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1 Korean Chem. Eng. Res., Vol. 43, No. 6, December, 005, pp Poly(4-vnylphenol)(PVPh)/Ethyl Acetate 및 PVPh/Butyl Acetate 용액계의액 - 액상평형 Ç y o o }e q 9- (005 9o p r, 005 0o 3p }ˆ) Lqud-Lqud Equlbra of Poly(4-vnylphenol)(PVPh)/Ethyl Acetate and PVPh/Butyl Acetate Solutons M Kyung Km and K-Chang Km Department of Chemcal Engneerng, Kangwon Natonal Unversty, 9-, Hyoja- dong, Chunchon 00-70, Korea (Receved September 005; accepted 3 October 005) k l l Poly(4-vnylphenol)(PVPh)/Ethyl Acetate PVPh/Butyl Acetate nk p k-k p TOA(thermal optcal analyss) p r, r p PC-SAFT ˆ rep pn k-k m. e p PVPh/Ethyl Acetate PVPh/Butyl Acetate nk p p nk LCST ˆp p m m qp q p v l kv p mp n p q l p m p n p q p rp PVPh/Ethyl Acetate nkp m PVPh/Butyl Acetate nkp n p m mll p m., PVPh/Ethyl Acetate nkl PVPhm n q p l p FT-IR d p r, r PC-SAFT p Ž m. Ž pn l PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp bnodal curvem spnodal curve mp, bnodal curve e l r m ( m ) curvem l r q p p m. h Abstract Phase separatons of Poly(4-vnylphenol)(PVPh)/Ethyl Acetate and PVPh/Butyl Acetate solutons were measured usng the thermal optcal analyss (TOA) method. The expermental phase separaton data were correlated wth lqud-lqud equlbra relatons based on PC-SAFT equaton of state. The phase separatons of these system showed the behavors of LCST (lower crtcal soluton temperature)-type. The measured cloud temperatures were lowered wth ncreasng n molecular weghts of polymer(pvph), and cloud temperatures of PVPh/Ethyl Acetate solutons shfted to lower temperature regons, compared to the PVPh/Butyl Acetate solutons. Extents of cross-assocaton between solvent molecule and polymer n the PVPh/Ethyl Acetate solutons were measured usng the FT-IR spectrum analyss method, and cross-assocaton parameters of PC-SAFT model were estmated from expermental extents of cross-assocaton. By usng the estmated cross-assocaton parameters between PVPh and solvent molecule, bnodal and spnodal curves of lqud-lqud equlbra n PVPh/Ethyl Acetate and PVPh/Butyl Acetate solutons were calculated from PC-SAFT equaton of state. The calculated bnodal curves of these system were shown to be well agreeable wth the expermental cloud temperature curves. Key words: Poly(4-vnylphenol), Ester, Phase Separatons, PC-SAFT EoS, Cloud Temperature, Cross-Assocaton. qnk q l m m k l p p p q rp nr rl n tne tp p. q l p q p p To whom correspondence should be addressed. E-mal: kchang@kangwon.ac.kr q p qn p p l p p, q l UCST(upper crtcal soluton temperature) LCST(lower crtcal soluton temperature) p p UCSTm LCST p el p nm (closed loop) ˆp p p n p []. q nkl UCST p p m l q (dsperson force)p l p p p, LCST p pp v np, v qm n q p lž} p p 704

2 p l p. n p lž} qp lž} n n m v l n q q Ž} l pl, n m q p p p p n l l p p(negatve)p p l pp l l p l m v l p p k r p []. pm p l p r r p p npp q p, q p qn q p p p ll r l p r p. q p k-k l ll r p ˆ rep kml v rn ˆ rep pn l p l q p ep r m [3]. q p l t n lm ˆ rep qo~(lattceflud)p l p ˆ re[4] Hung Radosz[5] ll r p (TPT)l l rk SAFT ˆ rep pp, qo~p l p ˆ rep p p l o~(assocatng flud)l rn r l [6], SAFT ˆ rep - o~(non-assocatng flud) l rn ˆ rep p p l l s p ˆ rep l [7]. l Grossm Sadowsk[8] SAFT ˆ rel q p p r l PC(perturbedchan)-SAFT ˆ rep pp q q p l p pn p [9-]. ol l LF SAFT p ˆ rep - o~p nl 3 p ˆ re Ž rp o~l q p p Ž l ˆ rep Ž 5., l ˆ q l (cross-assocaton) p pl nl p rp n. pm p o~ l ˆ rep Ž p ˆp r q p n v k p Ž m q (self-assocaton) Ž p p, qp nl p m p el l q Ž p [9]. pm p l Ž p 5 rp Ž l o p r p r p n., q nkl qm n q l p pl n qm n q p Ž, n qm q qp n (combnng rule)l p l rp pp, q n q - (non-self assocatng) qp n ( -k k-k ) p p p pn l. p r p l Ž p p l lp q p l p, FT-IR p pn r d p l p p l l. Wolbachm Sandler[, 3], k m o p l l q p l p l q p l ll r v( H, S o C P )p p SAFT ˆ rep Ž p., o~l p p IR d p PVPh nkp k-k 705 p p n m l k p l lˆ ( H ) l assoc ( S ) e rp lp pp [4], 980 assoc d p p p np FT-IR p n p d p r rp p k vp l [5] q nk q l p p r rp l kl q v pn l m p. l l r p l [6]m p q nkl q m n q p p pl np k-k l ep, k-k p PC-SAFT ˆ rep p n k-k l q m. q r p l [6]l m p q (self-assocatng) qp Poly(4-vnyl phenol)(pvph)p ˆ m n ld (ethyl acetate butyl acetate)p ˆ mp, q nkp e p TOA(thermal optcal analyss) p m., FT-IR d p p PVPhm n p ld p (extents of cross-assocaton) r m. r q m n q p PC-SAFT ˆ rep Ž l PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp k-k l q m.. m n l l Perturbed-Chan SAFT(PC-SAFT) ˆ re[8] p n l q nkp k-k Š q m. PC-SAFT ˆ rel q ~ (hard sphere) p e d(chan) ˆ d q r, d q p qn p k l m p } (repulsve) p (attractve)p l l p l k p p rp m. Z + Z hc + Z dsp + Z assoc p Z hc d q p } l p l p l p p v Z hs mz hs + Z chan op Z hs Z chan p SAFT l m p pp ep. ζ Z hs ζ 3 Z chan x 3 3 3ζ ζ ζ ζ 3 ζ ( ) 3 m ζ 0 ( ζ 3 ) hs ( )( g ) g ρ ζ 0 ζ 3 d q p p l, v (dsperson) l Z dsp d qp q p p p p Barkerm Henderson[7]p l Š l rp k m p [8] n m. hs ρ Korean Chem. Eng. Res., Vol. 43, No. 6, December, 005 () () (3) (4)

3 706 rë } Z dsp Z dsp Z dsp dsp dsp Z + Z ( ) πρ ηi m εσ 3 η ( ) ηi πρm C C ηi m ε σ 3 η o ep I I p p v I I 6 ( η, m) a ( m)η 0 6 ( η, m) b ( m)η 0 (5) (6) (7) (8) (9) Z assoc ρx N G α X A α (9) ρ X A α α + ρ x j j A α X A α N G βj X B βj A α B βj βj B βj (0) p jl sq α β p s (α, β, γ... )l p p,, Aα Bβ p α j p β l sq q (A, B, C... )l p p., op p ql s p sq p p n k m p j p. a ( m ) b ( m ) k m. a b m m a m m m m m ( ) a 0 m ( ) b 0 m b m m m m m b a (0) () (6)e (7)ep m, p p p εσ 3 m ε σ 3 3 σj e m εσ 3 x x j m m j j () kt j 3 σ j e m ε σ 3 x x j m m j j (3) kt j p l p e p Ž σ j ε j p p (Berthelot-Lorentz)l p l rp p. σ j -- ( σ + σ jj ) ε j ε ε jj k j ( ) (4) (5) q p l p k p l z assoc SAFT l p p rp Z assoc ρ x X A (6) ρ A X A oep X A l p q A v kp qp p p p. X A A B j + ρ x hs g j B j e A B j exp kt XB j A B j σ j 3k A B j (7) (8) p o (6~8)ep, p p ql q p ( OH, NH, COOH )p s s p sq p sq n r p [6]l m p ql sq p l p p p. o43 o6 005 k Z assoc ρx N X A G () ρ X A A + ρx N G X A B j () op el l p ql sq ( q p )p N G q(homo polymer)p n qp t q ( M w ) op q p p p r p. N G X B j B j A M w M.W.of repeatng unt (3) l l ()~(5)ep m (8)~(0)ep l p rp ˆ rep pn l q nkp q m. 3. l l q nkp PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp k-k e p mp, q n kl FT-IRp pn l q(pvph)m n q p (extents of cross-assocaton) r e p m. e l np p. 3-. h-h e l PVPh/Ethyl Acetate PVPh/Butyl Acetate nk p k-k pl m ( m, cloud temperature) TOA(thermal optcal analyss) p pn l r m. e l n q PVPh q p 3s p ežn(polyscences, Inc.) p n mp PVPhp q p GPC(Waters, 50 model) l p M w p 6,9, 4,378, 4,67 g/mole pl., n p ethyl acetate butyl acetate 99.9Í p p ek n(aldrch Chem. Co.)p n m. e p qnkp PVPh/Ethyl Acetate nkp n PVPhp pp 0.030~0.50 o m, PVPh/Butyl Acetate nkp 0.09~0.38 o m., e l n e q e p r p [6] p l q np p q.

4 3-. FT-IRl mk mj k m m y ~o e l q nkl qm n q p d (spectroscopc spectrum analyss method)p r o l q nkp FT-IR d p p r m s l ll. e l n q q ( M w )p 6,9p PVPh n m n ethyl acetate ˆ l, PVPh p pp PVPh/Ethyl Acetate nkp d p Š m. PVPh/Ethyl Acetate nkl PVPhl sq p e (-C 6 H 4 -OH) tp -OH m n p ld tp -CO l l p p pl PVPhp p e p -OH l q p el pl. p m p nv qm n q p p nv qp q qrp pl nk l nv qm n q p FT-IR d p r p Walsh [9,0]p l q pp p p l nkl p p 3s (type I, II, III) l Š m. l l p l p type IIp nkl m p, n p ethyl acetatep pr ov ˆl PVPhp v l n q qm v l ˆ, v n p ld tp -COp e p (,738 cm }) p Š l n p r q m. pm p n p FT-IR d p r o n p pr ov lk n pp l l (nert) n rp n l ethyl acetatep C s 5.676[mole/ lter] pr ov PVPhm ethyl acetatep pp nkp rs m. rs nkl PVPhp p( rp r n ˆl )p 0.07~0.35 o m. l p e l n FT-IRp In-stu FT-IR(ASI, React IR TM 000)p, Fg. p e q pn l q nkp FT-IR d p r m. Fg. p e p e p rl rq q(pyrex) r p p 3 cm, p k 8 cm pl. e l k 0 cm p q nkp }n 3 In-stu IRp r probe(atr probe, damond sensor) p q e n l PVPh nkp k-k 707 q l pr m ov m s(jeio Tech., RBC-30)p p e e p q nkp m pr ov m. q nkp m 98.5, 308.5, 38.5 K ov mp FT-IR d p p cm, dƒ 8p s l r m. 4. h-h 4-. PVPh/Ethyl acetate Butyl acetate khm l p e l TOA l p l r PVPh/Ethyl acetate PVPh/Butyl acetate nk p m p p m o l LCST ˆp p m. p LCST ˆp p r p [6]l PVPh/Ketone nkp p LCST ˆp p p nm p, PVPhp p e p -OHm n p ld tp -COmp l p l p p. PVPh/Ethyl Acetate Butyl Acetate nkl q l r m (cloud temperature) Fg. m p e p s l r m n p p m l r m n p p m tp m Trp k 0.76~0.95p mlpl. Fg. l qp q p m p k p. p p qp q p n q mp p v p l n l qp n p r l m p., p q Fg.. Schematc dagram of expermental equpment. Fg.. Cloud temperatures of PVPh/Ethyl Acetate and PVPh/Butyl Acetate solutons. Korean Chem. Eng. Res., Vol. 43, No. 6, December, 005

5 708 rë } p ql n ethyl acetatep n butyl acetatep n m p p p pp p q l qmp p v l m kv p. 4-. FT-IR ŒŠ y k p e 3-l m p p PVPh/Ethyl acetate nk p l FT-IR d p r mp r d p t 3,600-3,00 cm,800~,650 cm op d p Fg. 3. p l p 3,400 cm }p p p PVPhl sq p e tp -OH q l p m p.,,800~,650 cm ol n p ld l p p k,740 cm,70 cm }p p ˆ p p.,740 cm }p p, ethyl acetatep ld tp -COp e p,738 cm ˆ rp k, q nk ˆl qm v kp n q tp -COp p,,70 cm }p p, n qp -CO PVPhp -OHm l p l -COp p r l v y p p, n qp -CO PVPhp -OHm ~(cross-assocaton complex) tp -COp p., PVPhp v n qp v l ~p v Fg. 3l p p PVPhp v l,70 cm p p p (ntensty) v p. Fg. 3p d p PVPh/Ethyl Acetate nkl n p ethyl acetatep (C s mole/lter)p pr ov s l p d p, v kp n p -COp p (monomec p )p,740 cm p p p r ~p -CO p p (hydrogen bonded p )p,70 cm } p p rp n p lp p. FT-IR d l l v po p p t~ n t ~ p l rp l Fg. 4. Spectrum analyss of PVPh/Ethyl Acetate soluton. l Relly [5]p l q pp d p p p rp p lv. n raw d p fourer self-deconvoluton Ž (wave number)l (frst dervatve)p ll t~ p p m p p Ž r l p, p l r rp l p p rp raw d p rp p p (wdth) p r l srp t~ p. l l p k vp n softwarep Curve ft(bo-rad Co.)p pn l Fg. 3 p,800~,650 cm op d p m. Software pn d rl FT-IR d p p Vogt r m, r FT-IR d p p s l p m Fg. 4 l ˆ l. Fg. 4l p t~ d (raw d )p peak peak peak p v kp ld tp -COp p (monomerc peak)l peak PVPhp p e tp -OHm ~ tp -COp p (hydrogen bonded peak)l. p p rp softwarel p l. PVPh/ Ethyl acetate nkl r FT-IR d p om p p l v kp -COp p (monomerc p )p rp llp Fg. 5m. p l m l -COp monomerc p p r(ppp scale e )p qp l rp p mp, qp p s l m v l monomerc p p r p v p ˆ p p k 0.0 p l p m pp 0.0 p p mll p k ƒv p m. Fg. 5m p llv -COp monomerc p p rp p p l p l n p ethyl acetatep ll. Γ A A o A o (4) Fg. 3. FT-IR spectra of PVPh/Ethyl Acetate solutons. o43 o6 005 k p A o n (Ethyl acetate/benzene nk, C s mole/

6 PVPh nkp k-k 709 rp llv pn l PC-SAFT p Ž q m. PVPh/Ethyl acetate nkl PVPh ethyl acetatel sq q k m p A, B C r PC-SAFT p Ž l v Ž p ε B C /k m Ž p k B C, q v kp qp X A, X B X C e ()p p p. Fg. 5. Monomerc peak area of carbonyl group of solvent n PVPh/ Ethyl Acetate solutons. X A ρx N G X B A B + X B ρx N G X A A B ρx N G X C B C + + (5) (6) X C ρx N G X B B C + (7) op (5)~(7)ep X C l 3 rep pp, l p l X C lp p., n p ethyl acetatep Γ p p rp pp Γ n C O n C O ( ) hydrogen ( ) total n C O ( ) total ( n C ) O non hydrogen n C O ( ) total, n q t q C v kp qp p X C k m p v Fg. 6. Extents of cross-assocaton n the PVPh/Ethyl Acetate solutons. lter) ˆl -COp monomerc p p rp, A qnkl v kp ethyl acetate tp -COp p v, monomerc p p rp. pm p ll v n p ethyl acetatep Fg. 6. p l PVPhp l v p mp, qp p s l m v l p m PC-SAFT m y m o k m, k o p p p k~ l q p p FT-IR d p l l enthalpyp entropyp l 950 p l v l [3]. p l l r p l p l H assoc S p assoc mp, l l Fg. 6 p e ( ) non hydrogen X C n C O n C O ( ) total Γ p p. Γ X C (8) k p 4-l Fg. 6 p e rp r Γ exp m op (8)e p PC-SAFT l p l rp Γ cal p pn l k m p r δ s l δ Γ exp Γ cal Γ exp (9) l l v Ž ε BC /km Ž k BC m. Ž rl n PVPhp PC-SAFT ˆ re Ž r p [6]l p n m (Table s), ethyl acetate( butyl acetate)p Ž m p o 0.55<Tr<0.95p s l k~p m v k p [] pn l Table p m., q sq p qp n N G p (3)ep Korean Chem. Eng. Res., Vol. 43, No. 6, December, 005

7 70 rë } Table. Parameters of PC-SAFT equaton of state for pure chemcals Chemcals Parameters ADD( )** m M σ[å] ε/k[k] k AB [ ] ε AB /k[k] V l P s w * Remark Ethyl acetate Ths work Butyl acetate Ths work PVPh T T Prevous work [6] N Q M Molecular weght: for solvent; QQAAD( )d(/n) (X exp X cal )/X exp 00; XV l, P s w Table. Parameters of cross-assocaton between polymer and solvent molecule Systems PC-SAFT Chemcal Theory k BC [ ] ε BC /k[k] Remark H assoc /R[K] Ths work : PVPh/PVAc blend [4] : Phenol/Ethyl Acetate [4] Prevous work [6] 35.5 : Phenol/Acetone [5] rp m n p n N G m. p p p l v Ž ε /km Ž BC k BC p Table m. Table l r p [6]l PVPhm ketone n q p Ž -k p p n l m. p l l p ld n p np l v ketone n p n qp p p pp, Ž ketone n p p p. pm p n l Ž p r p l p l pn l l k. Gupta [] Kontogeorgs [3]p l SAFT r p p - Š l SAFT l p l v Ž ε /k r p l p ABj lˆ ( H /R)m r rp assoc re pp, l pl p q p p l p PVPh/Ethyl Acetate nk o p p p l l l lˆ p q Š m. Moskala [4]p PVPh/PVAc p l PVPhp p e tp -OHm PVAcp l d mp FT-IR p r l r p l p lˆ ( H ) assoc 5. [kcal/mole] p., Pmentel p q [4]l p Phenol/Ethyl Acetate nkl p -OH m ld p l p l ˆ 5.7 [kcal/mole]p, Wdom [5]p Phenol/Acetone nkl FT-IR l p l p -OH m ketonep -CO p l lˆ p 7.0 [kcal/mole] lp p. pm p r q H assoc /R p l Table l r m. Table l PVPh/PVAc p H assoc /R p l l PVPh/Ethyl acetate nkp ε BC /k n p k p., Phenol/Ethyl Acetate nk Phenol/Acetone nkp H assoc /R p q nkp ε BC /k rp l n, Phenol/Ethyl Acetate nkp H /Rp assoc Phenol/Acetone nkp rp p l o43 o6 005 k d tp -COp k q n (proton-acceptng power) p acetonep -CO r l p pp, q nkl p po l l PVPh/Ethyl Acetate nkp ε BC /k p r p [6]l PVPh/ Acetonep rp p. SAFT l l Ž (k ) r p l p l p ABj ( S )m r r pp r rp vr assoc p r kv v lp l l l l v Ž l l mp, m p Š l l l PVPh/Ethyl Acetate nk p Ž l r ˆ p h-h m q nk( k~ )l k-k pl bnodal s l p p s µ ( PTx,, ) µ PTx,, ( ) for, (30) pr k ˆl op s bnodal curve(t-x ' -x ") m ( m ) curve p., k~nkp t kr(metastable) ml kr(unstable) ml p p spnodal s p pp s. µ ( PT,,{ x }) x P, T µ ( PT,,{ x }) x for or (3) p p rl k m p s p s. µ ( PT,,{ x }) µ ( PT,,{ x }) x T, P x T, P for or (3) P, T

8 l l k p p r l m p PC-SAFT ˆ rep rp chemcal potentalp ep pn l op (30)~(3)ep k-k m. k-k p Leem Danner[6]p p n mp, p p (30)ep p bnodal r (3)ep s spnodal r p el p qrp p. l l PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp k-k p p p p v p m. ~ w l PVPhm n p ld q p Ž k p Table m p FT-IR d l p l Ž p n l k-k p m. FT-IR d l p l Ž p PVPh/Ethyl Acetate nkp p m ( m l l) ol r p, p Ž p p m ol pl k-k l rn v p l, n PVPh/Butyl Acetate nkl rn vp l p Š q m. w l Ž v r k-k p s Ž p k-k p m. p p q nkp l Ž l p q lp e rp n p, p l p l Ž p FT-IR d p Ž Š q m. ~ w p rl PVPh ethyl acetatem butyl acetatep PC-SAFT ˆ re Ž Table p p n m, PVPhm n p ld q p Ž ˆ FT- IR d p Table p p n m. pm p p n (30)ep k-k p v (5)ep qn Ž k. k p e 3-l TOA p r Fg. p p s k p mp, k p s l bnodal curve spnodal curve Fg. 7 Fg. 8l e m. Fg. 7p PVPh/ Ethyl Acetate nkp p, bnodal curve PVPh p q ( M w )p 6,9p n r m l l p mp PVPhp q p 4,378 4,67p n r m m l r q p p m., qn Ž k p qp q l v p m., Fg. 8p PVPh/Butyl Acetate nk p k-k p, bnodal curve q p q(pvph) 3s p nk m p e l r q p p m., qn Ž k p k p PVPh/Ethyl Acetate nkl m p q p q l v p m. w l p k-k l, k-k p (30)ep v Ž (ε BC k BC ) m (5)ep qn Ž k 3. rl PVPhp p e p -OHm n p ld p -COm Ž n l p v pp, p n p PVPh nkl PVPhp q l pr p r m. pm p rl p l PVPh nkp k-k 7 Fg. 7. Phase dagram for PVPh/Ethyl Acetate solutons. Fg. 8. Phase dagram for PVPh/Butyl Acetate solutons. k-k p Fg. 9 0l m. Fg. 9 PVPh/Ethyl Acetate nk p p Korean Chem. Eng. Res., Vol. 43, No. 6, December, 005

9 7 rë } Fg. 9. Phase dagram for PVPh/Ethyl Acetate solutons. v p m. bnodal curve PVPhp q p 69p n ~ w p (Fg. 7)m p r p l l p mp q p PVPhp n e p m l r p m., Fg. 0p PVPh/Butyl Acetate nk p p Ž p ε BC /k70.0, κ BC pl qn Ž k PVPhp q l v p mp, bnodal curve q p 3s p PVPh nk e p m p m. p p v p k-k p l, l p bnodal curvep p e p mp p d p p pp w l p l PVPhm n q p Ž p FT-IR d l p l (Table s) rp p p. p rp l Ž p k ε BC /k554.0~70.0 k ~0.0480p ol Ž p BC bnodal curvep l m p n rp p., FT-IR d l p l Ž p w l k-k p pn l p p p, Ž t l v Ž p p(k ε /k66) l v p BC k H assoc 0.33 kcal/molep rp k, FT-IR d p e r m p p e r m l p r p. p p Š l, l l FT-IR d p l p l PC-SAFT ˆ rep Ž v, PVPhp p e p -OHm n p ld p -COm Ž p PVPh/Ethyl Acetate PVPh/ Butyl Acetate nkp k-k l n p, l l r q ll n ethyl acetate butyl acetate pnp ld p n Š v mp ethyl acetate butyl acetate pnp l d p n PVPh/Ester nkp k-k l n pp p. k p k-k rl qn Ž k ((5)ep ) p qp q l v p mp, k l q q ( M w )p ps p Chen [7]p l k m p ep p. w k A + exp( ) ) A ( ) A 3) M (33) Fg. 0. Phase dagram for PVPh/Butyl Acetate soluton. Ž p ε BC 70.0, k BC pl, q n Ž k l p p PVPhp q l o43 o6 005 k l k-k ~ w l p l k (Fg. 7 8) l q q p ps, PVPh/Ethyl Actate nkp n o ep p A () 0.053, A () 0.56, A (3) plp, PVPh/Butyl Acetate nkl p A () 0.045, A () 0.063, A (3) pl., k-k rl (3)ep s p s p m v, LCST p pp (~ w w )l p p m. ~ w l p, PVPh/Ethyl

10 PVPh nkp k-k 73 Acetate nkp nl PVPhp q p 69 n 45. K, 4378p n K, 467p n 43. K pl, PVPh/ Butyl Acetate nkl PVPhp q p 69p n K, 4378p n K, 467p n K plp, PVPh/ Ethyl Acetate nkp p m PVPh/Butyl Acetate nkl l k 7~7 K r p p m. 5. l l q nkl p qm n q p l ep PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp k-k p PC-SAFT ˆ rep pn k-k l k. TOA p r PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp p nk LCST ˆ ˆ lp p LCST ˆp p PVPhm n q p l p p. r m (v m ) qp q p v l mp n p q l p m p n p q p rp PVPh/Ethyl Acetate nkp m PVPh/ Butyl Acetate nkp n p p m. p p n m q p p p n l qp n p r l p p., PVPh/Ethyl Acetate nkl PVPhp p e tp -OH m n p ld tp -CO mp FT-IR d p r mp, r PC- SAFT ˆ rep Ž m. Ž pn l PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp k-k p mp bnodal curve e l r m m l r q p p m. l l FT-IR d l p l PC-SAFT ˆ rep Ž p PVPh/Ethyl Acetate PVPh/Butyl Acetate nkp k-k l n p, n ethyl acetate butyl acetate pnp ld p PVPh/Ester nk l rn p. k AAD(Í) : average of absolute devaton a 0 -a : PC-SAFT unversal dsperson constants b 0 -b : PC-SAFT unversal dsperson constants C : + C : C m 4η 0η ( m) η3 η 48η ( η) 5 [( η) ( η) ] 3 C s : mole concentraton of ethyl acetate n the mxed solvent [mole/lter] d : temperature-dependent segment dameter of chemcal component d σ 0. 3 ε exp kt hs g j 8η η 0η 7η + η 3 η 4 + m ( m ) ( η) 4 [( η) ( η) ] : radal dstrbuton functon for a mxture H k k m m M w N G : enthalpy : Boltzman constant : bnary nteracton parameter used to adjust ε j : number of segments per chan of chemcal component : x m : weght-average molecular weght of polymer : number of functonal group on chemcal component (n CO ) total : total number of ester molecule (n CO ) hydrogen : number of ester molecule hydrogen bonded wth PVPh (n CO ) non-hydrogen : number of ester molecule non-hydrogen bonded R : gas constant S : entropy T : temperature [K] x : mole fracton of chemcal component : weght fracton of polymer X w X A Z m m ρ σ lzm chan dsp hc hs assoc d d jj 3ζ ( ζ 3 ) d + d jj ( ) : fracton of molecules of component not bonded at assocaton ste A : compressblty factor : total number densty of molecules : segment dameter of chemcal component : chan term : dsperson term : hard chan term : hard sphere term : assocaton term ζ 3 g zm, j : chemcal component, j, : polymer, solvent y d d jj + ζ d d jj ( ζ 3 ) 3 Γ : extents of cross-assocaton ε /k : dsperson energy parameter between chans of pure component ε ABj /k : energy parameter of assocaton between ste A on chemcal speces and ste B on chemcal speces j π n ζ n : --ρσx m d n 0,,, 3 6 η : packng fracton ζ 3 k ABj : volume parameter of assocaton between assocaton ste A on chemcal speces and B ste on chemcal speces j µ : chemcal potental of chemcal component. Olabs, O., Robenson, L. M. and Shaw, M. T., Polymer-Polymer Mscblty, Academc Press, New York(979). Korean Chem. Eng. Res., Vol. 43, No. 6, December, 005

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44(3)-16.fm Korean Chem. Eng. Res., Vol. 44, No. 3, June, 2006, pp. 270-276 지능형헬스케어욕조시스템개발을위한온수온도변화 r ~r l o l l e l 561-756 r rte v v 1 664-14 (2006 3o 9p r, 2006 6o 20p }ˆ) Change of the Warm Water emperature for