基于超支化聚合物两性水凝胶的制备及性能

doi:10.7503/cjcu2015956

摘要/Abstract

摘要：

通过N-丙烯酰-1,2-乙二胺盐酸盐(ADE)的Michael加成反应制备阳离子超支化低聚物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE), 以HADE为大分子单体, 以丙烯酰胺(AAm)和丙烯酸(AAc)为单体, 在无需外加有机交联剂的条件下制备具有高机械强度的两性聚电解质水凝胶(HAH 凝胶). 结果表明, HAH凝胶可以被压缩超过99%的形变而不断裂, 压缩强度高达61.2 MPa; HAH凝胶的断裂伸长率和断裂强度分别达到1700%和70.2 kPa. 由于HADE末端伯胺基与强氧化引发剂通过氧化还原反应生成胺自由基和自身结构中的双键同时参与聚合反应, 因而为凝胶网络形成提供了必要的化学交联作用. 同时HADE结构中胺基正电荷与AAc的羧基负电荷之间的离子交联也为凝胶网络提供了物理交联作用. 2种交联作用的协同作用是HAH凝胶具有良好机械性能的根本原因.

关键词: 超支化聚合物, 两性聚电解质水凝胶, 优良机械性能, pH敏感

Abstract:

The cationic hyperbranched oligomer poly(N-acryloyl-1,2-diaminoethane hydrochloride)(HADE) was firstly synthesized by Michael addition reaction. And then, polyampholyte hydrogels(HAH gels) with good mechanical strength were prepared with HADE as macromonomer, acrylamide(AAm) and acrylic acid(AAc) as comonomers in the absence of chemical crosslinking agent. The results of mechanical testing showed that HAH gels could sustain compressive strain of 99% without breaking and the optimized compressive strength was up to 61.2 MPa. And they also could be stretched over 1700% and tensile strength was 70.2 kPa in tensile test. During the fabrication of HAH gels, amino free radicals derived from the oxidation-reduction reaction between amino groups of HADE and oxidation initiator and double bonds on the end of HADE could simultaneously participate in copolymerization with AAm and AAc. Therefore, HADE could be considered as a chemical cross-linking agent. Meanwhile, physical cross-linking action originated from static-electronic inte-raction between cationic amino groups of HADE and anionic carboxyl groups of AAc could also improve the mechanical performance of HAH gels. Thus, HAH gels could exhibit excellent mechanical performance due to the synergetic effect of chemical and physical cross-linking action.

Key words: Hyperbranched polymer, Polyampholyte hydrogel, High mechanical strength, pH responsive

中图分类号:

O631.2

TrendMD:

王海卫, 梁学称, 徐昆, 谭颖, 路璀阁, 王丕新. 基于超支化聚合物两性水凝胶的制备及性能. 高等学校化学学报, 2016, 37(4): 752.

WANG Haiwei, LIANG Xuechen, XU Kun, TAN Ying, LU Cuige, WANG Pixin. Synthesis and Characterization of Polyampholyte Hydrogels Based on Hyperbranched Polymer^†. Chem. J. Chinese Universities, 2016, 37(4): 752.

图/表 10

Table 1 Properties of the gels

Hydrogel	Mass ratio of AAm∶HADE∶AAc	Swell ratio		Compression test^a		Tensile tes $t b$
Hydrogel	Mass ratio of AAm∶HADE∶AAc	Water	NaCl	σ_c/MPa	E_c/kPa	ε_t(%)	σ_t/kPa
HAH-1	100∶1.5∶1.5	187	33	29.3	12.7	1303	61.1
HAH-2	100∶2.0∶1.5	162	26	41.6	16.9	1267	63.9
HAH-3	100∶2.5∶1.5	138	20	61.2	31.2	1734	70.2
HAH-4	100∶3.0∶1.5	149	24	40.4	15.5	1032	67.1
HAH-5	100∶3.5∶1.5	162	29	30.2	13.1	989	68.1
MAH-1	100∶2.5∶0					825	44.7
MAH-2^c	100∶2.5∶1.5					1016	54.3
MAH-3^d	100∶2.5∶1.5				Dissolve

Table 1 Properties of the gels

Hydrogel	Mass ratio of AAm∶HADE∶AAc	Swell ratio		Compression test^a		Tensile tes $t b$
Hydrogel	Mass ratio of AAm∶HADE∶AAc	Water	NaCl	σ_c/MPa	E_c/kPa	ε_t(%)	σ_t/kPa
HAH-1	100∶1.5∶1.5	187	33	29.3	12.7	1303	61.1
HAH-2	100∶2.0∶1.5	162	26	41.6	16.9	1267	63.9
HAH-3	100∶2.5∶1.5	138	20	61.2	31.2	1734	70.2
HAH-4	100∶3.0∶1.5	149	24	40.4	15.5	1032	67.1
HAH-5	100∶3.5∶1.5	162	29	30.2	13.1	989	68.1
MAH-1	100∶2.5∶0					825	44.7
MAH-2^c	100∶2.5∶1.5					1016	54.3
MAH-3^d	100∶2.5∶1.5				Dissolve

Fig.1 FTIR spectra of Boc-EDA(a), Boc-EDA-AC(b), ADE(c) and HADE(d)

Fig.2 1H NMR spectra of Boc-EDA(A), Boc-EDA-AC(B), ADE(C) and HADE(D) Peaks in Fig.2 are corresponding to Schemes 1 and 2.

Fig.3 SEM images of the HAH-3 gels at different sizes

Fig.4 Synthesis mechanism and structure of HAH gels

Fig.5 Compressive stress-strain curves of HAH gels(A) and compressive modulus and compressive strain at 96% with various HADE content(B)HADE content(%): a. 1.5; b. 2.0; c. 2.5; d. 3.0; e. 3.5.

Fig.6 Compressive and recovery of HAH-3 gel(A) Before compression; (B) compression; (C) after compression.

Fig.7 Tensile stress-strain curves of HAH gels with various HADE content and MAH gelsHADE content(%):a. 1.5; b. 2.0; c. 2.5; d. 3.0; e. 3.5; f. MAH-1; g. MAH-2.

Fig.8 Equilibrium swelling ratio of HAH gels in deionized water and saline solution varying HADE content(A) and the swelling dynamic curves of HAH-3 gel in saline solution with different contents(B)a. Deionized water; b. 0.001 mol/L; c. 0.1 mol/L; d. 0.1 mol/L; e. 1 mol/L.

Fig.9 Swelling behavior of HAH-3 in solution with various pH values

参考文献 28

[1]	Gao C., Yan D. Y., Prog. Polym. Sci., 2004, 40, 183—275
[2]	Lin Y., Gao J. W., Liu H. W., Li Y. S., Macromolecules, 2009, 42(9), 3237—3246
[3]	Sato E., Uehara I., Horibe H., Matsumoto A., Macromolecules, 2014, 47(3), 937—943
[4]	Zhang Y.W., Huang W., Zhou Y. F., Yan D. Y.,Chem. Commun., 2007, (25), 2587—2589
[5]	Liu C., Gao C., Yan D. Y., Macromolecules, 2006, 39(23), 8102—8111
[6]	Frey H., Haag R., Rev. Mol. Biotechnol., 2002, 90, 257—267
[7]	He Q., Bai F., Yang J., Lin H., Huang H., Gui Y., Li Y., Thin Solid Films, 2002, 417, 183—187
[8]	Shi W.F., Acta Polym. Sinica, 1997, (5), 549—554(施文芳. 高分子学报, 1997, (5), 549—554)
[9]	Gu X.R., Zhu Y. P., Gel Chemistry, Chemical Industry Press, Beijing, 2005
	(顾雪蓉, 朱育平. 凝胶化学, 北京:化学工业出版社, 2005)
[10]	Xu K., Chen Q., Xiang S., Yue Y. M., Zhang W. D., Wang P. X., Chem. J. Chinese Universities, 2006, 27 (12),2417—2421
	(徐昆, 陈强, 项盛, 岳玉梅, 张文德, 王丕新. 高等学校化学学报, 2006, 27(12), 2417—2421)
[11]	Yamanlar S., Sant S., Boudou T., Biomaterials, 2011, 32(24), 5590—5599
[12]	Mukae K., You H. B., Okano T., Kim S. W., Polym. J., 1990, 22, 206—217
[13]	Na Y. H., Kurokawa T., Katsuyama Y., Tsukeshiba H., Gong J. P., Osada Y., Okabe S., Karino T., Shibayama M., Macromolecules, 2004, 37(14), 5370—5374
[14]	Okumura Y., Ito K., Adv. Mater., 2001, 13(7), 485—487
[15]	Shibayama M., Suda J., Karino T., Okabe S., Takehisa T., Haraguchi K., Macromolecules, 2004, 37(25), 9606—9612
[16]	Tao L. S., Takayuki K., Shinya K., Abu B. I., Taigo A., Koshiro S., Anamul H., Tasuku N., Gong J. P., Nat. Mater., 2013, 12(10), 932—937
[17]	Li P. C., Xu K., Tan Y., Lu C. G., Li Y. L., Wang P. X., Polymer, 2013, 54(21), 5830—5838
[18]	Li P. C., Xu K., Tan Y., Lu C. G., Li Y. L., Wang H. W., Liang X. C., Wang P. X., RSC Advances, 2014, 4(71), 37812—37815
[19]	Deng S., Wang R., Xu H., Jiang X., Yin J., J. Mater. Chem., 2012, 22(19), 10055—10061
[20]	Lutz P. J., Macromo. Symp., 2001, 164(1), 277—292
[21]	Wang Q., Mynar J. L., Yoshida M., Lee E., Lee M., Kou O., Kinbara K., Aida T., Nature, 2010, 463(7279), 339—343
[22]	Hobson L. J., Feast W. J., Polymer, 1999, 40(5), 1279—1297
[23]	GB/T 1041-2008, Plastics-Detemination of Compressive Properties, Standards Press of China, Beijing, 2008
	(中国国家标准化管理委员会, GB/T1041-2008, 塑料压缩性能的测定, 北京, 中国标准出版社, 2008)
[24]	Dai X., Zhang Y., Gao L., Bai T., Wang W., Cui Y., Liu W., Adv Mater., 2015, 27, 3566—3571
[25]	Varley R. J., Tian W., Polym. Int., 2004, 53(1), 69—77
[26]	Xia M., Luo Y. J., Zhang W. S., Eng. Plast. Appl., 2007, 35(3), 12—15
	(夏敏, 罗运军, 张文栓. 工程塑料应用, 2007, 35(3), 12—15)
[27]	Xu K., Wang J. H., Chen Q., Yue Y. M., Zhang W. D., Wang P. X., J. Colloid. Interf. Sci., 2008, 321(2), 272—278
[28]	Xue D. Y., Wang J. H., Su X. F., Xu K, Wu X. L., Zhang W. D., Wang P. X., Chem. J. Chinese Universities, 2008, 29(1), 212—216
	(薛冬桦, 王记华, 苏雪峰, 徐昆, 吴修利, 张文德, 王丕新. 高等学校化学学报, 2008, 29(1), 212—216)