PVPh39 PCL67--PVPh33 PCL83--PVPh17 pur PCL Wvnumr (m -1 ) Fiur 8. FT-IR sptr in th m 1 for PCL--PVPh opolymrs with vrious PVPh ontnts.

10 Synthss nd Spifi Intrtions of Poly(-prolton)-lok-poly(vinyl phnol) Copolymrs tind Tl 3. Curv fittin rsults of th PCL--PVPh lok opolymr t room tmprtur [n: wvnumr (m 1 ), W 1/2 : hlf-width (m 1 ), A f : r frtion, f : frtion of hydron ondd ronyl roup]. Copolymrs Amorphous C Crystllin C H-ondd C f n W 1/2 A f n W 1/2 A n W 1/2 A m 1 % m 1 % m 1 % Pur PCL PCL83--PVPh PCL67--PVPh PCL61--PVPh PCL57--PVPh lultd y usin n pproprit sorptivity rtio ( R ¼ HB / F ¼ 1.5) whih hs n disussd in our prvious study. [27] Th rsults from urv fittin r summrizd in Tl 3, inditin tht th hydron ondd frtion of th ronyl roup inrss with th PVPh ontnt. In ddition, th rystllinity of PCL drss with th inrs in th PVPh ontnt. It is onsistnt with th DSC nlyss tht th rystllinity dispprd for PVPh t 39 wt.-% in PCL--PVPh opolymr s shown in Fiur 5. Conlusion 1 H NMR, FT-IR sptrosopy, nd GPC nlyss iv vidn tht th PCL--PVPh dilok opolymrs prprd sussfully throuh omintion of rinopnin nd tom trnsfr rdil polymriztions. DSC rsults show tht th PCL--PVPh dilok opolymr hs sinl lss trnsition tmprtur ovr th ntir omposition rn, nd lso hs hihr lss trnsition tmprturs omprd to th orrspondin PCL/PVPh lnds. FT-IR nlysis onfirms th hydron-ondin intrtion twn th PVPh hydroxyl roup nd th PCL ronyl roup. Th rystlliztion nd mirostrutur hvior of this misil dilok opolymr will studid in th nr futur. Aknowldmnts: This rsrh ws finnilly supportd y th Ntionl Sin Counil, Tiwn, Rpuli of Chin, undr ontrt no. NSC E , nd th Ministry of Edution Aim for th Top Univrsity prorm (MEATU prorm). [1] M. Szwr, M. Lvy, R. Milkovih, J. Am. Chm. So. 1956, 78, [2]. W. Wstr, Sin 1991, 251, 887. [3] J. S. Wn, K. Mtyjszwski, Mromoluls 1995, 28, [4] D. M. Hddlton, M. C. Crossmn, B. H. Dn, D. J. Dunlf, A. M. Hmin, D. Kukulj, A. J. Shootr, Mromoluls 1999, 32, [5] K. Mtyjszwski, J. Xi, Chm. Rv. 2001, 101, [6] M. Kmiito, T. Ando, M. Swmoto, Chm. Rv. 2001, 101, [7] E. Rizzrdo, J. Chifri, B. Y. K. Chon, F. Erol, J. Krstin, J. Jffry, T. P. T. L, R. T. A. Mydunn, G. F. Mijs, C. L. Mod, G. Mod, S. H. Thn, Mromol. Symp. 1999, 143, 291. [8] M. K. Gors, R. P. N. Vrin, P. M. Kzmir, G. K. Hmr, Mromoluls 1993, 26, [9] P. Lroix-Dsmzs, J. Lutz, F. Chuvin, R. Svr, B. Boutvin, Mromoluls 2001, 34, [10] K. hno, Y. Tsujii, T. Miymoto, T. Fukud, M. Goto, K. Koyshi, T. Akik, Mromoluls 1998, 31, [11] C. J. Hwkr, A. W. Bosmn, E. Hrth, Chm. Rv. 2001, 101, [12] C. J. Hwkr, J. Am. Chm. So. 1994, 116, [13] J. Lutz, D. Nuur, K. Mtyjszwski, J. Am. Chm. So. 2003, 125, [14] J. Pyun, K. Mtyjszwski, Chm. Mtr. 2001, 13, [15] K. Mtyjszwski, Pro. Polym. Si. 2005, 30, 858. [16] S. W. Kuo, F. C. Chn, Mromoluls 2001, 34, [17] M. Vivs, J. M. J. Frht, Polymr 1988, 29, 477. [18] S. W. Kuo, C. L. Lin, F. C. Chn, Polymr 2002, 43, [19] H. L. Chn, S. F. Wn, T. L. Lin, Mromoluls 1998, 31, [20] B. B. Sur, B. S. Hsio, J. Polym. Si., Polym. Phys. Ed. 1993, 31, 901. [21] S. Tliuddin, J. Runt, L. Z. Liu, B. Chu, Mromoluls 1998, 31, [22] J. P. Pnnin, R. S. J. Mnly, Mromoluls 1996, 29, 77. [23] T. P. Russll, R. S. Stin, J. Polym. Si., Polym. Phys. Ed. 1982, 20, [24] P. Sdoo, M. Cntti, A. Svs, E. Mrtuslli, Polymr 1993, 34, [25] G. Dfiuw, G. Groninkx, H. Rynrs, Polymr 1989, 30, 595. [26] G. C. Estmond, Adv. Polym. Si. 1999, 149, 223. [27] S. W. Kuo, S. C. Chn, F. C. Chn, Mromoluls 2003, 36, [28] S. W. Kuo, S. C. Chn, H. D. Wu, F. C. Chn, Mromoluls 2005, 38, [29] S. W. Kuo, S. C. Chn, F. C. Chn, J. Polym. Si., Polym. Phys. Ed. 2004, 42, 117. [30] S. W. Kuo, C. F. Hun, F. C. Chn, J. Polym. Si., Polym. Phys. Ed. 2001, 39, [31] C. L. Lin, W. C. Chn, S. W. Kuo, F. C. Chn, Polymr 2006, 47, [32] S. W. Kuo, W. P. Liu, F. C. Chn, Mromol. Chm. Phys. 2005, 206, 2307.

11 2016 S.-W. Kuo, C.-F. Hun, C.-H. Lu, H.-M. Lin, K.-U. Jon, F.-C. Chn [33] C. L. Lin, W. C. Chn, C. S. Lio, Y. C. Su, C. F. Hun, S. W. Kuo, F. C. Chn, Mromoluls 2005, 38, [34] J. Wn, M. K. Chun, Y. Mi, Polymr 2001, 42, [35] E. L. Thoms, D. M. Andrson, C. S. Hnk, D. Hoffmn, Ntur 1988, 334, 598. [36] F. S. Bts, G. H. Frdrikson, Annu. Rv. Phys. Chm. 1990, 41, 525. [37] F. S. Bts, Sin 1991, 251, 898. [38] J. Wn, M. K. Chun, Y. Mi, Polymr 2002, 43, [39] T. Erdon, Z. zyurk, G. Hizl, U. Tun, J. Polym. Si., Polym. Chm. Ed. 2004, 42, [40] U. Tun, Z. zyurk, T. Erdon, G. Hizl, J. Polym. Si., Polym. Chm. Ed. 2004, 42, [41] W. Jkuowski, J. Lutz, S. Slomkowski, K. Mtyjszwski, J. Polym. Si., Polym. Chm. Ed. 2005, 43, [42] I. Ydns, P. Dé, P. Duois, J. Liiszowski, A. Dud, S. Pnzk, Mromol. Chm. Phys. 2003, 204, 171. [43] L. To, B. Lun, C. Pn, Polymr 2003, 44, [44] S. W. Kuo, F. C. Chn, Mromoluls 2001, 34, [45] S. W. Kuo, H. Xu, C. F. Hun, F. C. Chn, J. Polym. Si., Polym. Phys. Ed. 2002, 40, [46] S. W. Kuo, W. P. Liu, F. C. Chn, Mromoluls 2003, 36, [47] K. Jnkov, J. Kops, X. Chn, W. Btsr, Mromol. Rpid Commun. 1999, 20, 219. [48] B. D. Edom, J. A. Stin, J. M. J. Frht, Z. Xu, E. J. Krmr, Mromoluls 1998, 31, [49] B. Go, X. Chn, B. Ivn, J. Kops, W. Btsr, Mromol. Rpid Commun. 1997, 18, [50] C. F. Hun, S. W. Kuo, H. S. L, F. C. Chn, Polymr 2005, 46, [51] J. Q. Zho, E. M. Pr, T. K. Kwi, H. S. Jon, P. K. Ksni, N. P. Blsr, Mromoluls 1995, 28, [52] K. S, K. Miywki, K. Hirhr, A. Tkno, T. Fujimoto, J. Polym. Si., Polym. Chm. Ed. 1998, 36, [53] X. Y. Chn, B. Ivn, J. Kops, W. Btsr, Mromol. Rpid Commun. 1998, 19, 585. [54] T. S. Chow, Mromoluls 1990, 23, 333. [55] T. K. Kwi, J. Polym. Si., Polym. Ltt. Ed. 1984, 22, 307. [56] S. W. Kuo, C. F. Hun, P. H. Tun, W. J. Hun, J. M. Hun, F. C. Chn, Polymr 2005, 46, [57] E. J. Moskl, D. F. Vrnll, M. M. Colmn, Polymr 1985, 26, 228. [58] P. Duois, I. Brkt, R. Jrom, P. Tyssi, Mromoluls 1993, 26, 4407.