Citation: LIU Hengchang, FENG Yujun. CO₂-Induced Interaction between a Pentablock Nonionic Copolymer and an Anionic Fluorocarbon Surfactant[J]. Acta Physico-Chimica Sinica, ;2019, 35(4): 408-414. doi: 10.3866/PKU.WHXB201803051 shu

CO₂-Induced Interaction between a Pentablock Nonionic Copolymer and an Anionic Fluorocarbon Surfactant

LIU Hengchang ^1,2 ,
FENG Yujun ^1,3,,

1.
Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, R. P. China.
2.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
3.
Polymer Research Institute, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, P. R. China

Corresponding author: FENG Yujun, yjfeng@scu.edu.cn
Received Date: 3 February 2018
Revised Date: 1 March 2018
Accepted Date: 1 March 2018
Available Online: 5 April 2018
Fund Project: the National Natural Science Foundation of China 21773161The project was supported by the National Natural Science Foundation of China (21773161) and the Key Program of United Foundation (Class A) of Petrochemical Industry and NSFC (U176220036)the Key Program of United Foundation (Class A) of Petrochemical Industry and NSFC U176220036

A polymer-surfactant complex is significant in understanding the interactions between amphiphilic molecules and has great potential for use in a vast number of industries. In addition, the stimuli-responsive polymer-surfactant complex represents a hot research topic for the colloid community. However, the use of CO₂ gas to tune their interaction and the corresponding morphological change in the polymer-surfactant complex has been less documented. In this work, the commercially available triblock copolymer Pluronic F127 was used as a starting material and the macromolecular initiator Br-F127-Br was synthesized via esterification. Then, the pentablock copolymer poly(2-(diethylamino)ethyl methacrylate))-block-F127-block-poly(2-(diethylamino)ethyl methacrylate)) (PDEAEAM-b-F127-b-PDEAEMA) was prepared via atom transfer radical polymerization (ATRP) of Br-F127-Br and the monomer 2-(diethylamino)ethyl methacrylate. Both Br-F127-Br and PDEAEAM-b-F127-b-PDEAEMA were characterized by FT-IR and ¹H NMR spectroscopies as well as gel permeation chromatography (GPC). The results indicated that both Br-F127-Br and PDEAEAM-b-F127-b-PDEAEMA were synthesized successfully. The CO₂-responsive behavior of the pentablock copolymer was examined by tracking the changes in pH and electrical conductivity of the polymer solution after alternatingly bubbling CO₂ and N₂. It was found that cyclic streaming of CO₂/N₂ could alter the pH of the polymer solution between 7.2 and 5.3, leading to the protonation degree of PDEAEAM-b-F127-b-PDEAEMA varying between 0.26 and 0.96; this in turn varied the electrical conductivity of the polymer solution between 19.4 μS∙cm⁻¹ and 70.6 μS∙cm⁻¹. The reversible changes in pH and electrical conductivity of the polymer solution indicate the good CO₂-stimuli responsiveness of PDEAEAM-b-F127-b-PDEAEMA. The interaction of PDEAEAM-b-F127-b-PDEAEMA with an anionic fluorocarbon surfactant potassium nonafluoro-1-butanesulfonate (C₄F₉SO₃K) with and without CO₂ was studied by ultraviolet-visible absorption spectrometry (UV-Vis), dynamic light scattering (DLS), and transmission electron microscopy (TEM). The transmittance of the mixed solution of PDEAEAM-b-F127-b-PDEAEMA and C₄F₉SO₃K could be varied between 84% and 52% in the absence and presence of CO₂, indicating the formation of aggregates with different sizes. The DLS results showed that the size of aggregates could be modified reversibly between tens of nanometers and several micrometers by bubbling CO₂ and replacing CO₂ by N₂. The TEM image revealed the reversible morphological transition of the aggregates from spherical to wormlike micelles after bubbling CO₂. The carbonic acid formed from CO₂ and water can protonate the PDEAEMA in the pentablock copolymer to form PDEAEMA·H⁺, and thus the interaction between the pentablock copolymer and C₄F₉SO₃K becomes strong. When CO₂ is replaced by N₂, PDEAEMA·H⁺ reverts to PDEAEMA, and the interaction becomes weak once again. It can therefore be concluded that the protonation/deprotonation process of the pentablock copolymer can be controlled by bubbling CO₂/N₂. The protonation/deprotonation process can "switch" the electrostatic attraction of PDEAEAM-b-F127-b-PDEAEMA to C₄F₉SO₃K, thereby tuning the hydrophilic-lipophilic balance (HLB) of the polymer-surfactant complex reversibly, leading to the reversible morphological transition of the aggregates. The strategy of CO₂-controllable morphological alteration of a polymer–surfactant complex opens a new avenue for preparing gas-sensitive soft materials.
- CO₂-induced,
- Polymer-surfactant complex,
- Self-assembly,
- Wormlike micelles,
- Pluronic
1. [1]
  Goddard, E. D.; Hannan, R. B. J. Am. Oil Chem. Soc. 1977, 54, 561. doi: 10.1007/bf03027636 doi: 10.1007/bf03027636
2. [2]
  Goddard, E. D. Colloids Surf. 1986, 19, 255. doi: 10.1016/0166-6622(86)80340-7 doi: 10.1016/0166-6622(86)80340-7
3. [3]
  Goddard, E. D. Colloids Surf. 1986, 19, 301. doi: 10.1016/0166-6622(86)80341-9 doi: 10.1016/0166-6622(86)80341-9
4. [4]
  Chen, H.; Li, E. X.; Ye, Z. B.; Han, L. J.; Luo, P. Y. Acta Phys. -Chim. Sin. 2011, 27 (3), 671. doi: 10.3866/PKU.WHXB20110306
5. [5]
  Zhang, W. L. Interaction of Polymer with Surfactant. Master Dissertation, Henan Normal University, Xinxiang, 2008.
6. [6]
  Chen, H.; Wu, X. Y.; Ye, Z. B.; Han, L. J.; Luo, P. Y. Acta Phys. -Chim. Sin. 2012, 28(6), 903. doi: 10.3866/PKU.WHXB201202171
7. [7]
  Theato, P.; Sumerlin, B. S.; O'Reilly, R. K.; Epps, T. H., Ⅲ. Chem. Soc. Rev. 2013, 42, 7055. doi: 10.1039/c3cs90057f doi: 10.1039/c3cs90057f
8. [8]
  Liu, H. B.; Lin, S. J.; Feng, Y. J.; Theato, P. Polym. Chem. 2017, 8, 12. doi: 10.1039/c6py01101b doi: 10.1039/c6py01101b
9. [9]
  Jessop, P. G.; Mercer, S. M.; Heldebrant, D. J. Energy Environ. Sci. 2012, 5, 7240. doi: 10.1039/c2ee02912j doi: 10.1039/c2ee02912j
10. [10]
  Darabi, A.; Jessop, P. G.; Cunningham, M. F. Chem. Soc. Rev. 2016, 45, 4391. doi: 10.1039/c5cs00873e doi: 10.1039/c5cs00873e
11. [11]
  Sha, K.; Li, D. S.; Li, Y. P.; Zhang, B.; Wang, J. Y. Macromolecules2008, 41, 361. doi: 10.1021/ma0707234 doi: 10.1021/ma0707234
12. [12]
  Xiong, X. Y.; Tam, K. C.; Gan, L. H. Macromolecules 2003, 36, 9979. doi: 10.1021/ma035292d doi: 10.1021/ma035292d
13. [13]
  Xiong, X. Y.; Tam, K. C.; Gan, L. H. Macromolecules 2004, 37, 3425. doi: 10.1021/ma049662p doi: 10.1021/ma049662p
14. [14]
  Agarwal, A.; Unfer, R.; Mallapragada, S. K. J. Controlled Release 2005, 103, 245. doi: 10.1016/j.jconrel.2004.11.022 doi: 10.1016/j.jconrel.2004.11.022
15. [15]
  Determan, M. D.; Cox, J. P.; Seifert, S.; Thiyagarajan, P.; Mallapragada, S. K. Polymer 2005, 46, 6933. doi: 10.1016/j.polymer.2005.05.138 doi: 10.1016/j.polymer.2005.05.138
16. [16]
  Xiong, X. Y.; Tam, K. C.; Gan, L. H. J. Appl. Polym. Sci. 2006, 100, 4163. doi: 10.1002/app.23470 doi: 10.1002/app.23470
17. [17]
  He, J. L.; Ni, P. H.; Liu, C. C. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3029. doi: 10.1002/pola.22641 doi: 10.1002/pola.22641
18. [18]
  Abe, M. Curr. Opin. Colloid Interface Sci. 1999, 4, 354. doi: 10.1016/s1359-0294(99)90017-1 doi: 10.1016/s1359-0294(99)90017-1
19. [19]
  Esumi, K.; Takehana, K.; Nojima, T.; Meguro, K. Colloids Surf. 1992, 64, 15. doi: 10.1016/0166-6622(92)80157-w doi: 10.1016/0166-6622(92)80157-w
20. [20]
  Zhou, F.; Xie, M. X.; Chen, D. Y. Macromolecules 2014, 47, 365. doi: 10.1021/ma401589z doi: 10.1021/ma401589z
21. [21]
  Gröschel, A. H.; Walther, A.; Löbling, T. I.; Schmelz, J.; Hanisch, A.; Schmalz, H.; Müller, A. H. E. J. Am. Chem. Soc. 2012, 134, 13850. doi: 10.1021/ja305903u doi: 10.1021/ja305903u
22. [22]
  Wei, H. B.; Zhang, J. L.; Shi, N.; Liu, Y.; Zhang, B.; Zhang, J.; Wan, X. H. Chem. Sci. 2015, 6, 7201. doi: 10.1039/c5sc02020d doi: 10.1039/c5sc02020d
23. [23]
  Thavanesan, T.; Herbert, C.; Plamper, F. A. Langmuir 2014, 30, 5609. doi: 10.1021/la5007583 doi: 10.1021/la5007583
24. [24]
  Liu, H. B.; Guo, Z. R.; He, S.; Yin, H. Y.; Fei, C. H.; Feng, Y. J. Polym. Chem. 2014, 5, 4756. doi: 10.1039/c4py00258j doi: 10.1039/c4py00258j
25. [25]
  Wang, W.; Liu, H. B.; Mu, M.; Yin, H. Y.; Feng, Y. J. Polym. Chem. 2015, 6, 2900. doi: 10.1039/c5py00053j doi: 10.1039/c5py00053j
26. [26]
  Li, S.; He, J. L.; Zhang, M. Z.; Wang, H. R.; Ni, P. H. Polym. Chem. 2016, 7, 1773. doi: 10.1039/c5py02017d doi: 10.1039/c5py02017d
27. [27]
  MacKnight, W. J.; Ponomarenko, E. A.; Tirrell, D. A. Acc. Chem. Res. 1998, 31, 781. doi: 10.1021/ar960309g doi: 10.1021/ar960309g
28. [28]
  Discher, D. E.; Ahmed, F. Annu. Rev. Biomed. Eng. 2006, 8, 323. doi: 10.1146/annurev.bioeng.8.061505.095838 doi: 10.1146/annurev.bioeng.8.061505.095838
29. [29]
  Zhang, L.; Qian, J. S.; Miao, J. B.; Xia, R.; Chen, P.; Cheng, G. J. Mater. Rev. 2015, 29(12), 79. doi: 10.11896/j.issn.1005-023X.2015.12.018
30. [30]
  Ravey, J. C.; Stébé, M. J. Colloids Surf. A 1994, 84, 11. doi: 10.1016/0927-7757(93)02731-s doi: 10.1016/0927-7757(93)02731-s
31. [31]
  Li, L. Y.; Raghupathi, K.; Song, C. F.; Prasad, P.; Thayumanavan, S. Chem. Commun. 2014, 50, 13417. doi: 10.1039/c4cc03688c doi: 10.1039/c4cc03688c
1. [1]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
2. [2]
  Ruoxi Sun , Yiqian Xu , Shaoru Rong , Chunmiao Han , Hui Xu . The Enchanting Collision of Light and Time Magic: Exploring the Footprints of Long Afterglow Lifetime. University Chemistry, 2024, 39(5): 90-97. doi: 10.3866/PKU.DXHX202310001
3. [3]
  Wenjian Zhang , Mengxin Fan , Wenwen Fei , Wei Bai . Cultivation of Critical Thinking Ability: Based on RAFT Polymerization-Induced Self-Assembly. University Chemistry, 2025, 40(4): 108-112. doi: 10.12461/PKU.DXHX202406099
4. [4]
  Renjie Xue , Chao Ma , Jing He , Xuechao Li , Yanning Tang , Lifeng Chi , Haiming Zhang . Catassembly in the Host-Guest Recognition of 2D Metastable Self-Assembled Networks. Acta Physico-Chimica Sinica, 2024, 40(9): 2309011-0. doi: 10.3866/PKU.WHXB202309011
5. [5]
  Yukai Jiang , Yihan Wang , Yunkai Zhang , Yunping Wei , Ying Ma , Na Du . Characterization and Phase Diagram of Surfactant Lyotropic Liquid Crystal. University Chemistry, 2024, 39(4): 114-118. doi: 10.3866/PKU.DXHX202309033
6. [6]
  Ruolin CHENG , Yue WANG , Xiyao NIU , Huagen LIANG , Ling LIU , Shijian LU . Efficient photothermal catalytic CO₂ cycloaddition over W₁₈O₄₉/rGO composites. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1276-1284. doi: 10.11862/CJIC.20240424
7. [7]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
8. [8]
  Congying Lu , Fei Zhong , Zhenyu Yuan , Shuaibing Li , Jiayao Li , Jiewen Liu , Xianyang Hu , Liqun Sun , Rui Li , Meijuan Hu . Experimental Improvement of Surfactant Interface Chemistry: An Integrated Design for the Fusion of Experiment and Simulation. University Chemistry, 2024, 39(3): 283-293. doi: 10.3866/PKU.DXHX202308097
9. [9]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
10. [10]
  Ke Qiu , Fengmei Wang , Mochou Liao , Kerun Zhu , Jiawei Chen , Wei Zhang , Yongyao Xia , Xiaoli Dong , Fei Wang . A Fumed SiO₂-based Composite Hydrogel Polymer Electrolyte for Near-Neutral Zinc-Air Batteries. Acta Physico-Chimica Sinica, 2024, 40(3): 2304036-0. doi: 10.3866/PKU.WHXB202304036
11. [11]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
12. [12]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
13. [13]
  Xueting Feng , Ziang Shang , Rong Qin , Yunhu Han . Advances in Single-Atom Catalysts for Electrocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2305005-0. doi: 10.3866/PKU.WHXB202305005
14. [14]
  Huafeng SHI . Construction of MnCoNi layered double hydroxide@Co-Ni-S amorphous hollow polyhedron composite with excellent electrocatalytic oxygen evolution performance. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1380-1386. doi: 10.11862/CJIC.20240378
15. [15]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
16. [16]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-0. doi: 10.1016/j.actphy.2025.100054
17. [17]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
18. [18]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts. Acta Physico-Chimica Sinica, 2025, 41(1): 100002-0. doi: 10.3866/PKU.WHXB202309002
19. [19]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
20. [20]
  Xueqi Yang , Juntao Zhao , Jiawei Ye , Desen Zhou , Tingmin Di , Jun Zhang . 调节NNU-55(Fe)的d带中心以增强CO₂吸附和光催化活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100074-0. doi: 10.1016/j.actphy.2025.100074

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(794)
HTML views(157)

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

CO2-Induced Interaction between a Pentablock Nonionic Copolymer and an Anionic Fluorocarbon Surfactant

Metrics

通讯作者: 陈斌, bchen63@163.com

CO₂-Induced Interaction between a Pentablock Nonionic Copolymer and an Anionic Fluorocarbon Surfactant