离子交联纳米复合高强度水凝胶的制备与性能

游曼可; 周卿云; 柴子铧; 王大威; 吴江渝; 曾小平

离子交联纳米复合高强度水凝胶的制备与性能

1.
武汉工程大学　材料科学与工程学院, 武汉 430205
2.
湖北师范大学文理学院校团委, 黄石 435109

基金项目: 生物无机化学与药物湖北省重点实验室开放基金(BCMM2020003)

详细信息

通讯作者:
曾小平，博士，副教授，研究生导师，研究方向为智能响应水凝胶　E-mail: xpzeng@wit.edu.cn

中图分类号: TB332
计量
- 文章访问数: 29
- HTML全文浏览量: 26
- 被引次数: 0
出版历程
- 收稿日期: 2024-07-02
- 修回日期: 2024-07-28
- 录用日期: 2024-08-03
- 网络出版日期: 2024-08-24

Preparation and properties of ionic crosslinked nanocomposite high strength hydrogel

1.
School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430205, China
2.
Youth League Committee, College of Arts and Science of Hubei Normal University, Huangshi 435109, China

Funds: Open Fund of Hubei Key Laboratory of Bioinorganic Chemistry & Materia Medica (BCMM2020003)

摘要

摘要: 通过自由基聚合法和盐溶液浸泡法相结合，制备了一种综合性能良好的离子交联纳米复合水凝胶。首先用水溶性短链壳聚糖(CS)改性埃洛石纳米管(HNTs)，再与丙烯酰胺(AM)、丙烯酸(AA)等经过热引发自由基聚合得到纳米复合水凝胶基体，随后浸泡Fe(NO₃)₃溶液、Na₂SO₄溶液，得到力学性能优异、具有独特抗溶胀性且抗冻的离子交联纳米复合水凝胶。FTIR及TEM结果证实形成了CS修饰HNTs的结构，复合水凝胶的SEM结果显示浸泡离子后结构变得更加紧密、孔洞尺寸明显减少。考察了不同含量的AA、HNTs对复合水凝胶力学性能的影响。结果表明，当CS为2 wt%，AA占单体总量的12 mol%、AM占88 mol%，HNTs为3.5 wt%且浸泡了Fe³⁺和$\text{SO}_{4}^{2-} $离子溶液时，水凝胶的综合力学性能最佳，拉伸强度与断裂伸长率分别达到3.96 MPa与553%，85%应变下的抗压强度为13.4 MPa，且经过去离子水浸泡48小时后，拉伸强度增长到5.64 MPa，模量高达15 MPa，为设计和开发强韧水凝胶提供了新策略。
- 埃洛石纳米管 /
- 复合水凝胶 /
- 离子交联 /
- 双网络 /
- 高强度
Abstract: A high-performance ion crosslinked nanocomposite hydrogel was successfully synthesized by integrating free radical polymerization with salt solution immersion. Initially, halloysite nanotubes (HNTs) were modified with water-soluble short chain chitosan (CS), followed by the formation of the nanocomposite hydrogel matrix through thermal initiated radical polymerization with acrylamide (AM), acrylic acid (AA), and other components. Subsequently, soaking the hydrogel in Fe (NO₃)₃ and Na₂SO₄ solutions resulted in the formation of an ion crosslinked nanocomposite hydrogel with superior mechanical properties, unique anti-swelling characteristics, and frost resistance. FTIR and TEM analyses confirmed the formation of the HNTs @CS structure. SEM observations of the composite hydrogel revealed a more compact structure and significantly reduced pore size post-ion immersion. The impact of varying AA and HNTs contents on the mechanical properties of the composite hydrogels was investigated. Optimal results are obtained when CS is 2 wt%, AA accounts for 12 mol% of the total monomer, AM accounts for 88 mol%, HNTs is 3.5 wt%, and immersion in Fe³⁺ and $\text{SO}_{4}^{2-} $ ion solutions, yielding the best comprehensive mechanical properties with a tensile strength of 3.96 MPa, elongation at break of 553%, and compressive strength of 13.4 MPa at 85% strain. Following a 48-hour deionized water soaking period, the tensile strength increases to 5.64 MPa, and the modulus reaches 15 MPa, showcasing a new strategy for the design and development of robust and resilient hydrogels.
- halloysite nanotubes /
- composite hydrogel /
- ion crosslinking /
- double network /
- high strength

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图 1 埃洛石纳米管(HNTs)@壳聚糖(CS)制备流程示意图

Figure 1. Schematic diagram of halloysite nanotubes (HNTs)@chitosan (CS) preparation process

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图 2 HNTs @CS(左)与HNTs分散液(右)的稳定性

Figure 2. Stability of HNTs @CS (left) and HNTs dispersion (right)

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图 3 CS、HNTs和HNTs @CS的红外光谱

Figure 3. FTIR spectrums of CS, HNTs, and HNTs @CS

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图 4 HNTs(ab)和HNTs @CS(cd)的透射电镜图像

Figure 4. TEM images of HNTs (ab) and HNTs @CS (cd)

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图 5 DN-gel制备流程示意图

Figure 5. Schematic diagram of DN-gel preparation process

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图 6 纳米复合凝胶基体(ab)和DN-gel(cd)扫描电镜图像

Figure 6. SEM image of nano composite gel matrix (ab) and DN-gel (cd)

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图 7 DN-gel(a)打结(b)回弹和(c)悬挂反应釜

Figure 7. DN-gel (a) knotting (b) rebound and (c) suspension reaction kettle

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图 8 AA含量对水凝胶(a)应力应变曲线(b)模量(c)断裂强度(d)断裂伸长率的影响

Figure 8. Effect of AA content on (a) stress-strain curve (b) modulus (c) breaking strength (d) breaking elongation of hydrogel

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图 9 HNTs含量对水凝胶(a)断裂强度、断裂伸长率(b)模量影响

Figure 9. Effect of HNTs content on (a) breaking strength and elongation at break (b) modulus of hydrogel

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图 10 离子交联前后水凝胶压缩应力-应变曲线

Figure 10. Compressive stress-strain curves of hydrogels before and after ionic crosslinking

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图 11 DN-gel的(a)压缩循环曲线及(b)每个压缩循环应变50%时应力变化曲线

Figure 11. (a) Compression cycle curve of and (b) Stress variation curve at 50% strain per compression cycle DN-gel

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图 12 离子交联前后水凝胶溶胀性能变化曲线

Figure 12. Change curve of swelling property of hydrogel before and after ionic crosslinking

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图 13 去离子水浸泡前后DN-gel力学性能的变化曲线(a)应力应变曲线(b)模量

Figure 13. Changes in mechanical properties of DN-gel before and after immersion in deionized water (a) stress-strain curve (b) modulus

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图 14 低温下水凝胶的柔性变化示意图

Figure 14. Schematic diagram of flexibility change of hydrogel at low temperature

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