聚二甲基硅氧烷与聚四氢呋喃三嵌段共聚物的合成表征与性能

章琦; 魏梦娟; 邓金睿; 吴一弦

doi:10.11777/j.issn1000-3304.2018.18032

您当前的位置：

首页 >

文章列表页 >

聚二甲基硅氧烷与聚四氢呋喃三嵌段共聚物的合成表征与性能

研究论文 | 更新时间：2021-01-26

- 聚二甲基硅氧烷与聚四氢呋喃三嵌段共聚物的合成表征与性能
- Synthesis and Properties of Polytetrahydrofuran-b-Polydimethylsilane-b-Polytetrahydrofuran Triblock Copolymer
- 高分子学报 2018年0卷第9期页码：1202-1211
- 作者机构：
  
  北京化工大学化工资源有效利用国家重点实验室生物医用材料北京实验室　北京 100029
- 作者简介：
  
  E-mail: wuyx@mail.buct.edu.cn Yi-xian Wu(吴一弦), E-mail: wuyx@mail.buct.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 51521062，21574007)资助项目()
- DOI：10.11777/j.issn1000-3304.2018.18032
  中图分类号：
- 纸质出版日期：2018-9，
  
  收稿日期：2018-1-29，
  
  修回日期：2018-2-21，
扫描看全文
章琦, 魏梦娟, 邓金睿, 吴一弦. 聚二甲基硅氧烷与聚四氢呋喃三嵌段共聚物的合成表征与性能[J]. 高分子学报, 2018,0(9):1202-1211.

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.
章琦, 魏梦娟, 邓金睿, 吴一弦. 聚二甲基硅氧烷与聚四氢呋喃三嵌段共聚物的合成表征与性能[J]. 高分子学报, 2018,0(9):1202-1211. DOI： 10.11777/j.issn1000-3304.2018.18032.

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.

摘要

通过可控/活性正离子开环聚合设计合成一系列不同分子量的聚四氢呋喃活性链(PTHF

)，利用聚二甲基硅氧烷(PDMS)的双端胺基与PTHF

反应制备PDMS与聚四氢呋喃(PTHF)的新型三嵌段共聚物(PTHF-

-PDMS-

-PTHF). 通过FTIR与

H-NMR表征产物化学结构及共聚组成，由TGA、DSC及DMA研究嵌段共聚物热性能与动态力学性能，采用TEM和

in situ

POM观察嵌段共聚物的微观形态与结晶形态. 常温下表征共聚物材料自修复性能及37 °C 下表征其抗菌性能. 结果表明：采用AllylBr/AgClO

体系引发四氢呋喃可控/活性正离子开环聚合制备预期分子量的PTHF

，进一步与双端胺基官能化PDMS反应，反应效率可达95%左右，设计合成出一系列不同共聚组成的PTHF-

-PDMS-

-PTHF三嵌段共聚物. 该共聚物呈现双连续微观相分离结构和结晶现象，随着PTHF链段的增长(

PTHF

= 1000 ~ 2000)，结晶速率加快；与相同分子量均聚PDMS和PTHF相比，所制备的三嵌段共聚物的热稳定性明显提高；三嵌段共聚物链中存在2个―NH―基团，在分子链间形成氢键导致产生物理交联及聚合物网络，使材料具有较好的弹性、柔韧性和强度，同时具有自修复特性，将材料完全切开，常温下24 h后断面发生良好愈合，在应力作用下可被拉伸至原长的1.5倍；原位制备的三嵌段共聚物/银纳米复合材料对大肠杆菌表现出良好的抗菌性能. 基于可控/活性正离子开环聚合方法合成的PTHF-

-PDMS-

-PTHF三嵌段共聚物/银纳米复合材料兼具PTHF、PDMS及纳米银的优良性能，在生物医用材料领域具有应用前景.

Abstract

A series of polytetrahydrofuran (PTHF) and polydimethylsilane (PDMS) triblock copolymers (PTHF-

-PDMS-

-PTHF) have been synthesized

via

the combination of controlled termination of living PTHF chains (PTHF

) and ― NH

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/AgClO

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 (

H-NMR) were used to characterize the microstructure of as-prepared triblock copolymers. Thermal properties of the triblock copolymers PTHF-

-PDMS-

-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 (

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-

-PDMS-

-PTHF with silver nanocomposites could be successfully prepared

in situ

with very high efficiency of

. 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.

关键词

聚四氢呋喃聚二甲基硅氧烷聚合物网络自修复抗菌

Keywords

PolytetrahydrofuranPolydimethylsilanePolymeric networksSelf-healing performanceAntimicrobial activity

references

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.7b02910http://doi.org/10.1021/acsami.7b02910 .

David R, Michel P, Patrick N . Macromolecules , 1998 . 31 4301 - 4308 . DOI:10.1021/ma971577chttp://doi.org/10.1021/ma971577c .

Gabor E, Joseph P K . J Polym Sci, Part A: Polym Chem , 2005 . 43 4965 - 4971 . DOI:10.1002/(ISSN)1099-0518http://doi.org/10.1002/(ISSN)1099-0518 .

Prokopios G, Lo T, Ho R, Apostolos A . Polym Chem , 2017 . 8 843 - 850 . DOI:10.1039/C6PY01768Ahttp://doi.org/10.1039/C6PY01768A .

Jennifer M L, Leslie R B, Anthony K C C, John L B . J Biomater Sci, Polym Ed , 2014 . 25 786 - 801 . DOI:10.1080/09205063.2014.907669http://doi.org/10.1080/09205063.2014.907669 .

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.

Ibarboure E, Papon E, Rodríguez H J . Polymer , 2007 . 48 3717 - 3725 . DOI:10.1016/j.polymer.2007.04.046http://doi.org/10.1016/j.polymer.2007.04.046 .

Melissa A, Sherman, Joseph P . J Polym Sci, Part A: Polym Chem , 1998 . 36 1891 - 1899 . DOI:10.1002/(ISSN)1099-0518http://doi.org/10.1002/(ISSN)1099-0518 .

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.2006.11.025http://doi.org/10.1016/j.jconrel.2006.11.025 .

Juliane U, Rainer J, Robert L . Biomaterials , 2014 . 35 4848 - 4861 . DOI:10.1016/j.biomaterials.2014.02.029http://doi.org/10.1016/j.biomaterials.2014.02.029 .

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-yhttp://doi.org/10.1007/s10965-011-9808-y .

Bazoly R, Bruno P, Thomas H, Véronique B, Philippe G . Eur Polym J , 2017 . 88 689 - 700 . DOI:10.1016/j.eurpolymj.2016.09.042http://doi.org/10.1016/j.eurpolymj.2016.09.042 .

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/C7TB00419Bhttp://doi.org/10.1039/C7TB00419B .

Deng W, Lei Y, Zhou S, Zhang A, Lin Y . RSC Adv , 2016 . 6 51694 - 51702 . DOI:10.1039/C6RA07146Ehttp://doi.org/10.1039/C6RA07146E .

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)1521-3900http://doi.org/10.1002/(ISSN)1521-3900 .

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)1097-4628http://doi.org/10.1002/(ISSN)1097-4628 .

Wei X, Ying Y, Yu X . J Appl Polym Sci , 1988 . 70 1621 - 1626.

Guo A R, Yang F, Yu R, Wu Y X . Chinese J Polym Sci , 2015 . 33 ( 1 ): 23 - 35 . DOI:10.1007/s10118-015-1571-9http://doi.org/10.1007/s10118-015-1571-9 .

Guo A R, Yang W X, Yang F, Yu R, Wu Y X . Macromolecules , 2014 . 47 5450 - 5461 . DOI:10.1021/ma501060yhttp://doi.org/10.1021/ma501060y .

Liu Xiao(刘晓), Li Shengran(李晟冉), Wu Yixian(吴一弦). Acta Polymerica Sinica(高分子学报), 2017, (11): 1-8

Wei Mengjuan(魏梦娟), Guo Anru(郭安儒), Wu Yixian(吴一弦). Acta Polymerica Sinica(高分子学报), 2017, (3): 506-515

Wu Yixian(吴一弦), Zhou Qi(周琦), Du Jie(杜杰), Wang Nan(王楠). Acta Polymerica Sinica(高分子学报), 2017, (7): 1047-1057

Mu C, Fan X, Tian W, Bai Y, Yang Z, Fan W, Chen H . Polym Chem , 2012 . 3 3330 - 3339 . DOI:10.1039/c2py20586fhttp://doi.org/10.1039/c2py20586f .

Li Y, Bai T W, Li Y F, Ling J . Macromol Chem Phys , 2017 . 218 ( 3 ): 1600450 DOI:10.1002/macp.v218.3http://doi.org/10.1002/macp.v218.3 .

Pittsa K L, Abu-Mallouhb S, Fenecha M . J Mech Behav Biomed , 2013 . 17 333 - 336 . DOI:10.1016/j.jmbbm.2012.07.007http://doi.org/10.1016/j.jmbbm.2012.07.007 .

Murielle B, Sophie C, Odile F, Françoise P, Dominique T . Langmiur , 2010 . 26 ( 22 ): 17427 - 17434 . DOI:10.1021/la102384shttp://doi.org/10.1021/la102384s .

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.5b01287http://doi.org/10.1021/acs.biomac.5b01287 .

更多指标>

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能

通过正离子聚合原位制备壳聚糖-g-聚四氢呋喃接枝共聚物/银纳米复合材料

活性正离子聚合及原位制备聚醋酸乙烯酯-g-聚四氢呋喃共聚物/纳米银复合材料

聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)共聚物的微观结构与形态