Citation: Na-er Guang, Shou-xin Liu, Xuan Li, Lei Tian, Hong-guang Mao. Micellization and Gelation of the Double Thermoresponsive ABC-type Triblock Copolymer Synthesized by RAFT[J]. Chinese Journal of Polymer Science, ;2016, 34(8): 965-980. doi: 10.1007/s10118-016-1817-1 shu

Micellization and Gelation of the Double Thermoresponsive ABC-type Triblock Copolymer Synthesized by RAFT

Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China

Corresponding author: Shou-xin Liu, liushx@snnu.edu.cn
Received Date: 29 January 2016
Revised Date: 1 March 2016
Accepted Date: 30 March 2016

Fund Project: the Program for Changjiang Scholars and Innovative Research Team in University IRT_14R33This work was financially supported by the National Natural Science Foundation of China 20973106

A double thermoresponsive ABC-type triblock copolymer (poly(ethyleneglycol)-block-poly(2-(2-methoxyethoxy) ethyl methacrylate)-block-poly(2-(2-methoxy ethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate, PEG-b-PMEO₂MA-b-P(MEO₂MA-co-OEGMA)) was designed and synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT). The ABC-type triblock copolymer endowed a thermal-induced two-step phase transition at 29 and 39℃, corresponding to the thermosensitive properties of PMEO₂MA and P(MEO₂MA-co-OEGMA) segments, respectively. The two-step self-assembly of copolymer solutions was studied by UV transmittance measurement, dynamic light scattering (DLS), transmission electron microscopy (TEM) and so on. The triblock copolymers showed the distinct thermosensitive behavior with respect to transition temperatures, aggregate type and size, which was correlated to the degree of polymerization of thermosensitive blocks and the molar fraction of OEGMA in the P(MEO₂MA-co-OEGMA) segments. In addition, micelles could further aggregate to form the hydrogel by the self-associate of PEG chains under the abduction of the concentration and temperature. The transition from sol to gel was investigated by a test tube inverting method and dynamic rheological measurement.
- ABC-type triblock copolymer,
- Double thermoresponsive,
- Micellization,
- Sol-gel transition
1. [1]
  Joo, J.H., Ko, D.Y., Moon, H.J., Shinde, U.P., Park, M.H. and Jeong, B., Biomacromolecules, 2014, 15:3664 doi: 10.1021/bm500942p
2. [2]
  Shi, S., Yu, Y., Wang, T., Wang, Q.M., Wang, C. and Kuroda, S., Chinese J. Polym. Sci., 2014, 32(5):524 doi: 10.1007/s10118-014-1435-8
3. [3]
  Wu, Q.J.Y, Wang, R., Zhou, Y., Huang, Y.Q., Ghosh, R. and Chen, X.N., Chinese J. Polym. Sci., 2015, 33(7):1048 doi: 10.1007/s10118-015-1655-6
4. [4]
  Wang, X.L., Ma, X.Y. and Zang, D.Y., Soft Matter, 2013, 9:443 doi: 10.1039/C2SM26797G
5. [5]
  Iatridi, Z., Mattheolabakis, G., Avgoustakisb, K. and Tsitsilianis, C., Soft Matter, 2011, 7:11160 doi: 10.1039/c1sm06185b
6. [6]
  Xiao, J.J., Li, X.B., Wang, X., Yi, C.W. and Su, S.P., Chinese J. Polym. Sci., 2015, 33(3):456 doi: 10.1007/s10118-015-1598-y
7. [7]
  Tang, Y.F., Zhang, S.M., Wang, M., Zhu, J.L., Sun, T.M. and Jiang, G.Q., J. Polym. Res., 2014, 21:390 doi: 10.1007/s10965-014-0390-y
8. [8]
  Yang, L.L., Zhang, J.M., He, J.S., Zhang, J. and Gan, Z.H., Chinese J. Polym. Sci., 2015, 33(12):1640 doi: 10.1007/s10118-015-1703-2
9. [9]
  Cheng, C., Wei, H., Shi, B.X., Cheng, H., Li, C., Gu, Z.W., Cheng, S.X., Zhang, X.Z. and Zhuo, R.X., Biomaterials, 2008, 29:497 doi: 10.1016/j.biomaterials.2007.10.004
10. [10]
  Lutz, J.F., J. Polym. Sci., Part A:Polym. Chem., 2008, 46:3459 doi: 10.1002/(ISSN)1099-0518
11. [11]
  Trzebicka, B., Szweda, D., Rangelov, S., Kowalczuk, A., Mendrek, B., Wesołek, A.U. and Dworak, A., J. Polym. Sci., Part A:Polym. Chem., 2013, 51:614 doi: 10.1002/pola.26410
12. [12]
  Lutz, J.F. and Hoth, A., Macromolecules, 2006, 39:893 doi: 10.1021/ma0517042
13. [13]
  Sun, S.T. and Wu, P.Y., Macromolecules, 2013, 46:236 doi: 10.1021/ma3022376
14. [14]
  Hou, L. and Wu, P.Y., Soft Matter, 2014, 10:3578 doi: 10.1039/c4sm00282b
15. [15]
  Lutz, J.F., Weichenhan, K., Akdemir, Ö. and Hoth, A., Macromolecules, 2007, 40:2503 doi: 10.1021/ma062925q
16. [16]
  Boyer, C., Whittaker, M.R., Luzon, M. and Davis, T.P., Macromolecules, 2009, 42:6917 doi: 10.1021/ma9013127
17. [17]
  Weiss, J., Böttcher, C. and Laschewsky, A., Soft Matter, 2011, 7:483 doi: 10.1039/C0SM00531B
18. [18]
  Kotsuchibashi, Y., Yamamoto, K. and Aoyagi, T., J. Polym Sci., Part A:Polym. Chem., 2008, 46:6142 doi: 10.1002/pola.v46:18
19. [19]
  Jochum, F.D., Roth, P.J., Kessler, D. and Theato, P., Biomacromolecules, 2010, 11:2432 doi: 10.1021/bm1006085
20. [20]
  Savoji, M.T., Strandman, S. and Zhu, X.X., Macromolecules, 2012, 45:2001 doi: 10.1021/ma2027269
21. [21]
  Sugihara, S., Kanaoka, S. and Aoshima, S., Macromolecules, 2005, 38:1919 doi: 10.1021/ma048409m
22. [22]
  Synytska, A., Svetushkina, E., Puretskiy, N., Stoychev, G., Berger, S., Ionov L., Bellmann, C., Eichhorn, K.J. and Stamm, M., Soft Matter, 2010, 6:5907 doi: 10.1039/c0sm00414f
23. [23]
  Jochum, F.D., Borg, L., Roth, P.J. and Theato, P., Macromolecules, 2009, 42:7854 doi: 10.1021/ma901295f
24. [24]
  Li, N., Qi, L., Shen, Y., Li, Y.P. and Chen, Y., Appl. Mater. Interfaces, 2013, 5:12441 doi: 10.1021/am403510g
25. [25]
  Chang, L.L., Liu, J.J., Zhang, J.H., Deng, L.D. and Dong, A.J., Polym. Chem., 2013, 4:1430 doi: 10.1039/C2PY20686B
26. [26]
  Han, D.K. and Hubbell, J.A., Macromolecules, 1997, 30:6077 doi: 10.1021/ma970302u
27. [27]
  Yue, G.L., Cui, Q.L., Zhang, Y.X., Wang, E.J. and Wu, F.P., Chinese J. Polym. Sci., 2012, 30(5):770 doi: 10.1007/s10118-012-1179-2
28. [28]
  Chen, J., Spear, S.K., Huddleston, J.G. and Rogers, R.D., Green Chem., 2005, 7:64 doi: 10.1039/b413546f
29. [29]
  Wang, L.H., Wang, J., Gao, X.Y., Liang, Z.Y., Zhu, B.K., Zhu, L.P. and Xu, Y.Y., Polym. Chem., 2014, 5:2836 doi: 10.1039/c3py01619f
30. [30]
  Seidia, F. and Heshmati, P., Chinese J. Polym. Sci., 2015, 33(1):192 doi: 10.1007/s10118-015-1561-y
31. [31]
  Chen, J.C., Liu, M.Z., Chen, C., Gong, H.H. and Gao, C.M., Appl. Mater. Interfaces, 2011, 3:3215 doi: 10.1021/am2007189
32. [32]
  Lai, J.T., Filla, D. and Shea, R., Macromolecules, 2002, 35:6754 doi: 10.1021/ma020362m
33. [33]
  Puttick, S., Irvine, D.J., Licence, P. and Thurecht, K.J., J. Mater. Chem., 2009, 19:2679 doi: 10.1039/b817181p
34. [34]
  Wang, L.P., Wang, Y.P., Acta Chimica Sinica, 2007, 65:737
35. [35]
  Gody, G., Rossner, C., Moraes, J., Vana, P., Maschmeyer, T. and Perrier, S., J. Am. Chem. Soc., 2012, 134:12596 doi: 10.1021/ja3030643
36. [36]
  Liu, T. and Liu, S.Y., Anal. Chem., 2011, 83:2775 doi: 10.1021/ac200095f
37. [37]
  Dai, X.H., Hong, C.Y. and Pan, C.Y., Macromol. Chem. Phys., 2012, 213:2192 doi: 10.1002/macp.v213.20
38. [38]
  Chen, J.C., Liu, M.Z., Gao, C.M., Lu, S.Y., Zhang, X.Y. and Liu, Z., RSC Adv., 2013, 3:15085 doi: 10.1039/c3ra41832d
39. [39]
  Hwang, M.J., Suh, J.M., Bae, Y.H., Kim, S.W. and Jeong, B., Biomacromolecules, 2005, 6:885 doi: 10.1021/bm049347a
40. [40]
  Cui, Q.L., Wu, F.P. and Wang, E.J., J. Phys. Chem. B, 2011, 115:5913 doi: 10.1021/jp200659u
41. [41]
  Cao, Y., Zhao, N., Wu, K. and Zhu, X.X., Langmuir, 2009, 25:1699 doi: 10.1021/la802971s
42. [42]
  Peng, B.L., Grishkewich, N., Yao, Z.L., Han, X., Liu, H.L. and Tam, K.C., ACS Macro. Lett., 2012, 1:632 doi: 10.1021/mz300135x
1. [1]
  Tian Yang , Yi Liu , Lina Hua , Yaoyao Chen , Wuqian Guo , Haojie Xu , Xi Zeng , Changhao Gao , Wenjing Li , Junhua Luo , Zhihua Sun . Lead-free hybrid two-dimensional double perovskite with switchable dielectric phase transition. Chinese Chemical Letters, 2024, 35(6): 108707-. doi: 10.1016/j.cclet.2023.108707
2. [2]
  Changlin Su , Wensheng Cai , Xueguang Shao . Water as a probe for the temperature-induced self-assembly transition of an amphiphilic copolymer. Chinese Chemical Letters, 2025, 36(4): 110095-. doi: 10.1016/j.cclet.2024.110095
3. [3]
  Yunan Yuan , Zhimin Luo , Jie Chen , Chaoliang He , Kai Hao , Huayu Tian . Constructing thermoresponsive PNIPAM-based microcarriers for cell culture and enzyme-free cell harvesting. Chinese Chemical Letters, 2024, 35(7): 109549-. doi: 10.1016/j.cclet.2024.109549
4. [4]
  Yatian Deng , Dao Wang , Jinglan Cheng , Yunkun Zhao , Zongbao Li , Chunyan Zang , Jian Li , Lichao Jia . A new popular transition metal-based catalyst: SmMn₂O₅ mullite-type oxide. Chinese Chemical Letters, 2024, 35(8): 109141-. doi: 10.1016/j.cclet.2023.109141
5. [5]
  Zhi-Yuan Yue , Hua-Kai Li , Na Wang , Shan-Shan Liu , Le-Ping Miao , Heng-Yun Ye , Chao Shi . Dehydration-triggered structural phase transition-associated ferroelectricity in a hybrid perovskite-type crystal. Chinese Chemical Letters, 2024, 35(10): 109355-. doi: 10.1016/j.cclet.2023.109355
6. [6]
  Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
7. [7]
  Mengjun Sun , Zhi Wang , Jvhui Jiang , Xiaobing Wang , Chuang Yu . Gelation mechanisms of gel polymer electrolytes for zinc-based batteries. Chinese Chemical Letters, 2024, 35(5): 109393-. doi: 10.1016/j.cclet.2023.109393
8. [8]
  Pan Liu , Yanming Sun , Alberto J. Fernández-Carrión , Bowen Zhang , Hui Fu , Lunhua He , Xing Ming , Congling Yin , Xiaojun Kuang . Bismuth-based halide double perovskite Cs₂KBiCl₆: Disorder and luminescence. Chinese Chemical Letters, 2024, 35(5): 108641-. doi: 10.1016/j.cclet.2023.108641
9. [9]
  Yu ZHANG , Fangfang ZHAO , Cong PAN , Peng WANG , Liangming WEI . Application of double-side modified separator with hollow carbon material in high-performance Li-S battery. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1218-1232. doi: 10.11862/CJIC.20230412
10. [10]
  Zhiqiang Liu , Qiang Gao , Wei Shen , Meifeng Xu , Yunxin Li , Weilin Hou , Hai-Wei Shi , Yaozuo Yuan , Erwin Adams , Hian Kee Lee , Sheng Tang . Removal and fluorescence detection of antibiotics from wastewater by layered double oxides/metal-organic frameworks with different topological configurations. Chinese Chemical Letters, 2024, 35(8): 109338-. doi: 10.1016/j.cclet.2023.109338
11. [11]
  Chunqing Ou , Meijia Xiao , Xinyue Zheng , Xianzhou Huang , Suleixin Yang , Yingying Leng , Xiaowei Liu , Xiuqi Liang , Linjiang Song , Yanjie You , Shaohua Yao , Changyang Gong . Programmable double-unlock nanocomplex self-supplies phenylalanine ammonia-lyase for precise phenylalanine deprivation of tumors. Chinese Chemical Letters, 2024, 35(8): 109275-. doi: 10.1016/j.cclet.2023.109275
12. [12]
  Bin Dong , Ning Yu , Qiu-Yue Wang , Jing-Ke Ren , Xin-Yu Zhang , Zhi-Jie Zhang , Ruo-Yao Fan , Da-Peng Liu , Yong-Ming Chai . Double active sites promoting hydrogen evolution activity and stability of CoRuOH/Co₂P by rapid hydrolysis. Chinese Chemical Letters, 2024, 35(7): 109221-. doi: 10.1016/j.cclet.2023.109221
13. [13]
  Jinglin CHENG , Xiaoming GUO , Tao MENG , Xu HU , Liang LI , Yanzhe WANG , Wenzhu HUANG . NiAlNd catalysts for CO₂ methanation derived from the layered double hydroxide precursor. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1592-1602. doi: 10.11862/CJIC.20240152
14. [14]
  Xingwen Cheng , Haoran Ren , Jiangshan Luo . Boosting the self-trapped exciton emission in vacancy-ordered double perovskites via supramolecular assembly. Chinese Journal of Structural Chemistry, 2024, 43(6): 100306-100306. doi: 10.1016/j.cjsc.2024.100306
15. [15]
  Cheng-Yan Wu , Yi-Nan Gao , Zi-Han Zhang , Rui Liu , Quan Tang , Zhong-Lin Lu . Enhancing self-assembly efficiency of macrocyclic compound into nanotubes by introducing double peptide linkages. Chinese Chemical Letters, 2024, 35(11): 109649-. doi: 10.1016/j.cclet.2024.109649
16. [16]
  Xin He , Feng Liu , Tao Tu . Double redox-mediated intrinsic semiconductor photocatalysis: Practical semi-heterogeneous synthesis. Chinese Chemical Letters, 2025, 36(3): 110621-. doi: 10.1016/j.cclet.2024.110621
17. [17]
  Yikun Wang , Qiaomei Chen , Shijie Liang , Dongdong Xia , Chaowei Zhao , Christopher R. McNeill , Weiwei Li . Near-infrared double-cable conjugated polymers based on alkyl linkers with tunable length for single-component organic solar cells. Chinese Chemical Letters, 2024, 35(4): 109164-. doi: 10.1016/j.cclet.2023.109164
18. [18]
  Jinqiang Gao , Haifeng Yuan , Xinjuan Du , Feng Dong , Yu Zhou , Shengnan Na , Yanpeng Chen , Mingyu Hu , Mei Hong , Shihe Yang . Methanol steam mediated corrosion engineering towards high-entropy NiFe layered double hydroxide for ultra-stable oxygen evolution. Chinese Chemical Letters, 2025, 36(1): 110232-. doi: 10.1016/j.cclet.2024.110232
19. [19]
  Mohamed Saber Lassoued , Faizan Ahmad , Yanzhen Zheng . Film thickness effect on 2D lead-free hybrid double perovskite properties: Band gap, photocurrent and stability. Chinese Chemical Letters, 2025, 36(4): 110477-. doi: 10.1016/j.cclet.2024.110477
20. [20]
  Zhirong Yang , Shan Wang , Ming Jiang , Gengchen Li , Long Li , Fangzhi Peng , Zhihui Shao . One stone three birds: Ni-catalyzed asymmetric allenylic substitution of allenic ethers, hydroalkylation of 1,3-enynes and double alkylation of enynyl ethers. Chinese Chemical Letters, 2024, 35(8): 109518-. doi: 10.1016/j.cclet.2024.109518

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(924)
HTML views(45)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142