Citation: Wen-Kai Liu, Yun Zhao, Rong Wang, Feng Luo, Jian-Shu Li, Jie-Hua Li, Hong Tan. Effect of Chain Extender on Hydrogen Bond and Microphase Structure of Biodegradable Thermoplastic Polyurethanes[J]. Chinese Journal of Polymer Science, ;2018, 36(4): 514-520. doi: 10.1007/s10118-018-2020-3 shu

Effect of Chain Extender on Hydrogen Bond and Microphase Structure of Biodegradable Thermoplastic Polyurethanes

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, China

Corresponding author: Jie-Hua Li, jiehua_li@scu.edu.cn Hong Tan, hongtan@scu.edu.cn
Received Date: 19 June 2017
Accepted Date: 11 August 2017
Available Online: 1 November 2017

Thermomechanical properties of polyurethanes (PUs) strongly depend on the molecular interactions and microphase structure. In this work, two chain extenders with different ratios, flexile 1, 4-butanediol (BDO) and branched trimethylolpropane mono allyl ether (TMPAE), are used to tune the molecular interactions and microphase structures of a series of biodegradable thermoplastic polyurethanes (TPUs). In TPUs, the biodegradable polycaprolactone (PCL, M_n of 2000) is used as soft segment while 1, 6-diisocyanatohexane (HDI) and chain extenders are used as hard segment. Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscppy (¹H-NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and mechanical tests were performed to characterize the bulk structure and properties of TPUs. Compared with BDO, the steric bulk of TMPAE is larger. The increment of TMPAE can help to increase the hydrogen bond content, microphase separation, and the elastic modulus ratio (R), which would strongly affect the thermomechanical property of the TPUs. The results of this work verify the importance of the structure of chain extender on the properties of TPUs. It provides valuable information for further understanding the structure-property relationships of these polyurethanes.
- Chain extender,
- Hydrogen bond,
- Crystallinity,
- Polyurethane
1. [1]
  Cherng J. Y., Hou T. Y., Shih M. F., Talsma H., Hennink W. E.. Polyurethane-based drug delivery systems[J]. Int. J. Pharm., 2013,450(1):145-162.
2. [2]
  Zdrahala R. J., Zdrahala I. J.. Biomedical applications of polyurethanes:a review of past promises, present realities, and a vibrant future[J]. J. Biomater. Appl., 1999,14(1):67-90. doi: 10.1177/088532829901400104
3. [3]
  Guelcher S. A.. Biodegradable polyurethanes:synthesis and applications in regenerative medicine[J]. Tissue Eng., Part B:Reviews, 2008,14(1):3-17. doi: 10.1089/teb.2007.0133
4. [4]
  Guan J., Fujimoto K. L., Sacks M. S., Wagner W. R.. Preparation and characterization of highly porous, biodegradable polyurethane scaffolds for soft tissue applications[J]. Biomaterials, 2005,26(18):3961-3971. doi: 10.1016/j.biomaterials.2004.10.018
5. [5]
  Song N. J., Jiang X., Li J. H., Pang Y., Li J. S., Tan H., Fu Q.. The degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering[J]. Chinese J. Polym. Sci., 2013,31(10):1451-1462. doi: 10.1007/s10118-013-1315-7
6. [6]
  Ding M. M., Song N. J., He X. L., Li J. H., Zhou L. J., Tan H., Fu Q., Gu Q.. Toward the next-generation nanomedicines:design of multifunctional multiblock polyurethanes for effective cancer treatment[J]. ACS Nano, 2013,7(3):1918-1928. doi: 10.1021/nn4002769
7. [7]
  Eceiza A., Martin M., de la Caba K., Kortaberria G., Gabilondo N., Corcuera M., Mondragon I.. Thermoplastic polyurethane elastomers based on polycarbonate diols with different soft segment molecular weight and chemical structure:mechanical and thermal properties[J]. Polym. Eng. Sci., 2008,48(2):297-306. doi: 10.1002/(ISSN)1548-2634
8. [8]
  Spontak R. J., Patel N. P.. Thermoplastic elastomers:fundamentals and applications[J]. Curr. Opin. Colloid Interface Sci., 2000,5(5):333-340.
9. [9]
  Wang W. S., Ping P., Yu H. J., Chen X. S., Jing X. B.. Synthesis and characterization of a novel biodegradable, thermoplastic polyurethane elastomer[J]. J. Polym. Sci., Part A:Polym. Chem., 2010,44(19):5505-5512.
10. [10]
  Huang W., Yang B., Zhao Y., Di ng, Z; Huang W. M., Yang B., Zhao Y.. Thermo-moisture responsive polyurethane shape-memory polymer and composites:a review.[J]. J. Mater. Chem., 2010,20(17):3367-3381. doi: 10.1039/b922943d
11. [11]
  Lai S. M., Lan Y. C.. Shape memory properties of melt-blended polylactic acid (PLA)/thermoplastic polyurethane (TPU) bio-based blends[J]. J. Polym. Res., 2013,20(5):140-147. doi: 10.1007/s10965-013-0140-6
12. [12]
  Cui B., Wu Q. Y., Shen L., Yu H. B.. High performance bio-based polyurethane elastomers:effect of different soft and hard segments[J]. Chinese J. Polym. Sci., 2016,34(7):901-909. doi: 10.1007/s10118-016-1811-7
13. [13]
  Guelcher S. A., Srinivasan A., Dumas J. E., Didier J. E., McBride S., Hollinger , J. O.. Synthesis, mechanical properties, biocompatibility, and biodegradation of polyurethane networks from lysine polyisocyanates.[J]. Biomaterials, 2008,29(12):1762-1775. doi: 10.1016/j.biomaterials.2007.12.046
14. [14]
  Lee B. S., Chun B. C., Chung Y. C., Sul K. I., Cho J. W.. Structure and thermomechanical properties of polyurethane block copolymers with shape memory effect[J]. Macromolecules, 2001,34(18):6431-6437. doi: 10.1021/ma001842l
15. [15]
  Yang B., Huang W. M., Li C., Li L.. Effects of moisture on the thermomechanical properties of a polyurethane shape memory polymer[J]. Polymer, 2006,47(4):1348-1356. doi: 10.1016/j.polymer.2005.12.051
16. [16]
  Huang W. M., Yang B., An L., Li C., Chan Y.. Water-driven programmable polyurethane shape memory polymer:demonstration and mechanism[J]. Appl. Phys. Lett., 2005,86(11)114105. doi: 10.1063/1.1880448
17. [17]
  Altıntaş Z., Çakmakçı , E.; Kahraman M. V., Kayaman-Apohan N.. Thioether functional chain extender for thermoplastic polyurethanes[J]. Chinese J. Polym. Sci., 2015,33(6):850-856. doi: 10.1007/s10118-015-1636-9
18. [18]
  Ping P., Wang W. S., Chen X. S., Jing X. B.. Poly(ε-caprolactone) polyurethane and its shape-memory property[J]. Biomacromolecules, 2005,6(2):587-592. doi: 10.1021/bm049477j
19. [19]
  Zhou L. J., Yu L. Q., Ding M. M., Li J. S., Tan H., Wang Z. G., Fu Q.. Synthesis and characterization of pH-sensitive biodegradable polyurethane for potential drug delivery applications[J]. Macromolecules, 2011,44(4):857-864. doi: 10.1021/ma102346a
20. [20]
  Rabani G., Luftmann H., Kraft A.. Synthesis and characterization of two shape-memory polymers containing short aramid hard segments and poly(ε-caprolactone) soft segments[J]. Polymer, 2006,47(12):4251-4260. doi: 10.1016/j.polymer.2006.03.106
21. [21]
  Li F., Zhang X., Hou J., Xu M., Luo X., Ma D., Kim B. K.. Studies on thermally stimulated shape memory effect of segmented polyurethanes[J]. J. Appl. Polym. Sci., 1997,64(8):1511-1516. doi: 10.1002/(ISSN)1097-4628
22. [22]
  Kim B. K., Lee S. Y., Xu M.. Polyurethanes having shape memory effects[J]. Polymer, 1996,37(26):5781-5793. doi: 10.1016/S0032-3861(96)00442-9
23. [23]
  Bogdanov B., Toncheva V., Schacht E., Finelli L., Sarti B., Scandola M.. Physical properties of poly(ester-urethanes) prepared from different molar mass polycaprolactone-diols[J]. Polymer, 1999,40(11):3171-3182. doi: 10.1016/S0032-3861(98)00552-7
24. [24]
  Chen C. P., Dai S. A., Chang H. L., Su W. C., Wu T. M., Jeng R. J.. Polyurethane elastomers through multi-hydrogen-bonded association of dendritic structures[J]. Polymer, 2005,46(25):11849-11857. doi: 10.1016/j.polymer.2005.06.127
25. [25]
  Jiang X., Li J. H., Ding M. M., Tan H., Ling Q. Y., Zhong Y. P., Fu Q.. Synthesis and degradation of nontoxic biodegradable waterborne polyurethanes elastomer with poly(ε-caprolactone) and poly(ethylene glycol) as soft segment[J]. Eur. Polym. J., 2007,43(5):1838-1846. doi: 10.1016/j.eurpolymj.2007.02.029
26. [26]
  Seymour R., Estes G., Cooper S.. Infrared studies of segmented polyurethan elastomers[J]. I. Hydrogen bonding. Macromolecules, 1970,3(5):579-583.
27. [27]
  Su T., Wang G. Y., Xu D. X., Hu C. P.. Preparation and properties of waterborne poly-urethaneurea consisting of fluorinated siloxane units[J]. J. Polym. Sci., Part A:Polym. Chem., 2006,44(10):3365-3373. doi: 10.1002/(ISSN)1099-0518
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