Synthesis and Performance of Novel Modified Polycaprolactone Polyurethane Elastomers†

doi:10.7503/cjcu20160528

Abstract

Abstract:

Polycaprolactone(PCL) is a kind of excellent histocompatible and biodegradable materials due to the presence of amounts of esters that can be hydrolyzed by water or enzyme, which made PCL as one of Pure Food and Drug Administration(FDA) certified medical materials. However, the high crystallinity and poor hydrophility of polycaprolactone induce slow biodegradation rate, poor tenacity and fatigue durability although it has high mechanical strength. Therefore, modification on polycaprolactone was necessary. Herein, we used isocyanates[hexamethylene diisocyanate(HDI) and isophorone diisocyanate(IPDI)] to modify polycaprolactone and the phosphorylated prepolymers were reacted with bifunctional epoxy to form crosslinked and biodegradable elastomers. The test and analysis of mechanical properties, water contact angle, degradation/swelling and cell cytotoxicity in vitro indicated that the introduction of isocyanate helped to improve flexibility, fatigue resistance and degradation rate of the elastomers with no increased cytotoxicity.

Key words: Polycaprolactone, Isocyanate modification, Polyurethane elastomer, Biodegradable

TrendMD:

CHEN Chao, BAO Chunyan, YUAN Min, LIN Qiuning, ZHU Linyong. Synthesis and Performance of Novel Modified Polycaprolactone Polyurethane Elastomers^†[J]. Chem. J. Chinese Universities, 2016, 37(12): 2291.

Figures/Tables 9

Scheme 1 Synthetic routes of PCL 210 phosphoester(A), PCL 205/HDI phosphoester(B), PCL205/IPDI phosphoester(C) and 1,4-butanediol diglycidy ether(E)

Scheme 2 Synthetic route of AE, BE and CE elastomers

Fig.1 1H NMR spectra of PCL 210 phosphoester(A), PCL 205/HDI phosphoester(B) and PCL205/IPDI phosphoester(C)

Fig.2 31P NMR spectra of PCL 210 phosphoester(a), PCL 205/HDI phosphoester(b) and PCL205/IPDI phosphoester(c)

Fig.3 1H NMR spectrum of 1,4-butanediol diglycidy ether

Fig.4 ATR-IR spectra of E(a), AE(b), BE(c) and CE(d) elastomers

Fig.5 Tensile(A) and compression(B) tests of AE(a), BE(b) and CE(c) elastomers

Fig.6 Stress-strain(A, C) and stress-time(B, D) curves of AE(A, B) and BE(C, D) systems

Fig.7 Mass-change curves(A) and cytotoxicity in vitro(B) of AE, BE and CE elastomers in PBS

References 24

[1]	Nicolas A. P., Robert L., Science, 1994, 263(5154), 1715—1720
[2]	Luo Y., Zhuo R. X., Fan C. L., Chem. J. Chinese Universities, 1994, 15(5), 767—770
	(罗毅, 卓仁禧, 范昌烈. 高等学校化学学报,1994, 15(5), 767—770)
[3]	Serrano M. C., Chung E. J., Ameer G. A., Adv. Funct. Mater., 2010, 20(2), 192—208
[4]	Schroeter M., Wildemann B., Lendlein A., Biodegradable Materials, In Regenerative Medicine, Springer Press,Netherlands, 2013, 529—556
[5]	Williams D. F., Biomaterials, 2009, 30, 5897—5909
[6]	Yu H. Y., Tang Z. H., Song W. T., Deng M. X., Chen X. S., Chem. J. Chinese Universities, 2014, 35(5), 903—916
	(于海洋, 汤朝晖, 宋万通, 邓明虓, 陈学思. 高等学校化学学报,2014, 35(5), 903—916)
[7]	Wang Y. C., Tang L. Y., Sun T. M., Biomacromolecules, 2008, 9, 388—395
[8]	Yeong W. Y., Sudarmadji N., Yu H. Y., Chua C. K., Leong K. F., Venkatraman S. S., Boey Y. C. F., Tan L. P., Acta Biomaterialia, 2010, 6(6), 2028—2034
[9]	Bastioli C., Cerutti A., Guanella I., Romano G. C., Tosin M., J. Environm. Polym. Degrad., 1995, 3(2), 81—95
[10]	Dash T. K., Konkimalla V. B., Molecul. Pharm., 2012, 9(9), 2365—2379
[11]	Yoshii F., Darwis D., Mitomo H., Makuuchi K., Rad. Phys. Chem., 2000, 57(3—6), 417—420
[12]	Guelcher S. A., Srinivasan A., Dumas J. E., Didier J. E., McBride S., Hollinger J. O., Biomaterials, 2008, 29(12), 1762—1775
[13]	Yang J., Webb A. R., Ameer G. A., Adv. Mater., 2004, 16(6), 511—516
[14]	Yang J., Webb A. R., Pickerill S. J., Hageman G., Ameer G. A., Biomaterials, 2006, 27(9), 1889—18989
[15]	Liu Z. X., Wang L., Bao C. Y., Cao L., Dai K. R., Zhu L. Y., Biomacromolecules, 2011, 12(6), 2389—2395
[16]	Yuan M., Liu Z. X., Dong S. F., Lin Q. N., Bao C. Y., Zhu L. Y., Acta Polymerica Sinica, 2016, 1, 53—60
	(袁敏, 刘赵兴, 董珊凤, 林秋宁, 包春燕, 朱麟勇.高分子学报, 2016, 1, 53—60)
[17]	Li S.X., Liu Y. J., Polyurethane Resin and It’s Application, Chemical Industry Press, Beijing, 2002
	(李邵雄, 刘益军. 聚氨酯树脂及其应用, 北京: 化学工业出版社, 2002)
[18]	Wang X. C., Lu X. B., Qiang T. T., West Leather, 2009, 31(5), 18—19
	(王学川, 卢先博, 强涛涛. 西部皮革,2009, 31(5), 18—19)
[19]	Tracy D., Reierson R., J. Surfactants Deterg., 2002, 5(2), 169—172
[20]	Wang S. M., Zhou L.W., Liu Y. J., Duan T., Guangzhou Chemical Industry and Technology, 2011, 39(14), 53—55
	(王树民, 周伟良, 刘跃佳, 段涛. 广州化工,2011, 39(14), 53—55)
[21]	Tian X., Dong W. Z., Textile Auxiliaries, 2000, 17(3), 29—30
	(田欣, 董文增. 印染助剂,2000, 17(3), 29—30)
[22]	Penczek S., Kaluzynski K., Pretula J., J. Appl. Polym. Sci., 2007, 105(1), 246—254
[23]	GB/T 4612-2008, Epoxy Determination of Plastic and Epoxy Compounds, Standard Press of China, Beijing, 2008
	(GB/T 4612-2008B/T 4612-2008. 塑料、环氧化合物环氧当量的测定, 北京: 中国标准出版社, 2008)
[24]	ISO 10993-5. Biological Evaluation of Medical Devices—Part 5: Test for in Vitro Cytotoxicity,SO 10993-5. Biological Evaluation of Medical Devices—Part 5: Test for in Vitro Cytotoxicity, International Standard, 2009