功能单体配比对Ni2+配位增强AA/AM共聚物基暂堵剂用水凝胶的性能影响研究

Effect of functional monomer ratio on the performance of Ni2+ coordination-enhanced AA/AM copolymer hydrogels for temporary plugging applications

  • 摘要: 为解决传统暂堵聚合物凝胶体系吸水性能与力学强度难以兼顾的问题,并阐明丙烯酸(AA)/丙烯酰胺(AM)功能单体配比通过调控Ni2+配位交联网络结构进而影响水凝胶吸水—力学协同响应行为的作用机制。采用自由基聚合法制备Ni2+配位增强丙烯酸(AA)/丙烯酰胺(AM)共聚物基暂堵剂用水凝胶,通过调控AA/AM单体配比研究其对网络结构及吸水—力学响应行为的影响。傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)结果表明,Ni2+与羧酸盐基团形成Ni—O动态配位键,在共聚网络中构建附加离子交联结构,提高了体系结构与热稳定性。随着AM含量增加,凝胶吸水倍率呈先升后降趋势,而承压强度与吸水性能表现出明显负相关关系,反映出配位交联密度、链柔顺性及链缠结的协同调控作用。当m(AA)∶m(AM)=2∶1时,体系综合性能最佳,在70℃下吸水倍率达4.469 g·g−1,吸水后承压强度达13 KPa,实现吸水性与力学稳定性的平衡优化。体系同时具有良好的流变稳定性与温度适应性,可满足暂堵材料吸水膨胀、承压封堵及解体返排需求,研究结果为Ni2+配位增强AA/AM共聚物基暂堵剂用水凝胶的结构设计与性能调控提供了理论依据。

     

    Abstract: To address the trade-off between swelling capacity and mechanical strength in conventional temporary plugging hydrogels, the effect of the acrylic acid (AA) and acrylamide (AM) monomer ratio on the Ni2+ coordination-crosslinked network and its swelling–mechanical performance was investigated. A Ni2+ coordination-enhanced AA/AM copolymer-based hydrogel for temporary plugging applications was prepared via free radical polymerization. The effects of AA/AM monomer ratio on the network structure and the synergistic swelling–mechanical response behavior were systematically investigated by regulating the functional monomer composition. FTIR and XPS analyses confirmed that Ni2+ participated in network construction through the formation of dynamic Ni–O coordination bonds with carboxylate groups. On the basis of the copolymer network, an additional ionic crosslinking structure was established, which effectively enhanced the structural integrity and thermal stability of the hydrogel system. With increasing AM content, the swelling ratio of the hydrogel exhibited a non-monotonic variation characterized by an initial increase followed by a subsequent decrease. Meanwhile, a pronounced negative correlation between swelling capacity and compressive strength was observed. This behavior was mainly attributed to the synergistic regulation among coordination crosslinking density, polymer chain flexibility, and chain entanglement degree. By optimizing the monomer composition, a balanced network structure capable of coordinating swelling and mechanical performance was achieved. When the mass ratio of AA to AM was 2∶1, the hydrogel displayed the optimal comprehensive performance. Under 70℃ conditions, the swelling ratio reached 4.469 g·g−1, while the compressive strength after swelling achieved 13 KPa, indicating effective synergistic optimization between water absorption capability and mechanical stability. In addition, the hydrogel exhibited stable rheological behavior and favorable temperature adaptability, demonstrating its suitability for demanding reservoir environments. The developed hydrogel system satisfies the functional requirements of temporary plugging materials, including water absorption and expansion, pressure-bearing plugging, and subsequent degradation or flowback removal. This study provides theoretical guidance for the structural design, performance regulation, and practical development of metal-ion coordination-enhanced polymer hydrogels for temporary plugging applications. These findings provide a theoretical basis for the design and performance regulation of Ni2+ coordination-enhanced AA/AM copolymer-based hydrogel.

     

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