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®êÆ zÊ Þ:.

N FÂ&rê ÊF ŽrÒ OK®† Z®B, 1,4-butanediol(BD), 1,6-hexanediol(HD), 1,4-cyclohexanediol(CHD), Bê 1,4-cyclohexane- dimethanol(CHDM)R o– ÊVû‡ r2r² V²2Ò r®

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Wdh0Jrq#Ndqj#dqg#\dqj0N|rr#Kdq^%# Department of Chemistry, Hanyang University, Seoul 133-791, Korea Korea Center for Advanced Functional Polymers, KAIST, Daejeon 305-701, Korea

(Received March 22, 2005;accepted May 9, 2005)

5¨Ü _:Î stannous octoate Ê ®&r V²2Ò ÊVû‡ r2rÎ 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexane- diol, 1,4-cyclohexanedimethanol

succinic acid, adipic acid, – suberic acid– titanium(IV) isopropoxide _:®&r 170, 190, Bê 220 ×&r ë¿g¿

2r ÚæÂÆV 2¯W’² †Jr ² Ç J&ú¢Ê– Šr² ÂÆÒ lê J&ú¢ÊÒ WW 

:. Ê: Ç J&ú¢Ê:® vZÊ~(Tg)ê -40&r 30 × ÊV:. B² 170 ×&r rÆr ÚæÂÆ V 2¯W’² †Jr J&ú¢ÊV è– ~&r ¿‡r ÂÆV Šr² J&ú¢Ê:J: TgV 5-10 ×

&r VnÚÊãV æŽ:.G

Abstract:Four kinds of new aliphatic diols were synthesized by the ring opening reaction of glycolide with 1,4-butane- diol, 1,6-hexanediol, 1,4-cyclohexanediol, or 1,4-cyclohexanedimethanol, a difunctional initiator, in the presence of stannous octoate catalyst. The resulting diols were melt-polymerized with succinic acid, adipic acid, or suberic acid at 170, 190, or 220 × to produce new sequentially ordered aliphatic polyesters and their corresponding polyesters with random structure.

Their glass transition temperatures (Tg) ranged from -40 to 30 ×. The sequentially ordered polyesters prepared at 170 × had higher Tg of 5 to 10 × than the polyesters with random structure produced at higher temperature. From in-vitro degradation test, the sequentially ordered polyesters was slower in the rate of hydrolysis in a buffer solution than the polymers with random molecular structure.

Keywords: sequentially ordered aliphatic diol, biodegradable polyesters, transesterification, in-vitro degradation, degradation rate.

†To whom correspondence should be addressed. E-mail: ykhan@hanyang.ac.kr

2r ç &>& V²2 ÂÆV Ûr ÚæÂÆV 2¯W’² j‚:š succinic acid(SCA), adipic acid(APA), N6 suberic acid(SBA)

– ÿ: Ê g¿~Ò ª2úÊr ë¿n§š Ғr ª¯W NŽÂÆV 2¯W’² †Jr g¿– ÂÆV Šr² 6ÚæÒ WW rÆ®V:. B² Ê: g¿:® ª¯W NŽÂÆ® †JÊ JW‡ e VnÚÊ Æ/& N®ê Wûš Æ®V:.

2. /

2.1 ÷

ÊVû‡ r2r² ÿr BD, HD, CHD, CHDM G® j‚–

Aldrich® 2Ó(99%)š NV² ÿ®V:. V²2 IR e ¹H- NMRš Ê ÂÆÒ «Î²  NV² ÿ®V:. jÊK: SCA, APA, SBA:– Aldrich® 2Ó(99%)š ª 뒲 kr®B  ÿ®V:. _:² ÿr stannous octoate(Sn-oct, 95%)ê Sigma®

2Ӛ, titanium(IV) isopropoxide(TIP, 99.9%)R VnÚÊ :.&  ÿr ÎR šÿÿ·– Aldrich® 2Ӛ ÂÛ²V² ÿ®V :. † 2Ӗ 1_ 2Ӛ kr®  6 NV² ÿ®V:.

2.2 ·»Ïh

¿‡² ’:® ÂÆê FT-IR(Brucker IFS 48)R FT-NMR(Varian- 400)š ÿ®B Ús®V:. g¿® 6vfê Witeg® Cannon- Fenskek fÒ ÿ®B 25.0 ×&r ʲ²BÚ ÿ: &r

tific Ltd.® DSC Plus(~ã 5»10 ×/min) e TGA 1000(~ã

 10 ×/min)š ÿ®B â ÚZ† ®&r wk®V:. g¿

® Úæ e ÚæÚBê THF ÿ:– Styragel columnš ÿ®B Shimazu LC-4A GPC² wk®V:. B² g¿® šÚš pH 7.0®

šÿÿ· ã&r VnÚʲ  šÚ²Ê® ÚÊ2Ò Hitachi®

S-2500C SEM’² «Î®V:.

2.3 §ÿ t¼  _w£ ´|

BD 5.20 g(57.7 mmol), GL 13.387 g(115.4 mmol), Sn-oct 0.093 g(0.23 mmol)š 100 mL 2- »R bÒúÂ& y–  bÒúÂÒ 100 ×

² ^Jr :® †Ú g+& y6 â ÚZ† ®&r ¦n®Ê r 52Z n§2†:. n§  ʲ²BÚ 100 mLÒ n§’& y6

¦n®B ÏÎ :¢ ÿÊn  – Æ ¾Z’š BR®B rÆ

®V:. BRr ʲ²BÚ ÿ·š âZ3 ór†² ʲ²BÚ ÿ :Ò rƲ  40 ×® Kzf&r 242Z Ê ÊÆ®B ² Ç &ú¢Ê j‚(BD/GL diol: BGD)š ¿‡®V:.

ÊÎ&, r2r²r BD V6& HD, CHDÒ ÿ²  Z–

/Ò² Æʒ² n§2r ² j‚:²r HD/GL diol(HGD)R CHD/GL diol(CHGD)š rÆ®V:.

:" r2r²r CHDMš ÿ² &ê n§  ʲ²BÚ 100 mLÒ n§’& y6 ¦n®B ÏÎ :¢ ÿÊn  – Æ

¾Z’š BR®B rƲ  BRr ʲ²BÚ ÿ·š ó®n(100 mLÝ7â)² Žï®B n§®  6 þšÞê CHDMš rÆ®V :. N ʲ²BÚ ÿ·& Ó 3 g® Šn ¿ Nzîš þV

®B 22Z /ž ¦n®B ÿ· & þšÞê nښ rÆ®V:.

BRr ÿ·š âZ3 ór†² ʲ²BÚ ÿ:Ò rƲ  40 ×

® Kzf&r 242Z Ê ÊÆ®B CHDM/GL diol(CHMGD)š

rƮV:.

¿‡r 4Û®® ² j‚ ª¿’® ÂÆê IRR ¹H-NMR úï

R’²Ö† «Î®V’Æ, N:® ‡ ’Â:– šî– o:.

2.3.1#EJG#

IR(NaCl plate, Figure 1(a): 1105(C-O), 1197(OC-O), 1429(H-C-H), 1747(CO), 2960(C-H), 3469 cm^-1(O-H); ¹H-NMR(CDCl3 Figure 1(E/

1.75(4H, m, C-CH2-C), 3.3(2H, broad s, OH), 4.2(4H, t, COO-CH2-C), 4.3 (4H, s, COO-CH2-OH), 4.75(Ha, d, COO-CH2-COO), 4.85 ppm(Ha', d, COO-CH2-COO).

2.3.2 KJG/ /

IR(NaCl plate): 1100(C-O), 1179(OC-O), 1426(H-C-H), 1750(C

O), 2940(C-H), 3468 cm^-1(O-H); ¹H-NMR(CDCl3 / + P &-C- CH2-C-C), 1.7(4H, m, COO-C-CH2-C-COO), 3,2(2H, broad s, OH), 4.2(4H, t, COO-CH2-C), 4.3(4H, s, COO-CH2-OH), 4.75(Ha, d, COO- CH2-COO), 4.85 ppm(Ha', d, COO-CH2-COO).

2.3.3 FKJG##

IR(NaCl plate): 1103(C-O), 1184(OC-O), 1428(H-C-H), 1748(CO), 2950(alC-H), 3467 cm^-1(O-H); ¹H-NMR(CDCl3): δ 2.0-1.4(8H, m, CH² in cyclohexane), 3.0(2H, broad s, OH), 4.15(2H, d, COO-CH2-OH), 4.30(2H, d, COO-CH2-OH), 4.75(Ha, d, COO-CH2-COO), 4.85(Ha', d, COO-CH2-

COO), 4.95 ppm(2H, s, COO-CH-, methyne group in cyclohexane).

2.3.4 FKPJG/ /

IR(NaCl plate): 1104(C-O), 1190(OC-O), 1427 (H-C-H), 1749(CO), 2955(alC-H), 3465 cm^-1(O-H); ¹H-NMR(CDCl3/-1.4(10H, m, CH² in cyclohexane), 3.1(2H, broad s, OH), 4.0(Ha, d, COO-CH2-cyclohexyl), 4.1(Ha', d, CH2-cyclohexyl), 4.15(Hb, d, COO-CH2-OH), 4.30(Hb', d, COO- CH2-OH), 4.75(Hc, s, COO-CH2-COO), 4.85 ppm(Hc', s, COO-CH2-COO).

2.4 §ÿ t¼ ?÷£ ´|

1- »R bÒúÂ& ¿‡² BGDÒ 3.09 g(9.59 mmol), SCAÒ 1.10 g(9.30 mmol), _:²r titanium(IV) isopropoxide 11.0 mg(0.039 mmol)š y:. 170 ײ ^Jr :®†Ú g+& 1- »R b ÒúÂÒ šZÞ JN6 6 2"V ϖ ٚ «Î² , Kâ Z² >W’² f«(«, 62Z → 5 torr, 62Z → 3 torr, 122Z → 2 torr, 62Z → 1 torr, 122Z → 0.5 torr, 62Z → 0.1 torr, 242Z)®B

¦n®Êr 722Z /ž ÿ‹g¿n§š 2†:. g¿  ² ^ ÏÎ  BR² :¢, g¿ÿ·š 50 mL k² ãë² ú 500 mL Ý5â Ê)² Žï² ú 50 ×® Kzf&r 242Z /ž šZ

®~² :. ², SCA V6& APA– SBAÒ ÿ²  Z

– /Ò² 뒲 g¿n§š nß®V:.

ÊÎ&, g¿~Ò 170, 190, Bê 220 ײ ª2úÊr g¿2 r ÚæÂÆV 2¯W’² †Jr J&ú¢Ê– Šr®â † Jr J&ú¢ÊÒ rÆ®V:. B² BGD V6& HGD, CHGD,

– CHMGDÒ ÿ²  WW Z– /Ò² g¿~ Æʒ

² 3 Û®® jÊK:R g¿2r 36V® ² Ç J

&ú¢ÊÒ :.

2.5 ` '£ g»

rƲ ² Ç J&ú¢Ê 2.0 gš 20 mL® ʲ²BÚ ÿ:& ÏÎ  teflon sheetV ž Ê& ïÞê v(7Ý7 cm)

& y6 482Z /ž ~&r æFW’² ór2þ  Kzf&

r 242Z ÊÆ2r ÿ:V šZÞ rÆr šÚ(180» Pš r Æ®V:.

2.6 KcϿ /

Òk² ¦.® 6Úæ šÚš Wk †(10Ý10 mm)² æÎ :¢ pH 7® phosphate šÿÿ·š ÿ®B Î(in-vitro) VnÚÊ :.š :2®V:. ß šÚ ÆW® ŠâÒ   25 mL® vial& y 6 15 mL® šÿÿ·š V² :¢ 37 ×® Ã~Æ ž&r Òk2Z /ž VnÚÊ :.š nß®V:. ÚÊn§  šÿÿ·š BR

² BR®V:. ÚÊr k 2"Ò ó®n² ÿÚÞ Žï®B ² Ê& þšÞê šÿÿ·š rƲ :¢, 482Z /ž K ÊƲ

 ŠâÒ wk®V:. gfâ~(%)– šÚ® ^†Šâ– VnÚ Êr 2"® ÊƊ⮠~²Ö† ®V:.¹⁴

3. ûG Z ë«

3.1 §ÿ t¼  _w£ ´|

>Î GLš ÊVû‡ r2rÎ BD, HD, CHD, Bê CHDM’

² r®n§2r r2r® ç &>& GLÊ 1 Ûr 4Û®®

² Ç &ú¢Ê j‚Î BGD, HGD, CHGD, CHMGDš

¿‡®V:(Scheme 1). N:® ÂÆê ¹H-NMR e IR úïR:² r «Î®V:.

Figure 1ê V²WÊ j‚Î BGD® ¹H-NMR úïR’²r 6

k >Î GL® &ú¢Ê†: Ê® ªNb(-CH²-)†® nâV 5.0&r 4.8 ppm ÖR’² Ê/®V:. ÊF :– 6k® GLÊ r®n¢š q¾²:. ², ² BGD(Bê HGD)® &ú¢Ê

†: Ê& Ê®ê ªNb(-CH²-)†® nâê 4.85(H^a′)R 4.75 ppm (Ha)&r WW Ún î:. ÊÎ& CHGD&rê Þ2³2†

\® ªNb†– &ú¢Ê†: Ê® ªNb†V 4.15R 4.3, 4.75–

4.85 ppm&r WW r² :Î ¦ Û®® n⠒² î:. B² CHMGD® 2ʲ;:R &ú¢Ê†: Ê® ªNb†ê 4.0R 4.1 ppm&r, Þ2³2†® \& Þê ªNb†ê 4.15– 4.3 ppm&

r, &ú¢Ê†: Ê® ªNb†ê 4.75– 4.85 ppm&r WW î

:. B² Ê: ‡’® nâWښV ^Þ® ÂƖ î Ò®®V:. ÊF Z– CHGD– CHMGD j‚:Ê 2ʲ;:†

Ò Ê& ¦6 cis-trans ʇ® ’¿’² Ê®† ¢ŽÊ:.

†Òr ¿‡r j‚:– Ûr ÚæÂÆV 2¯W’² †Jr

² Ç &ú¢Ê j‚:ښ ¢®:.¹⁵

², BGDÒ IR úïRš wk² R > GL® &ú¢Ê

†&r îîê 1764 cm^-1ÖR® k² ·n ¶V n§  1751 cm^-1

² Ê/®V6, B GL&rê R n ® Þ2³2 NOÊ 3481 cm^-1

&r C iâ î:. ÊF :– 6k GL® &ú¢Ê†V r 2r² ÿr BD® Þ2³2 NO& ®Ê r®n vk® BGD  Ʋ Z®n:ê ٚ ®N²:. ÊÎ& HGD e CHGD– CHMGD

®  BGD– o– ûš JV:.

3.2 §ÿ ?÷£ ´|

´r ¿‡r 4Û®® ² Ç &ú¢Ê j‚R SCA, APA, Bê SBA– o– †Ê® Ç jÊK:R ÿ: Ê 170 ×&

r ë¿g¿2†:. N R ² j‚R Ç jÊK:& Ê

®ê ÚæÂÆ® †JÊ 6Úæ  & 2¯W’² Ûr 

² Ç J&ú¢Ò :(Scheme 2).

², rÆr ² J&ú¢Ê:® JW‡R 3ÚÊ ‡&

N®ê ÚæÂÆ® †J® Wûš Æ®† Z®B, ~Ò 170&

r 190R 220 ײ ‚z ÿ‹g¿ n§š Ғ†:. N R ‡û r 6Úæ : & Ê®ê &ú¢Ê NOR ÊK:(Bê ¢

²) NO: Ê& šî® n§†Â– o– &ú¢Ê¦® n§(trans- esterification)Ê^16,17 Òò:ê :š V†®V:. †Òr 170 ×&

r rÆr g¿– B ÚæÂÆV Šr®â †Jr Ç J

&ú¢ÊV ¢:.

Figure 1. ¹H-NMR spectrum of the BGD.

# :# 9# 8# 7# 6# 5# 4# ssp#

Scheme 1. Synthesis of the sequentially ordered aliphatic ester diols.

O O O

O O O

O O

O O O

O O

O

HO OH

O O

BGD / HGD / CHGD / CHMGD

+

O O O

O O

O O

O O

O O

O

O O

O O O

O O

O O

O O

O O

O

O O

if n=1, Succinic acid if n=2, Adipic acid if n=3, Suberic acid

n n

n n

m m

If n=1, HGSC if n=2, HGAP if n=3, HGSB If n=1, BGSC if n=2, BGAP if n=3, BGSB TIP Melt polymerization (170 ])

n n

If m=0, n=1, CHGSC m=0, n=2, CHGAP m=0, n=3, CHGSB If m=1, n=1, CHMGSC m=1, n=2, CHMGAP m=0, n=3, CHMGSB

Scheme 2. Synthesis of the new sequentially ordered aliphatic polyesters.

Table 1– ² Ç J&ú¢Ê® g¿ÆÊR RÊ:.

g¿Z®~– g¿~V 170, 190 ×Ò ¢ê Ó 70»90%Ê6, 220 ×Ò¢ê ^R B 35»80%² ®:. Êٖ  g¿

nn:ê :š ¢ n Þ:. ² >² ÿr j‚& Ê

®ê ªNb†® nV óV¶n³(BGD → HGD) ¿‡r g¿®

6vfê óV®V:. Êٖ g¿ : Ê® nâ¿Ê ó Vn† ¢Ž’² 3Wr:. ², 170 ×&r HGD– SB² rÆr g¿(HGSB-170)® Úæš GPC² wk² R MⁿhÊ 18000Ê

:. NBî 220 ×&r g¿r HGSB-220®  g¿Z®~– f â®V", Úæ– 29000’² óVn:.

rÆr g¿:® ª¯W NŽÂÆ® †Jš ¹H-NMR e ¹³C- NMR úïR’²Ö† ZgW’² «Î®V:. Figure 2ê CHGD–

SCA²Ö† ¿‡² V²WÎ ² Ç J&ú¢ÊÎ CHGSC

® g¿~& †Î ¹H-NMR úïRÊ:. 170 ×&r rÆr g¿

® , ‡ ’Â:® nâWښV ^Þ® ÂƖ î Ò®²

:²Ö† &®ê ÚæÂÆV 2¯W’² †Jr CHGSCV ¿‡n ¢š ¢®:(Figure 2(a)). NBî g¿~V 170&r 190 ×, Bê 220 ײ óV¾& †Ò ÚæÂÆV 2¯WÎ g¿&rê R n

® ² n⠒Â:Ê 3.4»3.7R 5.5»5.7 ppm Ê&r î

’Æ, B² ‡ ’Â:® nâWښV ®ê ûš JV:

(Figure 2(b)). ß g¿~V ¾& †Ò &ú¢Ê¦® n§Ê f

~ óVn6 à 6Úæ ÂÆ® 2¯‡Ê bŠn† ¢ŽÊ:. ÊF

– î Ò®²:.

², Figure 3– HGD– APA²Ö†  ÚæÂÆV 2¯W’

² †Jr ² Ç J&ú¢ÊÎ HGAP-170® ¹³C-NMR Ê:. g¿n§š ®B >Î HGD® OH \® ⠒ Z®

V 61&r 65 ppm’² Ê/n¢š «Î®V:. Êٖ g¿n§

& ®Ê j‚® ç &>& Ê®ê OHV &ú¢Ê†² Z®n

:ê ٚ ®N²:. B >Î HGD– APA® â Z®V g ÂÆV g¿ & Òk®â †Jn¢š ‘²:.

Ê® RÒ RƲ, g¿n§ g &ú¢Ê¦® n§š r®

6 ÚæÂÆV 2¯W’² †Jr Ç J&ú¢ÊÒ rÆ®†

ZÊrê g¿~Ò V_W â vÊÒ ²:.

3.3 §ÿ t¼ ?÷£ ?L|

DSC– TGAÒ Êÿ®B ¿‡r ² Ç J&ú¢Ê:®

JWÆ/ e JWžk‡š «Î®V:. Table 1& êÓr R&r Jê j– oÊ j‚²r HGD– jÊK:’²r SCA, APA, B ê SBAÒ WW g¿2r – g¿:® , ÿr jÊK:

® ªNb† ŽÊV Žn³ T^gV -15, -26, -32 ײ ff fâ

®ê ûš JV:. B SCA– BGD, HGD, CHGD, CHMGDÒ W W 170 ×&r g¿2r – g¿:®  ÿr j‚® ª Nb† ŽÊV BGD&r HGD² Žn³ T^gV 1.0&r -15 ×

² fâ®V:. Êٖ ªNb†® óVV 6Úæ ® vF‡š

óV2†† ¢ŽÊÒ 3Wr:.¹³nÊ& 2ʲ;:R o– 6k NOÊ Ûr CHGD– CHMGD® &ê vkÂÆÎ BGD B ê HGD j‚J: 6Úæ® kV óV®B rÆr g¿® T^g V èâ î:. ², CHGD– SCA Bê SBA²Ö† rÆr g¿:® T^gê g¿~V 170&r 190 ×, Bê 220 ײ ¾

& †Ò fâ®ê ûš JV:. ÊF Z– Zv² &ú¢Ê¦®

Figure 2. ¹H-NMR spectra of the CHGSC polyesters prepared at different polymerization temperature: (a) 170 × and (b) 190 ×.

# :# 9# 8# 7# 6# 5# 4# 3# ssp#

# ;# :# 9# 8# 7# 6# 5# 4# 3# ssp#

Table 1. Polymerization Conditions and Results of the New Aliphatic Polyesters

C onversion(% ) ηinha

Polym er D iol D iacid

170^b 190^b 220^b 170^b 190^b 220^b B G SB B G D Suberic A cid 72 76 36 0.16 0.24 0.30 H G SB H G D Suberic A cid 83 82 68 0.44 0.61 0.86 C H G SB C H G D Suberic A cid 90 83 73 0.26 0.29 0.20 C H M G SB C H M G D Suberic A cid 84 80 82 0.35 0.36 0.42 B G A P B G D A dipic A cid 72 70 77 0.22 0.18 0.26 H G A P H G D A dipic A cid 78 78 62 0.33 0.55 0.82 C H G A P C H G D A dipic A cid 90 82 ^c 0.19 0.29 ^c C H M G A P C H M G D A dipic A cid 84 78 71 0.20 0.21 0.15

B G SC B G D Succinic A cid 75 74 55 0.35 0.42 0.76 H G SC H G D Succinic A cid 77 71 37 0.34 0.36 0.49 C H G SC C H G D Succinic A cid 76 73 58 0.20 0.23 0.17 C H M G SC C H M G D Succinic A cid 64 67 ^c 0.23 0.31 ^c

aInherent viscosity was measured in CHCl3(0.5g/dL) at 25 ×. ^bMelt polymerization was caried out at 170, 190, or 220 ×. ^cDecomposed during melt polymerization.

Figure 3. ¹³C-NMR spectrum of the HGAP polyester prepared at 170 ×.

453# 433# ;3# 93# 73# 53# 3# ssp

n§’² β g¿ ÂÆ® †JÊ Šrʆ ¢ŽÊ:.

ÊÎ&, Table 2&r g¿:® JWžk‡š š¦Ê JÊ, j‚š

BGD&r HGD², jÊK:š SCA&r APA Bê SBA² ÿ¾

& †Ò ß j‚R jÊK:® ªNb†® nV óV¶n³ 10%

Šâfâ ~V óV®ê ûš JV:. Êٖ 6Úæ 

& Ê®ê ªNb†® ŽÊV Žn³, Úæ: Ê& nâ¿Ê óV®† ¢ŽÊ:. B g¿~V 170, 190, 220 ײ èšn³ g

¿® ÚæÊ óV¶ " šÒ JWžk‡ ûnê û

š JV:.

3.4 §ÿ t¼ ?÷£ (Ï¿| /

ÒnW’² Ç J&ú¢Ê 6Úæ® 3’¯W ÚÊê &

ú¢Ê†® VnÚÊ n§& ®Ê Òò:. VnÚÊ® ã& W ûš N®ê Îæ²ê 6Úæ® k‡, T^g, Úæ e ²Ê2 G Ê Þ:. ÊÎ& ÿr VnÚÊ ÿ·® pH– šÿÿ·® ã G

 ÚÊã& Wûš V:.¹⁸

N FÂ&rê ÚÊã– n§†Â& N®ê 6Úæ &  Ûr NŽÂÆ †J® Wûš Æ®† Z®B, 3– v² Æ ÊÎ pH 7® ÎR šÿÿ·š ÿ®B 37 ×&r rÆr šÚ

š VnÚÊ2r 2Z& †Î Šâ® fâÒ wk®V:.

Figure 4– ² j‚R APAÒ 170 ×&r g¿2r rƲ J

&ú¢Ê:® 2Z& †Î VnÚÊ ãÒ JBV:. ß j‚² r CHGD Bê HGD²Ö† rÆr J&ú¢Ê(CHGAP e HGAP) :® VnÚÊ ãV >‚ æŽ:. Êٖ g¿ Ê k®6 ÚæZ nâ¿Ê Ên³ 6Úæ® k‡Ê óVn VnÚÊ n

§&r Ûr Î ¢Ê~R ’Úæ:Ê 6Úæ  ʲ ¾‚

®† ‹† ¢ŽÊ:. ÊÎ& B :Î k‡ 6ÚæÎ CHGAP

BGAP, HGAP, CHMAP– š¦¶ ¢ ÚÊ ãV Vû æâ Ò þš V†®V:. ÊF Rê ¿‡r CHGSC e CHGAP® g¿

® T^mÊ WW 40– 30 ײ V†r R– î Ò®²:(Table 2). n Ê& J: vF² j‚:Î CHMGD– BGD²Ö† rÆr g¿

:® , ÚÊãV 1RÒ¢ : ¾ ßn:V N  ÚÊ V Æ® ßn  ®:. ÊF û– Ç J&ú¢Ê® Vn ÚÊ n§– ÒnW’² Škk WC&r ’V Òò :¢ k WC&r ÚÊV ßr:ê :² zÛv n Þ:.¹⁹ ß 2ʲ;

: NO® ç & ªNb†V ®î Ûr vF² CHMGD(Bê BGD)

ê HGAP)J: VnÚÊ ãV ^†& : ¾ ßn† ¢

ŽÊ:.

Figure 5ê g¿~ 170, 190, Bê 220 ×&r rƲ HGSC(a)–

Table 2. Thermal Transitions and Stabilities of the New Aliphatic Polyesters

Tg (×) Tem p. of 10% w t. loss(×) Polym er

170^b 190^b 220^b 170^b 190^b 220^b

B G SB -30 -22 -32 312 307 354

H G SB -32 -34 -38 328 342 346

C H G SB 5 1 -2 309 314 310

C H M G SB -5 -8 -10 341 335 345

B G A P -16 -13 -17 303 291 368

H G A P -26 -27 -29 322 318 365

C H G A P^a 12 13 ^c 303 343 ^c

C H M G A P -5 -8 -7 321 304 335

B G SC 1 3 -2 286 289 377

H G SC -15 -17 -13 305 312 342

C H G SC^a 29 20 23 298 305 326

C H M G SC 18 18 ^c 315 318 ^c

aCHGSC and CHGAP polyesters prepared at 170 × showed. Tm at 30 and 40×, respectively. ^bMelt polymerization was caried out at 170, 190, or 220 ×. ^cDecomposed during melt polymerization.

Figure 5. Effect of the polymerization temperature on the mass loss of the HGSC and HGAP at pH 7 and 37 ×: (a) 0, HGSC-170; 5, HGSC- 190; ;, HGSC-220; (b) 0, HGAP-170; 5, HGAP-190; ;, HGAP-220.

433

<3

;3 :3 93 83 73

%Mass remaining

4#zhhn# 5#zhhn# 6#zhhn# Time(week)

(a) 433

;3 93 73 53 3

%Mass remaining

4#zhhn# 5#zhhn# 6#zhhn# Time(week)

(b) 433

<3

;3 :3 93 83 73 63 53

%Mass remaining

4#zhhn# 5#zhhn# 6#zhhn# Time(week)

Figure 4. Effect of the different diol on the mass loss of the polyesters at pH 7 and 37 ×: 0, BGAP-170; 5, HGAP-170; ;, CHGAP-170; í, CHMGAP-170.

HGAP(b) g¿:® 2Z& †Î VnÚÊ ã® ªÒ JBV :. ß g¿~V óV¾& †Ò ¿‡r g¿® ÚæÊ è¢

& Þ®6, VnÚÊ ãV ¾Ò&š R n Þ:.

Figure 6– ² Ç J&ú¢ÊÎ CHGAP® šÚš Ò k2Z VnÚʲ  šÚ ²Ê® ªÒ SEM’² V†² ÙÊ:.

Figure 6(a), (b), (c)ê 170 ×&r rÆr ÚæÂÆV 2¯W’² †J r CHGAP-170 šÚ® ²Ê’²r VnÚÊ 2ZÊ óV¾&

†Ò šÚ ²Ê& ç– 6J:Ê ff óVnê ٚ R n Þ:.

², VnÚÊ 2ZÊ 2RÒ² /Ò®V¢& Þ®6 220 ×&

r rÆr šÚ® ²ÊÊ 170 ×J: 6JÊ >‚ Ââ Òþš

Figure 6(d)&r R n Þ:. ÊF Z– g¿~V ¾& †Ò

&ú¢Ê¦® n§Ê f~ óVn k‡ ÂÆ® 6ÚæV Ã

Škk® ÂƲ Z®n† ¢ŽÊ:. Ê: Rê g¿~V 

¶n³ ¿‡r g¿® T^gV fâ²:ê Table 1® R– î Ò®

²:.

4. û«

š g¿~Ò 2úÊr ë¿g¿ n§š Ғr ÚæÂÆ

V 2¯W’² †Jr ² Ç J&ú¢Ê– Šr®â

†Jr g¿Ò rÆ®V:. ², g¿~V 170&r 220 ײ è

šÊ 6Úæ : Ê& &ú¢Ê¦® n§Ê Òî J&ú

¢Ê® NŽÂÆV Šr®â †J~š «Î®V:. N R Úæ ÂÆV 2¯W’² †Jr g¿® T^g J: f⾖ ’¶ šÿÿ

· ã&r VnÚÊ® ãV ¾Òê Zš JV:. ÊÎ& rÆ r Ç J&ú¢Ê & Ê®ê ªNb†® ŽÊV óV

¶n³ T^gê fâ®V", JWžk‡– nV² óV®V:. ÊF

R:š RƲ 6Úæ  & Ûr ª¯W NŽÂÆ® †J Ê g¿® JW‡R VnÚÊ ã& Æ Wûš N²:ê :

š «Î®V:.

[÷£ KÜN FÂê KAIST †û‡6Úæ6âF’®  kWÎ &R ²çV¯¦® 2001š ¦Fš® ÒÖ &’² Ê>¢’Æ, Ê& f2:.

S+S

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(a) (b)

// /

(c) (d)

Figure 6. SEM micrographs of the CHGAP prepared at 170 ×. (a) before hydrolysis; (b) after hydrolysis for 2 weeks; (c) after hydrolysis for 3 weeks; and (d) after hydrolysis for 2 weeks(the CHGAP prepared at 220 ×); film thickness, 180 µm.