Citation: Qi Zhang, Meng-juan Wei, Jin-rui Deng, Yi-xian Wu. Synthesis and Properties of Polytetrahydrofuran-b-Polydimethylsilane-b-Polytetrahydrofuran Triblock Copolymer[J]. Acta Polymerica Sinica, ;2018, 0(9): 1202-1211. doi: 10.11777/j.issn1000-3304.2018.18032 shu

Synthesis and Properties of Polytetrahydrofuran-b-Polydimethylsilane-b-Polytetrahydrofuran Triblock Copolymer

State Key Laboratory of Chemical Resource Engineering, Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology, Beijing 100029

Corresponding author: Yi-xian Wu, wuyx@mail.buct.edu.cn
Received Date: 29 January 2018
Revised Date: 21 February 2018
Available Online: 3 May 2018

A series of polytetrahydrofuran (PTHF) and polydimethylsilane (PDMS) triblock copolymers (PTHF-b-PDMS-b-PTHF) have been synthesized via the combination of controlled termination of living PTHF chains (PTHF⁺) and ― NH₂ functional groups along PDMS macromolecular backbone with the copolymerization efficiency of near 100%. PTHF living chains and PTHF⁺ were in situ prepared through living cationic opening polymerization of tetrahydrofuran (THF) with AllylBr/AgClO₄ initiating system at 0 °C. The molecular weights of the PTHF chains were adjusted by mediating the molar ratio of the monomer to initiator. Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹H-NMR) were used to characterize the microstructure of as-prepared triblock copolymers. Thermal properties of the triblock copolymers PTHF-b-PDMS-b-PTHF were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Additionally, polarization microscopy (POM) was employed to investigate the effect of number-average molecular weight (M_n,PTHF) of PTHF segments on the crystallization of the triblock copolymers. To have a further insight of the structures of the triblock copolymers, transmission electron microscopy (TEM) was also used to study their micromorphology. The antimicrobial activity of the material was characterized by determination of the E. coli inhibition zone. All characterization results aforementioned demonstrate that the well-defined triblock copolymers of PTHF-b-PDMS-b-PTHF with silver nanocomposites could be successfully prepared in situ with very high efficiency of ca. 95%. The crystallization of the triblock copolymers increased with increasing molecular weight of PTHF segments. Compared to the corresponding homopolymers of PTHF and PDMS, the thermal stability of the triblock copolymers was obviously improved. Moreover, the existence of amino groups (＞N―H) in the macromolecular chains and a large number of ether bonds (―O―) from PTHF segments resulted in the formation of hydrogen bonds between the macro molecular chains of the triblock polymer, leading to the formation of physically cross-linked copolymer networks with more flexibility and better mechanical properties. Based on the strong hydrogen bonds, the obtained polymer networks show a pretty good self-healing performance at room temperature. The triblock copolymers were cut off at room temperature, then the cut section was self-healed for 24 h at room temperature, and the self-healed copolymers could be stretched to 1.5 times of the original length, which proved that the materials behaved good self-healing performance. Furthermore, the antimicrobial activity of the triblock copolymers was characterized by the inhibition zone method, and the diameter of inhibition zone of antibacterial was determined to be 13 mm, indicating a good antibacterial property. A novel nanocomposite, consisting of the triblock copolymer/silver, was synthesized in situ via controlled/living cationic ring-opening polymerization, and showed excellent properties resulted from PTHF, PDMS and Ag nano-particles, suggesting their potential applications in biological and medical fields.
- Polytetrahydrofuran,
- Polydimethylsilane,
- Polymeric networks,
- Self-healing performance,
- Antimicrobial activity
1. [1]
  Ryu I, Kim Y, Jung Y, Lim J, Caroline A R, Son J. ACS Appl Mater Interfaces, 2017, 9: 17427 − 17434 doi: 10.1021/acsami.7b02910
2. [2]
  David R, Michel P, Patrick N. Macromolecules, 1998, 31: 4301 − 4308 doi: 10.1021/ma971577c
3. [3]
  Gabor E, Joseph P K. J Polym Sci, Part A: Polym Chem, 2005, 43: 4965 − 4971 doi: 10.1002/(ISSN)1099-0518
4. [4]
  Prokopios G, Lo T, Ho R, Apostolos A. Polym Chem, 2017, 8: 843 − 850 doi: 10.1039/C6PY01768A
5. [5]
  Jennifer M L, Leslie R B, Anthony K C C, John L B. J Biomater Sci, Polym Ed, 2014, 25: 786 − 801 doi: 10.1080/09205063.2014.907669
6. [6]
  Zhang D D, Ruan Y B, Zhang B Q, Qiao X, Deng G H, Chen Y M, Liu C Y. Polymer, 2017, 120(30): 189 − 196
7. [7]
  Ibarboure E, Papon E, Rodríguez H J. Polymer, 2007, 48: 3717 − 3725 doi: 10.1016/j.polymer.2007.04.046
8. [8]
  Melissa A, Sherman, Joseph P. J Polym Sci, Part A: Polym Chem, 1998, 36: 1891 − 1899 doi: 10.1002/(ISSN)1099-0518
9. [9]
  Chang C, Choi D, Kim W, James W Y, Lane V C, Kim Y, Kim S. J Control Release, 2007, 118: 245 − 253 doi: 10.1016/j.jconrel.2006.11.025
10. [10]
  Juliane U, Rainer J, Robert L. Biomaterials, 2014, 35: 4848 − 4861 doi: 10.1016/j.biomaterials.2014.02.029
11. [11]
  Zhu M, Xiang L, Yang K, Shen L, Long F, Fan J, Yi H, Xiang J, Matthew P A. J Polym Res, 2012, 19: 9808 − 9818 doi: 10.1007/s10965-011-9808-y
12. [12]
  Bazoly R, Bruno P, Thomas H, Véronique B, Philippe G. Eur Polym J, 2017, 88: 689 − 700 doi: 10.1016/j.eurpolymj.2016.09.042
13. [13]
  Mi H, Jing X, Brett N N, Breanna S H, Chen G, Turng L. J Mater Chem B, 2017, 5: 4137 − 4151 doi: 10.1039/C7TB00419B
14. [14]
  Deng W, Lei Y, Zhou S, Zhang A, Lin Y. RSC Adv, 2016, 6: 51694 − 51702 doi: 10.1039/C6RA07146E
15. [15]
  Cheradame H, Sassatelli M, Pomel C, Sanh A, Gau-Racine J, Bacri L, Auvray L, Guegan P. Macromol Symp, 2008, 261: 167 − 181 doi: 10.1002/(ISSN)1521-3900
16. [16]
  Hourston D J, Williams G D, Santguru R, Padget J C, Pears D. J Appl Polym Sci, 1999, 74: 556 − 566 doi: 10.1002/(ISSN)1097-4628
17. [17]
  Wei X, Ying Y, Yu X. J Appl Polym Sci, 1988, 70: 1621 − 1626
18. [18]
  Guo A R, Yang F, Yu R, Wu Y X. Chinese J Polym Sci, 2015, 33(1): 23 − 35 doi: 10.1007/s10118-015-1571-9
19. [19]
  Guo A R, Yang W X, Yang F, Yu R, Wu Y X. Macromolecules, 2014, 47: 5450 − 5461 doi: 10.1021/ma501060y
20. [20]
21. [21]
22. [22]
23. [23]
  Mu C, Fan X, Tian W, Bai Y, Yang Z, Fan W, Chen H. Polym Chem, 2012, 3: 3330 − 3339 doi: 10.1039/c2py20586f
24. [24]
  Li Y, Bai T W, Li Y F, Ling J. Macromol Chem Phys, 2017, 218(3): 1600450 doi: 10.1002/macp.v218.3
25. [25]
  Pittsa K L, Abu-Mallouhb S, Fenecha M. J Mech Behav Biomed, 2013, 17: 333 − 336 doi: 10.1016/j.jmbbm.2012.07.007
26. [26]
  Murielle B, Sophie C, Odile F, Françoise P, Dominique T. Langmiur, 2010, 26(22): 17427 − 17434 doi: 10.1021/la102384s
27. [27]
  Li G F, Wu J, Wang B, Yan S F, Zhang K X, Ding J X, Yin J B. Biomacromolecules, 2015, 16: 3508 − 3518 doi: 10.1021/acs.biomac.5b01287
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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis and Properties of Polytetrahydrofuran-b-Polydimethylsilane-b-Polytetrahydrofuran Triblock Copolymer

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com