无规共聚物P(MEO<sub>2</sub>MA-co-OEGMA)的合成及其在水溶液中温度诱导相转变行为

引用本文: 郭奕, 刘恒江, 陈洁琼, 尚亚卓, 刘洪来. 无规共聚物P(MEO₂MA-co-OEGMA)的合成及其在水溶液中温度诱导相转变行为[J]. 物理化学学报, 2015, 31(10): 1914-1923. doi: 10.3866/PKU.WHXB201508263 shu

Citation: GUO Yi, LIU Heng-Jiang, CHEN Jie-Qiong, SHANG Ya-Zhuo, LIU Hong-Lai. Synthesis of P(MEO₂MA-co-OEGMA) Random Copolymers and Thermally Induced Phase Transition Behaviors in Aqueous Solutions[J]. Acta Physico-Chimica Sinica, 2015, 31(10): 1914-1923. doi: 10.3866/PKU.WHXB201508263 shu

无规共聚物P(MEO₂MA-co-OEGMA)的合成及其在水溶液中温度诱导相转变行为

基金项目:
国家自然科学基金(21173079, 91334203, 21476072)资助项目 (21173079, 91334203, 21476072)

摘要:

利用原子转移自由基聚合(ATRP)方法, 由单体2-(2-甲氧基乙氧基)甲基丙烯酸乙酯(MEO₂MA)和寡聚(乙二醇)甲基醚甲基丙烯酸酯(OEGMA, M_n = 500 g·mol^-1)合成了无规共聚物P(MEO₂MA-co-OEGMA). 并采用动态光散射(DLS)、紫外光谱及透射电子显微镜(TEM)等技术考察聚合物在水溶液中的温度响应性聚集行为, 获得其在水溶液中的最低临界溶解温度(LCST)及其随组成的变化规律. 结果表明, 该聚合物具有良好且可逆的温度响应行为, 这主要归因于聚合物与水分子之间氢键作用, 及其分子本身疏水作用之间为了保持一种微妙的动态平衡而自发对聚集形态进行的“自我调整”, 从而达到新的热力学平衡状态的结果. 该聚合物的LCST与聚合物中单体OEGMA所占的摩尔比例呈线性关系, 可以通过改变单体的摩尔配比实现对聚合物LCST的调控.

关键词:

English

Synthesis of P(MEO₂MA-co-OEGMA) Random Copolymers and Thermally Induced Phase Transition Behaviors in Aqueous Solutions

1.
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China
Received Date: 18 May 2015
Available Online: 10 October 2015
Fund Project:
国家自然科学基金(21173079, 91334203, 21476072)资助项目

Abstract:

Random copolymers of 2-(2-methoxyethoxy)ethyl methacrylate (MEO₂MA) and oli (ethylene glycol) methacrylate (OEGMA, M_n = 500 g·mol^-1) were synthesized by atom transfer radical polymerization (ATRP). Thermally induced aggregation of the co-polymers P(MEO₂MA-co-OEGMA) in aqueous solutions was investigated with dynamic light scattering (DLS), UV-Vis absorption, and transmission electron microscopy (TEM). In addition, the lower critical solution temperature (LCST) in aqueous solutions of P(MEO₂MA-co-OEGMA), and its change with respect to the composition of the copolymer, were obtained. The results indicate that the copolymers have an appreciably reversible thermal responsivity that can be attributed to a delicate balance between hydrogen bonds between the copolymers and water molecules and hydrophobic interactions of polymer segments. If the balance is broken, the polymers attain a new thermodynamic equilibrium by spontaneously changing the extent of aggregation. The LCST correlates linearly with the mole fraction of OEGMA units in the copolymer, and can be adjusted by changing the mole ratio of the two monomers.

Key words:

1. [1]
  
  (1) Gil, E. S.; Hudson S. M. Prog. Polym. Sci. 2004, 29, 1173. doi: 10.1016/j.progpolymsci.2004.08.003
  (1) Gil, E. S.; Hudson S. M. Prog. Polym. Sci. 2004, 29, 1173. doi: 10.1016/j.progpolymsci.2004.08.003
2. [2]
  (2) Dai, S.; Ravi P.; Tam K. C. Soft Matter 2009, 5, 2513. doi: 10.1039/6820044k(2) Dai, S.; Ravi P.; Tam K. C. Soft Matter 2009, 5, 2513. doi: 10.1039/6820044k
3. [3]
  (3) Schmaljohann, D. Adv. Drug Delivery Rev. 2006, 58, 1655. doi: 10.1016/j.addr.2006.09.020(3) Schmaljohann, D. Adv. Drug Delivery Rev. 2006, 58, 1655. doi: 10.1016/j.addr.2006.09.020
4. [4]
  (4) He, C. L.; Kim, S. W.; Lee, D. S. J. Controlled Release 2008, 127, 189. doi: 10.1016/j.jconrel.2008.01.005(4) He, C. L.; Kim, S. W.; Lee, D. S. J. Controlled Release 2008, 127, 189. doi: 10.1016/j.jconrel.2008.01.005
5. [5]
  (5) Cunliffe, D.; de las Heras Alarcon, C.; Peters, V. S. J. R.; Alexander, C. Langmuir 2003, 19, 2888. doi: 10.1021/la026358l(5) Cunliffe, D.; de las Heras Alarcon, C.; Peters, V. S. J. R.; Alexander, C. Langmuir 2003, 19, 2888. doi: 10.1021/la026358l
6. [6]
  (6) Cheng, Y.; Xia, M.; Meng, Z.; Wu, Y.; Ren, H.; Jiang, Y.; Liu, Y.; Zhou, Z.; Jiang, X.; Zhu, M. Acta Polym. Sin. 2014, 10, 1342. doi: 10.10.1007/s00396-014-3262-4(6) Cheng, Y.; Xia, M.; Meng, Z.; Wu, Y.; Ren, H.; Jiang, Y.; Liu, Y.; Zhou, Z.; Jiang, X.; Zhu, M. Acta Polym. Sin. 2014, 10, 1342. doi: 10.10.1007/s00396-014-3262-4
7. [7]
  (7) Ward, M. A.; Georgiou, T. K. Polymers 2011, 3, 1215. doi: 10.3390/polym3031215(7) Ward, M. A.; Georgiou, T. K. Polymers 2011, 3, 1215. doi: 10.3390/polym3031215
8. [8]
  (8) Kitano, H.; Hirabayashi, T.; Gemmei-Ide, M.; Kyo ku, M. Macromol. Chem. Phys. 2004, 205, 1651. doi: 10.1002/macp.20040013s(8) Kitano, H.; Hirabayashi, T.; Gemmei-Ide, M.; Kyo ku, M. Macromol. Chem. Phys. 2004, 205, 1651. doi: 10.1002/macp.20040013s
9. [9]
  (9) Ward, M. A.; Georgiou, T. K. Soft Matter 2012, 8, 2737. doi: 10.1039/c2sm06743a(9) Ward, M. A.; Georgiou, T. K. Soft Matter 2012, 8, 2737. doi: 10.1039/c2sm06743a
10. [10]
  (10) Watson, B. M.; Kasper, F. K.; Engel, P. S.; Mikos, A. G. Biomacromolecules 2014, 15, 1788. doi: 10.1021/bm500175e(10) Watson, B. M.; Kasper, F. K.; Engel, P. S.; Mikos, A. G. Biomacromolecules 2014, 15, 1788. doi: 10.1021/bm500175e
11. [11]
  (11) Schild, H. G. Prog. Polym. Sci. 1992, 17, 163. doi: 10.1016/0079-6700(92)90023-R(11) Schild, H. G. Prog. Polym. Sci. 1992, 17, 163. doi: 10.1016/0079-6700(92)90023-R
12. [12]
  (12) Feng, Q.; Li, F.; Yan, Q. Z.; Zhu, Y. C.; Ge, C. C. Colloid Polym. Sci. 2010, 288, 915. doi: 10.1007/s00396-010-2224-8(12) Feng, Q.; Li, F.; Yan, Q. Z.; Zhu, Y. C.; Ge, C. C. Colloid Polym. Sci. 2010, 288, 915. doi: 10.1007/s00396-010-2224-8
13. [13]
  (13) Wang, X.; Wu, C. Macromolecules 1999, 32, 4299. doi: 10.1021/ma9902450(13) Wang, X.; Wu, C. Macromolecules 1999, 32, 4299. doi: 10.1021/ma9902450
14. [14]
  (14) Cheng, H.; Shen, L.; Wu, C. Macromolecules 2006, 39, 2325. doi: 10.1021/ma052561m(14) Cheng, H.; Shen, L.; Wu, C. Macromolecules 2006, 39, 2325. doi: 10.1021/ma052561m
15. [15]
  (15) Kujawa, P.; Segui, F.; Shaban, S.; Diab, C.; Okada, Y.; Tanaka, F.; Winnik, F. M. Macromolecules 2006, 39, 341. doi: 10.1021/ma051876z(15) Kujawa, P.; Segui, F.; Shaban, S.; Diab, C.; Okada, Y.; Tanaka, F.; Winnik, F. M. Macromolecules 2006, 39, 341. doi: 10.1021/ma051876z
16. [16]
  (16) Xia, Y.; Burke, N. A. D.; Stover, H. D. H. Macromolecules 2006, 39, 2275. doi: 10.1021/ma0519617(16) Xia, Y.; Burke, N. A. D.; Stover, H. D. H. Macromolecules 2006, 39, 2275. doi: 10.1021/ma0519617
17. [17]
  (17) Lutz J. F. J. Polym. Sci. A: Polym. Chem. 2008, 46, 3459. doi: 10.1002/pola.22706(17) Lutz J. F. J. Polym. Sci. A: Polym. Chem. 2008, 46, 3459. doi: 10.1002/pola.22706
18. [18]
  (18) Prime, K. L.; Whitesides, G. M. J. Am. Chem. Soc. 1993, 115, 10714. doi: 10.1021/ja00076a032(18) Prime, K. L.; Whitesides, G. M. J. Am. Chem. Soc. 1993, 115, 10714. doi: 10.1021/ja00076a032
19. [19]
  (19) Stolnik, S.; Illum, L.; Davis, S. S. Adv. Drug Del. Rev. 1995, 16, 195. doi: 10.1016/0169-409X(95)00025-3(19) Stolnik, S.; Illum, L.; Davis, S. S. Adv. Drug Del. Rev. 1995, 16, 195. doi: 10.1016/0169-409X(95)00025-3
20. [20]
  (20) Ishizone, T.; Seki, A.; Hagiwara, M.; Han, S.; Yokoyama, H.; Oyane, A.; Deffieux, A.; Carlotti, S. Macromolecules 2008, 41, 2963. doi: 10.1021/ma702828n(20) Ishizone, T.; Seki, A.; Hagiwara, M.; Han, S.; Yokoyama, H.; Oyane, A.; Deffieux, A.; Carlotti, S. Macromolecules 2008, 41, 2963. doi: 10.1021/ma702828n
21. [21]
  (21) Das, S.; Samanta, S.; Chatterjee, D. P.; Nandi; A. K. J. Polym. Sci. A: Polym. Chem. 2013, 51, 1417. doi: 10.1002/pola.26514(21) Das, S.; Samanta, S.; Chatterjee, D. P.; Nandi; A. K. J. Polym. Sci. A: Polym. Chem. 2013, 51, 1417. doi: 10.1002/pola.26514
22. [22]
  (22) Dong, H.; Matyjaszewski K. Macromolecules 2010, 43, 4623. doi: 10.1021/ma100570s(22) Dong, H.; Matyjaszewski K. Macromolecules 2010, 43, 4623. doi: 10.1021/ma100570s
23. [23]
  (23) Li, Q. S.; Liu, Y.; Ji, S.; Zhou, Z.; Li, Q. Colloid Polym. Sci. 2014, 292, 2993. doi: 10.1007/s00396-014-3262-4(23) Li, Q. S.; Liu, Y.; Ji, S.; Zhou, Z.; Li, Q. Colloid Polym. Sci. 2014, 292, 2993. doi: 10.1007/s00396-014-3262-4
24. [24]
  (24) Lutz, J. F.; Hoth, A. Macromolecules 2006, 39, 893. doi: 10.1021/ma0517042(24) Lutz, J. F.; Hoth, A. Macromolecules 2006, 39, 893. doi: 10.1021/ma0517042
25. [25]
  (25) Matyjaszewski, K.; Davis, T. P. Handbook of Radical Polymerization; John Wiley & Sons. Inc.: Hoboken, NJ, 2003; pp 895-900.(25) Matyjaszewski, K.; Davis, T. P. Handbook of Radical Polymerization; John Wiley & Sons. Inc.: Hoboken, NJ, 2003; pp 895-900.
26. [26]
  (26) Wang, X.S.; Armes, S. P. Macromolecules 2000, 33, 6640. doi: 10.1021/ma000671h(26) Wang, X.S.; Armes, S. P. Macromolecules 2000, 33, 6640. doi: 10.1021/ma000671h
27. [27]
  (27) Lutz, J. F.; Weichenhan, K.; Akdemir, Ö.; Hoth, A. Macromolecules 2007, 40, 2503. doi: 10.1021/ma062925q(27) Lutz, J. F.; Weichenhan, K.; Akdemir, Ö.; Hoth, A. Macromolecules 2007, 40, 2503. doi: 10.1021/ma062925q
28. [28]
  (28) Ji, W. X. Fine and Specialty Chemicals 2010, 18 (8), 58. [计文希. 精细与专用化学品, 2010, 18 (8), 58.](28) Ji, W. X. Fine and Specialty Chemicals 2010, 18 (8), 58. [计文希. 精细与专用化学品, 2010, 18 (8), 58.]
29. [29]
  (29) Qiu, X. P.; Kwan, C. M. S.; Wu, C. Macromolecules 1997, 30, 6090. doi: 10.1021/ma970484s(29) Qiu, X. P.; Kwan, C. M. S.; Wu, C. Macromolecules 1997, 30, 6090. doi: 10.1021/ma970484s
30. [30]
  (30) Taha, M.; Gupta, B. S.; Khoiroh, I.; Lee, M. J. Macromolecules 2011, 44, 8575. doi: 10.1021/ma201790c(30) Taha, M.; Gupta, B. S.; Khoiroh, I.; Lee, M. J. Macromolecules 2011, 44, 8575. doi: 10.1021/ma201790c
31. [31]
  (31) Bhargava, P.; Tu, Y. F.; Zheng, J. X.; Xiong, H. M.; Quirk, R. P.; Cheng, S. Z. D. J. Am. Chem. Soc. 2007, 129, 1113. doi: 10.1021/ja0653019(31) Bhargava, P.; Tu, Y. F.; Zheng, J. X.; Xiong, H. M.; Quirk, R. P.; Cheng, S. Z. D. J. Am. Chem. Soc. 2007, 129, 1113. doi: 10.1021/ja0653019
32. [32]
  (32) Israelachvili. Proc. Natl. Acad. Sci. U. S. A. 1997, 94, 8378. doi: 10.1073/pnas.94.16.8378(32) Israelachvili. Proc. Natl. Acad. Sci. U. S. A. 1997, 94, 8378. doi: 10.1073/pnas.94.16.8378
33. [33]
  (33) Begum, R.; Matsuura, H. J. Chem. Soc. Faraday Trans. 1997, 93, 3839. doi: 10.1039/a703436i(33) Begum, R.; Matsuura, H. J. Chem. Soc. Faraday Trans. 1997, 93, 3839. doi: 10.1039/a703436i
34. [34]
  (34) Tasaki, K. J. Am. Chem. Soc. 1996, 118, 8459. doi: 10.1021/ja951005c(34) Tasaki, K. J. Am. Chem. Soc. 1996, 118, 8459. doi: 10.1021/ja951005c
35. [35]
  (35) Han, S.; Hagiwara, M.; Ishizone, T. Macromolecules 2003, 36, 8312. doi: 10.1021/ma0347971(35) Han, S.; Hagiwara, M.; Ishizone, T. Macromolecules 2003, 36, 8312. doi: 10.1021/ma0347971
36. [36]
  (36) Mertoglu, M.; Garnier, S.; Laschewsky, A.; Skrabania, K.; Storsberg, J. Polymer 2005, 46, 7726. doi: 10.1016/j.polymer. 2005.03.101
  (36) Mertoglu, M.; Garnier, S.; Laschewsky, A.; Skrabania, K.; Storsberg, J. Polymer 2005, 46, 7726. doi: 10.1016/j.polymer. 2005.03.101

扫一扫看文章

计量

PDF下载量: 83
文章访问数: 783
HTML全文浏览量: 39

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

无规共聚物P(MEO₂MA-co-OEGMA)的合成及其在水溶液中温度诱导相转变行为

English

Synthesis of P(MEO₂MA-co-OEGMA) Random Copolymers and Thermally Induced Phase Transition Behaviors in Aqueous Solutions

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

无规共聚物P(MEO2MA-co-OEGMA)的合成及其在水溶液中温度诱导相转变行为

English

Synthesis of P(MEO2MA-co-OEGMA) Random Copolymers and Thermally Induced Phase Transition Behaviors in Aqueous Solutions

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

无规共聚物P(MEO₂MA-co-OEGMA)的合成及其在水溶液中温度诱导相转变行为

Synthesis of P(MEO₂MA-co-OEGMA) Random Copolymers and Thermally Induced Phase Transition Behaviors in Aqueous Solutions

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs