Citation: Zi-lu Zhang, Liang Xu, Chun-yu Zang, Kakuchi Toyoji, Xian-de Shen. Precise Synthesis and Thermoresponsive Property of Block Copolymers Consisting of N,N-diethylacrylamide and N,N-dimethylacrylamide[J]. Acta Polymerica Sinica, ;2019, 50(4): 384-392. doi: 10.11777/j.issn1000-3304.2018.18240 shu

Precise Synthesis and Thermoresponsive Property of Block Copolymers Consisting of N,N-diethylacrylamide and N,N-dimethylacrylamide

Corresponding author: Kakuchi Toyoji, kakuchi@eng.hokudai.ac.jp Xian-de Shen, shenXiande@cust.edu.cn
Received Date: 12 November 2018
Revised Date: 13 December 2018
Available Online: 26 January 2019

The thermoresponsive property of poly(N,N-diethylacrylamide) (PDEAAm) and its copolymer with N,N-dimethylacrylamide (DMAAm) has been studied using various types of the copolymers. The group transfer polymerization (GTP) of N,N-diethylacrylamide (DEAAm) and N,N-dimethylacrylamide (DMAAm) was carried out using tris(pentafluorophenyl borane (B(C₆F₅)₃) as the organocatalyst and triethyl((1-methoxy-2-methylprop-1-en-1-yl)o-xy)silane (SKA^Et) as the initiator to produce the random, di-, tri-, and penta-block copolymers along with the homopolymers of PDEAAm and PDMAAm. The polymerization degrees (PDs) of homopolymers were 25, 50, 100, 200, 300, and 500 for PDEAAm, 25, 50, and 100 for PDMAAm and those of all copolymers was 100, and their dispersity was in the range of 1.05–1.26. The monomer compositions (m/n) in the copolymers were 90/10, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 25/75, and 10/90 for the random copolymer of PDEAAm_m-r-PDMAAm_n and 90/10, 75/25, 50/50, 25/75, and 10/90 for the di-block copolymer of PDEAAm_m-b-PDMAAm_n. The monomer compositions in the tri-block copolymer were PDEAAm₂₅-b-PDMAAm₅₀-b-PDEAAm₂₅ and PDMAAm₂₅-b-PDEAAm₅₀-b-PDMAAm₂₅, and those in the penta-block copolymer were PDEAAm₂₀-b-PDMAAm₂₅-b-PDEAAm₅₀-b-PDMAAm₂₅-b-PDEAAm₂₀ and PDMAAm₂₀-b-PDEAAm₂₀-b-PDMAAm₂₀-b-PDEAAm₂₀-b-PDMAAm₂₀. The thermoresponsive property concerning with a coil-globule phase transition was estimated using the temperature of cloud point (T_cp) of aqueous polymer solutions, i.e., the lower critical solution temperature (LCST). The T_cp of PDEAAm increased with the increasing PD from 36.5 °C to 29.5 °C. For PDEAAm_m-r-PDMAAm_n, the T_cp increased with the increasing DMAAm unit from 38.5 °C to 68.0 °C and none of the T_cps was observed for the copolymers with the m/n ratios of 25/75 and 10/90. For PDEAAm_m-b-PDMAAm_n, the T_cp increased with the increasing segment length of PDMAAm from 34.5 °C to 44.5 °C and no phase transition was observed for PDEAAm₁₀-b-PDMAAm₉₀. For the tri- and penta-block copolymers, which consist of the PDMAAm segment at both copolymer ends, PDEAAm₂₅-b-PDMAAm₅₀-b-PDEAAm₂₅ and PDEAAm₂₀-b-PDMAAm₂₅-b-PDEAAm₅₀-b-PDMAAm₂₅-b-PDEAAm₂₀ only exhibited the phase transition, such as the T_cps of 51.5 and 55.0 °C, respectively. These phase transition behaviors were confirmed by nuclear magnetic resonance spectroscopy (NMR) and dynamic light scattering (DLS) measurements. The hydrodynamic radius (Rh) of PDEAAm₂₅-b-PDMAAm₅₀-b-PDEAAm₂₅ and PDEAAm₂₀-b-PDMAAm₂₀-b-PDEAAm₂₀-b-PDMAAm₂₀-b-PDEAAm₂₀ surged from lower temperature of 45 °C to higher temperature of 75 °C.
- Termoresponeive property,
- Block acrylamide copolymer,
- Poly(N,N-diethylacrylamide),
- Poly(N,N-dimethylacrylamide),
- Temperature of cloud point
1. [1]
  Liu F, Urban M W. Prog Polym Sci, 2010, 35(1-2): 3 − 23 doi: 10.1016/j.progpolymsci.2009.10.002
2. [2]
  Gil E, Hudson S. Prog Polym Sci, 2004, 29(12): 1173 − 1222 doi: 10.1016/j.progpolymsci.2004.08.003
3. [3]
  Mura S, Nicolas J, Couvreur P. Nat Mater, 2013, 12(991): 991 − 1003 doi: 10.1039/c6py90169g
4. [4]
  Roth P J, Lowe A B. Polym Chem, 2017, 8(1): 10 − 11 doi: 10.1039/C6PY90169G
5. [5]
  Scarpa J S, Mueller D D, Klotz I M. J Am Chem Soc, 1967, 89(24): 6024 − 6030 doi: 10.1021/ja01000a006
6. [6]
  Crespy D, Rossi R M. Polym Int, 2007, 56(12): 1461 − 1468 doi: 10.1002/(ISSN)1097-0126
7. [7]
  Liu R, Fraylich M, Saunders B R. Colloid Polym Sci, 2009, 287(6): 627 − 643 doi: 10.1007/s00396-009-2028-x
8. [8]
  Hocine S, Li M H. Soft Matter, 2013, 9(25): 5839 − 5861 doi: 10.1039/c3sm50428j
9. [9]
  Saeki S, Kuwahara N, Nakata M, Kaneko M. Polymer, 1976, 17(8): 685 − 689 doi: 10.1016/0032-3861(76)90208-1
10. [10]
  Wei H, Cheng S X, Zhang X Z, Zhuo R X. Prog Polym Sci, 2009, 34(9): 893 − 910 doi: 10.1016/j.progpolymsci.2009.05.002
11. [11]
  Schild H G. Prog Polym Sci, 1992, 17(2): 163 − 249 doi: 10.1016/0079-6700(92)90023-R
12. [12]
  Plamper F A, Ruppel M, Schmalz A, Borisov O, Ballauff M, Müller A H E. Macromolecules, 2007, 40(23): 8361 − 8366 doi: 10.1021/ma071203b
13. [13]
  Plamper F A, Ballauff M, Müller A H E. J Am Chem Soc, 2007, 129(47): 14538 − 14539 doi: 10.1021/ja074720i
14. [14]
  Meeussen F, Nies E, Berghmans H, Verbrugghe S, Goethals E, Du Prez F. Polymer, 2000, 41(24): 8597 − 8602 doi: 10.1016/S0032-3861(00)00255-X
15. [15]
  Salzinger S, Seemann U B, Plikhta A, Rieger B. Macromolecules, 2011, 44(15): 5920 − 5927 doi: 10.1021/ma200752d
16. [16]
  Vancoillie G, Frank D, Hoogenboom R. Prog Polym Sci, 2014, 39(6): 1074 − 1095 doi: 10.1016/j.progpolymsci.2014.02.005
17. [17]
  Xia Y, Yin X, Burke N A D, Stöver H D H. Macromolecules, 2005, 38(14): 5937 − 5943 doi: 10.1021/ma050261z
18. [18]
  Zhang Y, Furyk S, Bergbreiter D E, Cremer P S. J Am Chem Soc, 2005, 127(41): 14505 − 14510 doi: 10.1021/ja0546424
19. [19]
  Kikuchi S, Chen Y, Kitano K, Takada K, Satoh T, Kakuchi T. Polym Chem, 2015, 6(38): 6845 − 6856 doi: 10.1039/C5PY01104C
20. [20]
  Hasegawa A, Naganawa Y, Fushimi M, Ishihara K, Yamamoto H. Org Lett, 2006, 8(15): 3175 − 3178 doi: 10.1021/ol060939a
21. [21]
  Lessard D G, Ousalem M, Zhu X X. Can J Chem, 2001, 79(12): 1870 − 1874 doi: 10.1139/v01-180
22. [22]
  Huber S, Jordan R. Colloid Polym Sci, 2007, 286(4): 395 − 402
23. [23]
  Sakai N, Jin M, Sato S I, Satoh T, Kakuchi T. Polym Chem, 2014, 5(3): 1057 − 1062 doi: 10.1039/C3PY00972F
24. [24]
  Tao X, Deng Y, Shen Z, Ling J. Macromolecules, 2014, 47(18): 6173 − 6180 doi: 10.1021/ma501131t
1. [1]
  Caixia Lin , Ting Liu , Zhaojiang Shi , Hong Yan , Keyin Ye , Yaofeng Yuan . Innovative Experiment of Electrochemical Dearomative Spirocyclization of N-Acyl Sulfonamides. University Chemistry, 2025, 40(4): 359-366. doi: 10.12461/PKU.DXHX202406107
2. [2]
  Shiyi Chen , Jialong Fu , Jianping Qiu , Guoju Chang , Shiyou Hao . Waste medical mask-derived carbon quantum dots enhance the photocatalytic degradation of polyethylene terephthalate (PET) over BiOBr/g-C₃N₄ S-scheme heterojunction. Acta Physico-Chimica Sinica, 2026, 42(1): 100135-0. doi: 10.1016/j.actphy.2025.100135
3. [3]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
4. [4]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-0. doi: 10.3866/PKU.WHXB202309027
5. [5]
  Xiaoyang Li , Xiaowei Huang , Yimeng Zhang , Huan Liu , Shao Jin , Junpeng Zhuang . Comprehensive Chemical Experiments on the Synthesis of 1,3-Dibromo-5,5-Dimethylhydantoin and Its Application as a Brominating Reagent. University Chemistry, 2025, 40(7): 286-293. doi: 10.12461/PKU.DXHX202408035
6. [6]
  Cong-Bin Ji , Ding-Xiong Xie , Mei Chen , Ye-Ying Lan , Bao-Hua Zhang , Ji-Ying Yang , Zheng-Hui Kang , Shu-Jie Chen , Yu-Wei Zhang , Yun-Lin Liu . Green synthesis of 2-trifluoromethylquinoline skeletons via organocatalytic N-[(α-trifluoromethyl)vinyl]isatins CN bond activation. Chinese Chemical Letters, 2025, 36(7): 110598-. doi: 10.1016/j.cclet.2024.110598
7. [7]
  Xiaofeng Xia , Jielian Zhu . Innovative Comprehensive Experimental Design: Synthesis of 6-Fluoro-N-benzoyl Tetrahydroquinoline. University Chemistry, 2024, 39(10): 344-352. doi: 10.12461/PKU.DXHX202405063
8. [8]
  Hongling Yuan , Jialin Xie , Jiawei Wang , Jixiang Zhao , Jiayan Liu , Qing Feng , Wei Qi , Min Liu . Cyclic Olefin Copolymer (COC): The Agile Vanguard in the Realm of Materials. University Chemistry, 2024, 39(7): 294-298. doi: 10.12461/PKU.DXHX202311041
9. [9]
  Junjun Huang , Ran Chen , Yajian Huang , Hang Zhang , Anran Zheng , Qing Xiao , Dan Wu , Ruxia Duan , Zhi Zhou , Fei He , Wei Yi . Discovery of an enantiopure N-[2-hydroxy-3-phenyl piperazine propyl]-aromatic carboxamide derivative as highly selective α_1D/1A-adrenoceptor antagonist and homology modelling. Chinese Chemical Letters, 2024, 35(11): 109594-. doi: 10.1016/j.cclet.2024.109594
10. [10]
  Huixian Weng , Lefei Hu , Lei Hu , Yihan Zhou , Aohua Wang , Ning Wang , Wenzhe Li , Chunliu Zhu , Shiyan Guo , Miaorong Yu , Yong Gan . Corrigendum to "The complexation of insulin with sodium N-[8-(2-hydroxybenzoyl)amino]-caprylate for enhanced oral delivery: Effects of concentration, ratio, and pH" [Chinese Chemical Letters 33 (2022) 1889-1894]. Chinese Chemical Letters, 2025, 36(8): 111316-. doi: 10.1016/j.cclet.2025.111316
11. [11]
  Xiaojing Tian , Zhichun Huang , Qingsong Zhang , Xu Wang , Ning Yang , Nanping Deng . PNIPAm Thermo-Responsive Nanofibers Mats: Morphological Stability and Response Behavior under Cross-Linking. Acta Physico-Chimica Sinica, 2024, 40(4): 2304037-0. doi: 10.3866/PKU.WHXB202304037
12. [12]
  Xiaorui Chen , Xuan Luo , Tongming Su , Xinling Xie , Liuyun Chen , Yuejing Bin , Zuzeng Qin , Hongbing Ji . Ga-doped Cu/γ-Al₂O₃ bifunctional interface sites promote the direct hydrogenation of CO₂ to DME. Acta Physico-Chimica Sinica, 2025, 41(10): 100126-0. doi: 10.1016/j.actphy.2025.100126
13. [13]
  Meijin Li , Xirong Fu , Xue Zheng , Yuhan Liu , Bao Li . The Marvel of NAD⁺: Nicotinamide Adenine Dinucleotide. University Chemistry, 2024, 39(9): 35-39. doi: 10.12461/PKU.DXHX202401027
14. [14]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
15. [15]
  Zhanhui Yang , Jiaxi Xu . (m+n+…) or [m+n+…]cycloaddition?. University Chemistry, 2025, 40(3): 387-389. doi: 10.12461/PKU.DXHX202406032
16. [16]
  Hao Wu , Zhen Liu , Dachang Bai . ¹H NMR Spectrum of Amide Compounds. University Chemistry, 2024, 39(3): 231-238. doi: 10.3866/PKU.DXHX202309020
17. [17]
  Laiying Zhang , Yinghuan Wu , Yazi Yu , Yecheng Xu , Haojie Zhang , Weitai Wu . Innovation and Practice of Polymer Chemistry Experiment Teaching for Non-Polymer Major Students of Chemistry: Taking the Synthesis, Solution Property, Optical Performance and Application of Thermo-Sensitive Polymers as an Example. University Chemistry, 2024, 39(4): 213-220. doi: 10.3866/PKU.DXHX202310126
18. [18]
  Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang . Recent Progress of Microstructure-Regulated g-C₃N₄ in Photocatalytic NO Conversion: The Pivotal Roles of Adsorption/Activation Sites. Acta Physico-Chimica Sinica, 2025, 41(5): 100039-0. doi: 10.1016/j.actphy.2024.100039
19. [19]
  .
  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
  . CCS Chemistry, 2025, 7(0): -.
20. [20]
  Le Ye , Wei-Xiong Zhang . Structural phase transition in a new organic-inorganic hybrid post-perovskite: (N,N-dimethylpyrrolidinium)[Mn(N(CN)2)3]. Chinese Journal of Structural Chemistry, 2024, 43(6): 100257-100257. doi: 10.1016/j.cjsc.2024.100257

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(214)
HTML views(10)

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

Precise Synthesis and Thermoresponsive Property of Block Copolymers Consisting of N,N-diethylacrylamide and N,N-dimethylacrylamide

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

Metrics

通讯作者: 陈斌, bchen63@163.com