스타형 폴리락티드의 합성과 분해특성

이재삼; 주동준; 김수현; 김영하

Polymer(Korea), Vol.22, No.6, 880-889, November, 1998

Export Citation

스타형 폴리락티드의 합성과 분해특성

Synthesis and Degradation Property of Star-shaped Polylactide

이재삼, 주동준, 김수현, 김영하

초록

촉매인 stannous octoate(Sn-oct)하에서 개시제인 1-dodecanol, 1,6-hexanediol, glycerol, pentaerythritol(PEr), dipentaerythritol(diPEr), tripentaerythritol(triPEr)로 L-lactide(LL)를 개환중합시켜 선형 및 스타형의 poly-L-lactide(PLLA)를 제조하고 이의 구조 및 물리적 특성을 조사하였다. 락티드에 대한 각각의 알콜양을 변화하여 선형 PLLA 및 스타형 PLLA를 제조하고 이를 NMR로 분석한 결과 [LL]/[polyol]의 몰비가 증가하여 어느 한계이상의 농도에 이르게 되면 각각의 알콜 가지수에 해당하는 선형 및 스타형 PLLA가 제조되었다. DSC에 의한 열분석 결과 스타형 PLLA는 선형 PLLA에 비해 낮은 유리전이온도 및 낮은 용융온도를 나타내었으며 빠른 결정화 속도를 보였다. 80℃에서 저분자량 모형화합물의 in-vitro 가수분해 결과 스타형 PLLA는 선형 PLLA에 비해 높은 초기분해 속도를 나타내었으며 시간이 경과함에 따라 이 경향은 계속적으로 유지되었다.

L-lactide(LL) was melt-polymerized by stannous octoate(Sn-oct) with various alcohols such as 1-dodecanol 1,6-hexanediol, glycerol, pentaerythritol(PEr), dipentaerythritol(diPEr), and tripentaerythritol(triPEr) to yield linear or star-shaped poly-L-lactide(PLLA). Star-shaped PLLA would be interesting polymers as the physical properties and degradation rates should be different from those of linear PLLAs. NMR technique was used for the characterization of polymer structure. The numbers of chain arm were evaluated from NMR peak areas of OH groups and methylene groups. Star-shaped structures were obtained when [LL]/[polyol] ratios were over certain value. By the DSC analysis, the starshaped PLLA showed lower T_g and T_m than linear PLLA. As a results of in-vitro degradation, the star-shaped PLLAs showed faster degradation rate than linear PLLAs at 80 ℃.

Keywords:degradable polylactide;melt-polymerization;star-shaped polylactide;in-vitro degradation

[References]

Vert M, Die Angew. Macromol. Chem., 166-167, 155 (1989)
Sinhai JS, Singh H, Ray AR, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C28(384), 475 (1988)
Kumor GS, Kalpagam V, Nandi US, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C22(2), 225 (1982)
Gutch CF, Annu. Rev. Biophys. Bioeng., 4, 405 (1975)
Harrison JH, Am. J. Surg., 95, 3 (1958)
Gilding DK, Reed AM, Polymer, 20, 1459 (1979)
Anon, (FDA), Fed. Regist., 40(121), C, 23, June (1975)
Kim SH, Han YK, Kim YH, Hong SI, Macromol. Chem., 193, 1623 (1992)
Arvanitoyannis I, Nakayama A, Kawasaki N, Yamamoto N, Polymer, 36(15), 2947 (1995)
Arvanitoyannis I, Nakayama A, Kawasaki N, Yamamoto N, Polymer, 36(11), 2271 (1995)
Arvanitoyannis I, Nakayama A, Psomiadou E, Kawasaki N, Yamamoto N, Polymer, 37(4), 651 (1996)
Makino K, Ohshma H, Kondo T, J. Microencaps, 3(3), 203 (1986)
Williams DF, J. Mater. Sci., 17, 1233 (1982)
Leenslag JW, Pennings AJ, Boss RRM, Rozema FR, Boering G, Biomaterials, 8, 311 (1987)
Mari HV, Paula V, Jukka S, Pertti T, Macromol. Chem. Phys., 1197, 1503 (1996)
Suming L, Garreau H, Vert M, J. Mater. Sci. Mater. Med., 1, 198 (1990)
Pistner H, Bendix DR, Muhling J, Reuther JF, Biomaterials, 14, 291 (1993)

[Referenced By]

[1] Vert M, Die Angew. Macromol. Chem., 166-167, 155 (1989)

[2] Sinhai JS, Singh H, Ray AR, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C28(384), 475 (1988)

[3] Kumor GS, Kalpagam V, Nandi US, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C22(2), 225 (1982)

[4] Gutch CF, Annu. Rev. Biophys. Bioeng., 4, 405 (1975)

[5] Harrison JH, Am. J. Surg., 95, 3 (1958)

[6] Gilding DK, Reed AM, Polymer, 20, 1459 (1979)

[7] Anon, (FDA), Fed. Regist., 40(121), C, 23, June (1975)

[8] Kim SH, Han YK, Kim YH, Hong SI, Macromol. Chem., 193, 1623 (1992)

[9] Arvanitoyannis I, Nakayama A, Kawasaki N, Yamamoto N, Polymer, 36(15), 2947 (1995)

[10] Arvanitoyannis I, Nakayama A, Kawasaki N, Yamamoto N, Polymer, 36(11), 2271 (1995)

[11] Arvanitoyannis I, Nakayama A, Psomiadou E, Kawasaki N, Yamamoto N, Polymer, 37(4), 651 (1996)

[12] Makino K, Ohshma H, Kondo T, J. Microencaps, 3(3), 203 (1986)

[13] Williams DF, J. Mater. Sci., 17, 1233 (1982)

[14] Leenslag JW, Pennings AJ, Boss RRM, Rozema FR, Boering G, Biomaterials, 8, 311 (1987)

[15] Mari HV, Paula V, Jukka S, Pertti T, Macromol. Chem. Phys., 1197, 1503 (1996)

[16] Suming L, Garreau H, Vert M, J. Mater. Sci. Mater. Med., 1, 198 (1990)

[17] Pistner H, Bendix DR, Muhling J, Reuther JF, Biomaterials, 14, 291 (1993)