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
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通讯作者: 陈斌, bchen63@163.com

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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

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通讯作者: 陈斌, bchen63@163.com