화학공학소재연구정보센터
Macromolecular Research, Vol.24, No.4, 323-335, April, 2016
Influence of a low content of PEO segment on the thermal, surface and morphological properties of triblock and diblock PCL copolymers
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Two series, one of triblock (PCL/PEO/PCL) and the other of diblock (PCL/PEO) copolymers were prepared by ring-opening polymerization of ε-caprolactone catalized with tin(II) octoate and by using dihydroxy or monohydroxy poly(ethylene oxide) as the macroinitiator. The PEO block length was fixed (M n 1,000 g/mol) and the PCL block lengths (M n 10,000-40,000 g/mol) were tailored by changing weight ratio of ε-CL/PEO. The copolymers’ structure was confirmed by 1H and quantitative 13C NMR spectroscopy while their molecular weights were determined by GPC analysis. The thermal properties and the degree of crystallinity of the copolymers were investigated and compared by using DSC and WAXS. Both types of copolymers were semicrystalline with the orthorhombic PCL crystal lattice. The surface morphology of the copolymer films was investigated by using optical microscopy and AFM analysis, which confirmed the spherulitic lamellar structure with spherulites of different diameters. Data indicated that a low content of PEO segment had an influence on thermal degradation behavior, crystallinity and morphology of copolymers. Roughness of copolymer films was affected by the content of PEO and correlated with the spherulites’ diameter. The small changes in water and moisture absorption properties of copolymers compared to homopolymer PCL were observed.
  1. Vert M, Prog. Polym. Sci, 32, 755 (2007)
  2. Wurth JJ, Shastri VP, J. Polym. Sci. A: Polym. Chem., 51(16), 3375 (2013)
  3. Woodruff MA, Hutmacher DW, Prog. Polym. Sci, 35, 1217 (2010)
  4. Castilla-Cortazar I, Mas-Estelles J, Meseguer-Duenas JM, Ivirico JLE, Mari B, Vidaurre A, Polym. Degrad. Stabil., 97, 1241 (2012)
  5. Pastorino L, Pioli F, Zilli M, Converti A, Nicolini C, Enzyme Microb. Technol., 35(4), 321 (2004)
  6. Wei X, Gong C, Gou M, Fu S, Guo Q, Shi S, Luo F, Guo G, Qiu L, Qian Z, Int. J. Pharm., 381, 1 (2009)
  7. Bogdanov B, Vidts A, Van Den Bulcke A, Verbeeck R, Schacht E, Polymer, 39(8-9), 1631 (1998)
  8. Cerrai P, Tricoli M, Andruzzi F, Paci M, Paci M, Polymer, 30, 338 (1989)
  9. Perret R, Skoulios A, Makromol. Chem., 156, 143 (1972)
  10. Piao LH, Dai ZL, Deng MX, Chen XS, Jing XB, Polymer, 44(7), 2025 (2003)
  11. Wei ZY, Liu L, Yu FY, Wang P, Qi M, J. Appl. Polym. Sci., 111(1), 429 (2009)
  12. Xu Y, He Y, Wei J, Fan Z, Li S, Macromol. Chem. Phys., 209, 1836 (2008)
  13. Castillo RV, Muller AJ, Prog. Polym. Sci, 34, 516 (2009)
  14. Sun J, He C, Zhuang X, Jing X, Chen X, J. Polym. Res., 18, 2161 (2011)
  15. Takeshita H, Fukumoto K, Ohnishi T, Ohkubo T, Miya M, Takenaka K, Shiomi T, Polymer, 47(24), 8210 (2006)
  16. Du ZX, Yang Y, Xu JT, Fan ZQ, J. Appl. Polym. Sci., 104(5), 2986 (2007)
  17. He CL, Sun J, Deng C, Zhao T, Deng MX, Chen XS, Jing XB, Biomacromolecules, 5(5), 2042 (2004)
  18. Li YG, Huang HY, Wang ZB, He TB, Macromolecules, 47(5), 1783 (2014)
  19. Causa A, Filippone G, Acierno D, Domingo C, Salerno A, Macromol. Chem. Phys., 216, 49 (2015)
  20. You JH, Choi SW, Kim JH, Kwak YT, Macromol. Res., 16(7), 609 (2008)
  21. Stankovic M, Tomar J, Hiemstra C, Steendam R, Frijlink HW, Hinrichs WLJ, Eur. J. Pharm. Biopharm., 87, 329 (2014)
  22. Kim J, Nurunnabi M, Oh YJ, Park SY, Lee YK, Macromol. Res., 80, 875 (2012)
  23. Lee JS, Hwang SJ, Lee DS, Kim SC, Kim DJ, Macromol. Res., 17(2), 72 (2009)
  24. Penczek S, Cypryk M, Duda A, Kubisa P, Slomkowski S, Prog. Polym. Sci, 32, 247 (2007)
  25. Penczek S, Duda A, Kowalski A, Libiszowski J, Majerska K, Biela T, Macromol. Symp., 157, 61 (2000)
  26. Storey RF, Sherman JW, Macromolecules, 35(5), 1504 (2002)
  27. Biela T, Kowalski A, Libiszowski J, Duda A, Penczek S, Macromol. Symp., 240, 47 (2006)
  28. Duda A, Biela T, Libiszowski J, Penczek S, Dubois P, Mecerreyes D, Jerome R, Polym. Degrad. Stabil., 59, 215 (1998)
  29. Kim IY, Yoo MK, Kim BC, Park IY, Lee HC, Cho CS, J. Polym. Sci. A: Polym. Chem., 46(11), 3629 (2008)
  30. Huang MH, Li S, Coudane J, Vert M, Macromol. Chem. Phys., 204, 1994 (2003)
  31. Yu J, Wu PY, Polymer, 48(12), 3477 (2007)
  32. Jiang YQ, Mao KJ, Cai XH, Lai SJ, Chen XX, J. Appl. Polym. Sci., 122(4), 2309 (2011)
  33. Persenaire O, Alexandre M, Degee P, Dubois P, Biomacromolecules, 2(1), 288 (2001)
  34. Su TT, Jiang H, Gong H, Polym. Plast. Technol. Eng., 47, 398 (2008)
  35. Lapi AM, Altomare A, Alderighi M, Corti A, Dessy A, Chiellini F, Solimando A, Solaro R, J. Polym. Sci. A: Polym. Chem., 51(18), 3800 (2013)
  36. Bittiger H, Marchessault RH, Niegisch WD, Acta Crystallogr. Sect. B-Struct. Sci., 26, 1923 (1970)
  37. Zong XH, Wang ZG, Hsiao BS, Chu B, Zhou JJ, Jamiolkowski DD, Muse E, Dormier E, Macromolecules, 32(24), 8107 (1999)
  38. Wurth JJ, Blumenthal NR, Shastri VP, PLoS ONE, 9, e99157 (2014)
  39. Huang MH, Li SM, Hutmacher DW, Coudane J, Vert M, J. Appl. Polym. Sci., 102(2), 1681 (2006)
  40. Cometa S, Bartolozzi I, Corti A, Chiellini F, De Giglio E, Chiellini E, Polym. Degrad. Stabil., 95, 2013 (2010)
  41. Erbil HY, Yasar B, Suzer S, Baysal BM, Langmuir, 13(20), 5484 (1997)
  42. Min Y, Lee S, Park JK, Cho KY, Sung SJ, Macromol. Res., 16(3), 231 (2008)
  43. Park SJ, Yang YJ, Lee HB, Colloids Surf. B: Biointerfaces, 38, 35 (2004)
  44. Park SJ, Kim KS, Kim SH, Colloids Surf. B: Biointerfaces, 43, 238 (2005)