Article

Synthesis and Characterization of Biodegradable MethoxyPoly(ethylene glycol)-Poly(ε-caprolactone-co-L-lactide) Block Copolymers
Hyun H, Cho YH, Jeong SC, Lee B, Kim MS, Khang G, Lee HB
메톡시폴리(에틸렌 글리콜)-폴리(카프로락톤-co-L-락타이드) 공중합체의 합성 및 특성 분석
현훈, 조영호, 정성찬, 이봉, 김문석, 강길선, 이해방

Abstract

A series of methoxypoly(ethylene glycol) (MPEG)-poly(ε-caprolactone-co-L-lactide) (PCLA) diblock copolymers were synthesized by ring-opening polymerization of a mixture of ε-caprolactone and L-lactide with different ratios in the presence of Sn(Oct)2. The characterization of MPEG-PCLA diblock copolymers were examined by 1H-NMR, GPC, DSC, and XRD. Kinetic study on ring-opening polymerization of monomer mixtures was carried out in various conditions such as a variation with polymerization time, amount of catalyst, and temperature. The highest conversion obtained in 1.2 ratio of initiator versus catalyst at 110 ℃. The biodegradable characterization of MPEG-PCLA diblock copolymers in aqueous solution was carried out by using GPC for 1~14 weeks. The biodegradability of MPEG-PCLA diblock copolymers increased as the L-lactide content of diblock copolymers increased. In conclusion, we confirmed the dependence of polymerization rate according to various conditions. In addition, we can control the biodegradability of MPEG-PCLA diblock copolymers by changing the ratio of PCL and PLA block segment.

메톡시폴리에틸렌글리콜(MPEG)과 카프로락톤(CL)과 L-락타이드(LA)로 구성된 MPEG-PCLA 블록공중합체의 단량체를 다양한 비율로 Sn(Oct)2의 존재 하에서 개환중합을 통해 합성하였다. MPEG-PCLA 블록공중합체의 특성은 1H-NMR, GPC, DSC 그리고 XRD를 이용하여 결정하였다. 동역학적 변화를 측정하기 위하여 Sn(Oct)2의 존재 하에서 MPEG-PCLA 블록공중합체의 중합 시 중합시간, 온도, 첨가하는 촉매의 양을 달리하면서 중합을 실시하였다. 그 결과 110 ℃의 중합온도와 첨가하는 촉매의 양은 개시제 대비 1.2배의 경우에서 가장 높은 중합률을 보였다. 또한 합성된 블록공중합체의 수용액상에서의 시간에 따른 생분해 거동은 GPC를 이용한 분자량 분포의 비교를 통해 측정하였다. 합성된 블록공중합체의 생분해 거동을 측정한 결과 MPEG-PCLA 블록공중합체의 L-락타이드 함량이 증가할수록 생분해성도 증가하는 것을 확인하였다. 본 연구를 통해 MPEG-PCLA 블록공중합체의 Sn(Oct)2의 존재 하에서 개환중합을 실시함에 있어 다양한 중합조건에 따른 중합속도를 확인하였으며 MPEG-PCLA 블록공중합체는 PCLA 블록의 PCL 대비 PLA의 함량 비율에 따라 생분해 기간을 조절할 수 있는 가능성을 확인하였다.

Keywords: MPEG-PCLA; ε-caprolactone; L-lactide; ring-opening polymerization; kinetics; biodegradability

References

1. Domb AJ, Kost J, Wiseman DMHandbook of Biodegradable Polymers, Harwood Academic Publishers, Amsterdam, Netherland (1997)
2. Atala A, Mooney D, Vacanti JP, Langer RSynthetic Biodegradable Polymer Scaffolds, Birkhauser Boston, USA (1997)
3. Steinbuchel A, Doi YBiopolymers Polyesters III Applications and Commercial Products, WILEY-VCH Verlag GmbH, Weinheim, FRG (2002)
4. Igartua M, Hernandez RM, Esquisabel A, Gascon AR, Calvo MB, Pedraz JL, J. Microencapsul., 14(3), 349 (1997)
5. Panyam J, Labhasetwar V, Adv. Drug Deliv. Rev., 55, 329 (2002)
6. Coombes AG, Yeh MK, Lavelle EC, Davis SS, J. Control. Release, 52, 311 (1998)
7. Penco M, Marchioni S, Ferruti P, D'antone S, Deghenghi P, Biomaterials, 17, 1583 (1996)
8. Huh KM, Bae YH, Polymer, 40(22), 6147 (1999)
9. Qian H, Bei J, Wang S, Polym. Degrad. Stabil., 68, 423 (2000)
10. Kim JK, Park DJ, Lee MS, Ihn KJ, Polymer, 42(17), 7429 (2001)
11. Tsuji H, Ikarashi K, Biomaterials, 25, 5449 (2004)
12. Chae GS, Lee JS, Jeong JK, Cho SH, Lee HB, Khang G, Polym.(Korea), 28(4), 335 (2004)
13. Khang G, Lee JH, Lee JW, Cho JC, Lee HB, Korea Polym. J., 8(2), 80 (2000)
14. Seo KS, Chon SK, Kim MS, Cho SH, Lee HB, Khang G, Polym.(Korea), 28(3), 232 (2004)
15. Suh H, Jeong B, Rathi R, Kim SW, J. Biomed. Mater. Res., 42, 331 (1998)
16. Leong BM, Lee DS, Shon JI, Bae YH, Kim SW, J. Polym. Sci. A: Polym. Chem., 37(6), 751 (1999)
17. Jeong B, Bae YH, Kim SW, Macromolecules, 32(21), 7064 (1999)
18. Choi SW, Choi SY, Jeong B, Kim SW, Lee DS, J. Polym. Sci. A: Polym. Chem., 37(13), 2207 (1999)
19. Huh KM, Bae YH, Polymer, 40(22), 6147 (1999)
20. Li YX, Christian V, Kissel T, J. Control. Release, 32, 121 (1994)
21. Sung YK, Kim SW, Korea Polym. J., 8(5), 199 (2000)
22. Lee JH, Kopecek J, Andrade JD, J. Biomed. Mater. Res., 23, 351 (1989)
23. Seo KS, Park CS, Kim MS, Cho SH, Lee HB, Khang G, Polym.(Korea), 28(3), 211 (2004)
24. Seo KS, Park CS, Kim MS, Cho SH, Lee HB, Khang G, Polym.(Korea), 28(4), 344 (2004)
25. Bogdanov B, Vidts A, Van Den Bulcke A, Verbeeck R, Schacht E, Polymer, 39(8-9), 1631 (1998)
26. Deng MX, Chen XS, Piao LH, Zhang XF, Dai ZL, Jing XB, J. Polym. Sci. A: Polym. Chem., 42(4), 950 (2004)
27. Zhu Z, Xiong C, Zhang L, Yuan M, Deng X, Eur. Polym. J., 35, 1821 (1999)
28. Choi HS, Kim SW, Yun DI, Khang G, Rhee JM, Kim YS, Lee HB, Polym.(Korea), 25(3), 334 (2001)
29. Seong HS, Moon DS, Khang G, Lee HB, Macromol. Chem. Symp., 4, 95 (2001)
30. Choi HS, Khang G, Shin H, Rhee JM, Lee HB, Int. J. Pharm., 234, 195 (2002)
31. An TK, Kang HJ, Moon DS, Lee JS, Seong H, Jeong JK, Khang G, Lee HB, Polym.(Korea), 26(5), 670 (2002)
32. Yoo JY, Kim SW, Khang G, Seong HS, Jeong JK, Kim HJ, Lee JS, Lee HB, Polym.(Korea), 26(5), 680 (2002)
33. Kumaran V, Fredrickson GH, Physica A:Statist. Theo. Physics, 204, 378 (1994)
34. Kim MS, Seo KS, Khang G, Lee HB, Macromol. Rapid Commun., 26, 643 (2005)
35. Kowalski A, Duda A, Penczek S, Macromolecules, 33(20), 7359 (2000)
36. Kricheldorf HR, Boettcher C, Tonnes KU, Polymer, 33, 2817 (1992)
37. Tsuji H, Ono T, Saeki T, Daimon H, Fujie K, Polym. Degrad. Stabil., 89, 336 (2005)
38. Pamula E, Dobrzynski P, Bero M, Paluszkiewicz C, J. Mol. Struct., 744, 537 (2005)
39. Paul MA, Delcourt C, Alexandre M, Monteverde F, Dubois P, Polym. Degrad. Stabil., 87, 535 (2005)
40. Jeong SI, Kim BS, Kang SW, Kwon JH, Lee YM, Kim SH, Kim YH, Biomaterials, 25, 5939 (2004)
41. Teramoto N, Kogure H, Kimura Y, Shibata M, Polymer, 45(23), 7927 (2004)
42. Kister G, Cassanas G, Bergounhon M, Hoarau D, Vert M, Polymer, 41(3), 925 (2000)

Polymer(Korea) 폴리머
Frequency : Bimonthly(odd)
ISSN 0379-153X(Print)
ISSN 2234-8077(Online)
Abbr. Polym. Korea
2023 Impact Factor : 0.4
Indexed in SCIE

This Article

2006; 30(1): 28-34

Published online Jan 25, 2006
Received on Jul 28, 2005
Accepted on Nov 15, 2005

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