磁性PASP/PAM半互穿水凝胶的制备及性能

doi:10.16085/j.issn.1000-6613.2022-1477

摘要/Abstract

摘要：

以聚天冬氨酸（PASP）和聚丙烯酰胺（PAM）为原料，利用原位共沉淀法并结合半互穿技术在水凝胶上负载纳米Fe₃O₄粒子，制备磁性 PASP/PAM 半互穿水凝胶，采用红外光谱（FTIR）、热重分析（TG）、扫描电镜（SEM）、透射电镜（TEM）、能谱仪（EDS）等对水凝胶进行表征，并测试了水凝胶的磁学性能、磁响应时间、溶胀性能及温度敏感性。结果表明：所制备的磁性PASP/PAM水凝胶具有优异的热稳定性，纳米Fe₃O₄粒子呈现球状，粒径约18nm，且分散得比较均匀。磁滞回线整体呈“S”形，最大饱和磁强度为0.35emu/g（1emu/g=1A·m²/kg），且具有超顺磁性，磁响应时间表明Fe₃O₄的浓度以1.0mol/L为宜。纳米Fe₃O₄浓度1.5mol/L和0.5mol/L时平衡溶胀率分别为38g/g和47g/g，且温度低于45℃时，磁性水凝胶的溶胀率会出现温度敏感性和正向的特征。

关键词: 磁性, 聚天冬氨酸, 半互穿, 水凝胶

Abstract:

Using polyaspartic acid (PASP) and polyacrylamide (PAM) as raw materials, magnetic PASP/PAM semi-interpenetrating (semi-IPN) hydrogels loaded with nano Fe₃O₄ particles were prepared by in-situ coprecipitation and semi-interpenetrating technology. The hydrogels were characterized by FTIR, TG, SEM, TEM and EDS. The magnetic properties, swelling properties and temperature sensitivity of the hydrogels were tested. The results showed that the prepared magnetic hydrogel had excellent thermal stability, and the nano Fe₃O₄ particles were spherical with a particle size of about 18nm and evenly dispersed. The hysteresis loop was “S” shaped, the maximum saturated magnetic intensity was 0.35emu/g, and it had superparamagnetic. The magnetic response time showed that the appropriate concentration of Fe₃O₄ was 1.0mol/L. When the concentration of nano Fe₃O₄ was 1.5mol/L and 0.5mol/L, the equilibrium swelling rate was 38g/g and 47g/g, respectively, and when the temperature was lower than 45℃, the swelling rate of hydrogels showed temperature sensitive and positive characteristics.

Key words: magnetism, polyaspartic acid, semi-interpenetrating, hydrogel

中图分类号:

TQ322.4

冯琬淇, 哈尼夏·巴合提null, 葛雨璇, 赵俭波. 磁性PASP/PAM半互穿水凝胶的制备及性能[J]. 化工进展, 2023, 42(6): 3130-3137.

FENG Wanqi, HANISHA·Bhahti , GE Yuxuan, ZHAO Jianbo. Preparation and properties of magnetic polyaspartic acid/polyacrylamide semi-interpenetrating hydrogel[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3130-3137.

图/表 11

图1 磁性PASP/PAM半互穿水凝胶结构模拟图

图2 水凝胶红外光谱图

图3 磁性PASP/PAM半互穿水凝胶的 TG 曲线

图4 半互穿水凝胶扫描电镜照片

图5 磁性PASP/PAM半互穿水凝胶TEM照片

图6 磁性PASP/PAM半互穿水凝胶mapping谱图

图7 磁性PASP/PAM半互穿水凝胶EDS能谱

图8 含不同Fe离子浓度的磁性PASP/PAM半互穿水凝胶磁滞回线

图9 磁场响应时间测试曲线

图10 不同纳米Fe3O4负载量磁性水凝胶的溶胀性能曲线

图11 不同纳米Fe3O4负载量磁性水凝胶的温敏曲线

参考文献 25

1	LI Z, LI Y, CHEN C, et al. Magnetic-responsive hydrogels: From strategic design to biomedical applications[J]. Journal of Controlled Release, 2021, 335:541-556.
2	XU F, WU C, RENGARAJAN V, et al. Three-dimensional magnetic assembly of microscale hydrogels[J]. Advanced Materials, 2011, 23(37):4254-4260.
3	范治平, 程萍, 张德蒙, 等. 天然高分子基刺激响应性智能水凝胶研究进展[J]. 材料导报, 2020, 34(21): 21012-21025.
	FAN Zhiping, CHENG Ping, ZHANG Demeng, et al. Progress on stimulus responsive smart hydrogels based on natural polymers [J]. Materials Reports, 2020, 34(21): 21012-21025.
4	YU P, ZHOU G, YANG R, et al. Green synthesis of ion-imprinted macroporous composite magnetic hydrogels for selective removal of nickel (‍Ⅱ) from wastewater[J]. Journal of Molecular Liquids, 2021, 344:117963.
5	SATARKAR N S, HILT J Z. Magnetic hydrogel nanocomposites for remote controlled pulsatile drug release[J]. Journal of Controlled Release, 2008, 130(3): 246-251.
6	POPA E G, SANTO V E, RODRIGUES M T, et al. Magnetically-responsive hydrogels for modulation of chondrogenic commitment of human adipose-derived stem cells[J]. Polymers, 2016, 8(2): 28.
7	OZAY O, EKICI S, BARAN Y, et al. Utilization of magnetic hydrogels in the separation of toxic metal ions from aqueous environments[J]. Desalination, 2010, 260(1/2/3): 57-64.
8	赵俭波, 魏军, 曹辉, 等. 聚天冬氨酸水凝胶的研究与应用进展[J]. 化工进展, 2019, 38(7): 3355-3364.
	ZHAO Jianbo, WEI Jun, CAO Hui, et al. The research and application progress of PASP hydrogel[J]. Chemical Industry and Engineering Progress, 2019, 38(7): 3355-3364.
9	LIU W, ZENG H, XIA Z, et al. Streptomyces polyasparticus sp. nov. isolated from cotton field soil by a medium applied with polyaspartic acid[J]. Antonie van Leeuwenhoek, 2021, 114: 777-786.
10	ZHAO J, LIANG X, CAO H, et al. Preparation of injectable hydrogel with near-infrared light response and photo-controlled drug release[J]. Bioresources and Bioprocessing, 2020, 7(1): 1.
11	董怡麟, 张浩, 陈金龙. 化妆品级聚天冬氨酸钠的制备[J]. 应用化学, 2020, 37(8): 883-888.
	DONG Yilin, ZHANG Hao, CHEN Jinlong. Preparation of cosmetic-grade sodium polyaspartate[J]. Chinese Journal of Applied Chemistry, 2020, 37(8): 883-888.
12	RANA A, KUMAR A, SHARMA G, et al. Pharmaceutical pollutant as sacrificial agent for sustainable synergistic water treatment and hydrogen production via novel Z-scheme Bi₇O₉I₃/B₄C heterojunction photocatalysts[J]. Journal of Molecular Liquids, 2021, 343: 117652.
13	杜亮, 卢福麟, 吴昌强. 聚天冬氨酸-多巴胺接枝聚合物-铁（‍Ⅲ）配合物用于磁共振可视化光热治疗剂[J]. 生物医学工程学杂志, 2022, 39(2): 398-404.
	DU Liang, LU Fulin, WU Changqiang. Polyaspartic acid grafted dopamine polymer chelated Fe³⁺for magnetic resonance imaging visual photothermal therapy agent[J]. Journal of Biomedical Engineering, 2022, 39(2): 398-404.
14	张浩, 胡晓婷, 杨宁, 等. 胶原温敏半互穿水凝胶的制备及其对L929细胞行为的影响[J]. 高分子学报, 2016(3): 300-306.
	ZHANF Hao, HU Xiaoting, YANG Ning, et al. Thermo-sensitive semi-interpenetrating collagen hydrogels and effects on L929 cell’s behavior[J]. Acta Polymerica Sinica, 2016(3): 300-306.
15	ZHU B, MA D, WANG J, et al. Structure and properties of semi-interpenetrating network hydrogel based on starch[J]. Carbohydrate Polymers, 2015, 133: 447-455.
16	崔莉, 贾军芳, 熊子豪, 等. 羧甲基壳聚糖/海藻酸钠半互穿网络水凝胶的制备及性能研究[J]. 高分子学报, 2014(3): 361-368.
	CUI Li, JIA Junfang, XIONG Zihao, et al. Preparation and properties of carboxymethyl chitosan and sodium alginate semi-interpenetrating hydrogels[J]. Acta Polymerica Sinica, 2014(3): 361-368.
17	赵俭波, 罗楠, 曹辉. PASP/PAA互穿网络水凝胶的制备及其作为保水剂的应用[J]. 精细化工, 2020, 37(8): 1601-1607, 1635.
	ZHAO Jianbo, LUO Nan, CAO Hui. Preparation of PASP/PAA interpenetrate network hydrogel and its application in water retaining agent[J]. Fine Chemicals, 2020, 37(8): 1601-1607， 1635.
18	HU X, WANG Y, ZHANG L, et al. Design of a pH-sensitive magnetic composite hydrogel based on salecan graft copolymer and Fe₃O₄@SiO₂ nanoparticles as drug carrier[J]. International Journal of Biological Macromolecules, 2018, 107: 1811-1820.
19	丁齐, 邢晓东, 李丽霞. 多孔半互穿温敏水凝胶点击反应固定化酶[J]. 化工进展, 2014, 33(4): 971-976.
	DING Qi, XING Xiaodong, LI Lixia. Enzyme immobilization on porous semi-interpenetrating thermosensitive hydrogel carriers via thiol-based click reaction[J]. Chemical Industry and Engineering Progress, 2014, 33(4): 971-976.
20	王毓, 任俊鹏, 赵君, 等. 磁性壳聚糖半互穿热膨胀水凝胶的制备及对Cr(Ⅵ)的吸附性能[J]. 材料导报, 2021, 35(10): 10205-10210.
	WANG Yu, REN Junpeng, ZHAO Jun, et al. Preparation of magnetic chitosan semi-interpenetrating thermo-swelling hydrogels and its adsorption for Cr(‍Ⅵ)[J]. Materials Reports, 2021, 35(10): 10205-10210.
21	ZHAO J, WEI J, CAI D, et al. Polyaspartic acid-derived micro-/mesoporous carbon for ultrahigh H₂ and CH₄adsorption[J]. ACS Omega, 2020, 5: 10687-10695.
22	RODRIGUES S H, LIMA I S, NERIS L M L, et al. Superabsorbent hydrogels based to polyacrylamide/cashew tree gum for the controlled release of water and plant nutrients[J]. Molecules, 2021, 26(9): 2680.
23	毛晨, 鄂毅, 邹姝燕, 等. 交变电磁场对CoFe₂O₄/Fe³⁺/聚丙烯酸水凝胶自修复性能的影响[J]. 高分子材料科学与工程, 2022, 38(3): 18-23， 31.
	MAO Chen, Yi E, ZOU Shuyan, et al. Effect of alternating electromagnetic field on the self-healing properties of CoFe₂O₄/Fe³⁺/polyacrylic acid hydrogel[J]. Polymer Materials Science and Engineering, 2022, 38(3): 18-23， 31.
24	赵璐婷, 张健, 李娜, 等. 半纤维素基磁性水凝胶的制备及其对染料吸附性能的研究[J]. 材料工程, 2020, 48(11): 85-91.
	ZHAO Luting, ZHANG Jian, LI Na, et al. Preparation of hemicellulose-based magnetic hydrogel and its adsorption properties for dye[J]. Journal of Materials Engineering, 2020, 48(11): 85-91.
25	CHEN Y, HAO Y, LI S, et al. Preparation of hydroxybutyl starch with a high degree of substitution and its application in temperature-sensitive hydrogels[J]. Food Chemistry, 2021, 355: 129472.

[1]	王少凡, 周颖, 郝康安, 黄安荣, 张如菊, 吴翀, 左晓玲. 具有pH响应性的自愈合蓝光水凝胶[J]. 化工进展, 2023, 42(9): 4837-4846.
[2]	于丁一, 李圆圆, 王晨钰, 纪永升. pH响应性木质素水凝胶的制备及药物控释[J]. 化工进展, 2023, 42(6): 3138-3146.
[3]	刘宇龙, 姚俊虎, 舒闯闯, 佘跃惠. 磁性Fe₃O₄纳米颗粒的生物合成及其在提高采收率中的应用[J]. 化工进展, 2023, 42(5): 2464-2474.
[4]	刘念, 陈葵, 武斌, 纪利俊, 吴艳阳, 韩金玲. 蛋黄-壳介孔磁性炭微球的制备及其对红霉素的高效吸附[J]. 化工进展, 2023, 42(5): 2724-2732.
[5]	张赫, 李小可, 熊颖, 文劲. 基于水凝胶界面光蒸发的压裂返排液脱盐降污处理[J]. 化工进展, 2023, 42(2): 1073-1079.
[6]	张英杰, 陆加越, 王方刚. 新型磁性树脂的合成及其在水中去除Cu(Ⅱ)的性能[J]. 化工进展, 2023, 42(10): 5558-5566.
[7]	刘慧慧, 史笑飞, 王倩男, 刘锦博, 张静. pH响应性磁性介孔纳米载药系统的制备[J]. 化工进展, 2023, 42(10): 5390-5398.
[8]	仉洁, 王旭东, 杨逸飞, 任玥, 陈立成. 响应面优化温敏水凝胶汲取剂的制备及性能[J]. 化工进展, 2023, 42(10): 5363-5372.
[9]	叶好, 胡平, 王策, 刘勇. 磁性纤维电磁波吸收剂研究进展[J]. 化工进展, 2023, 42(10): 5310-5321.
[10]	王子航, 梁瑞升, 邓超和, 王佳韵. 离子凝胶复合吸附剂的制备及空气取水性能[J]. 化工进展, 2022, 41(S1): 389-396.
[11]	岳瑶, 蒲梦凡, 王文瑞, 赵俭波, 曹辉. 聚天冬氨酸凝胶的制备及生物降解性[J]. 化工进展, 2022, 41(8): 4491-4497.
[12]	邱艺娟, 林佳伟, 秦济锐, 吴嘉茵, 林凤采, 卢贝丽, 唐丽荣, 黄彪. 双重动态共价键交联纳米纤维素导电水凝胶及其柔性传感器[J]. 化工进展, 2022, 41(8): 4406-4416.
[13]	常炜, 史秋兰, 赵正阳, 王瑞婷, 王志福, 赵俭波. 高内相乳液法制备聚丙烯酰胺多孔水凝胶及应用[J]. 化工进展, 2022, 41(7): 3832-3839.
[14]	蒋华义, 胡娟, 齐红媛, 游琰真, 王玉龙, 武哲. 磁性纳米粒子类型和质量浓度对微波热解含油污泥的影响[J]. 化工进展, 2022, 41(7): 3908-3914.
[15]	陈彰旭, 陈冰冰, 王荣财, 叶晨光, 郑炳云. β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄复合水凝胶材料的制备及其应用[J]. 化工进展, 2022, 41(6): 3146-3154.