醋酸铬-酚醛树脂预聚体/HPAM体系的复合交联反应机理研究

Mechanism of Composite Crosslinking Reaction of Chromium Acetate-phenolic Resin Prepolymer/HPAM System

展转盈 王仙仙 张磊

ZHAN Zhuanying WANG Xianxian ZHANG Lei

复合醋酸铬和酚醛树脂预聚物（PRP）既可以提高HPAM/Cr3+ 凝胶的热稳定性，也可以降低HPAM/PRP凝胶的反应活化能，同时还可以提高凝胶的力学性能。但是，目前关于Cr3+ -PRP 与HPAM的复合交联反应机理尚不清楚。先通过表征Cr3+ -PRP溶液与PRP溶液的性能差异，明确了Cr3+ 与PRP之间的化学反应过程；随后通过对比Cr3+ -PRP/HPAM与Cr3+ /HPAM、PRP/HPAM之间的反应差异，揭示了Cr3+ -PRP/HPAM的复合交联反应机理。在Cr3+ -PRP 溶液中，由于PRP苯环上的羟甲基和酚羟基的活性高于醋酸根，从而形成了一种新的多核羟桥络合物离子（Cr3+ -PRP络合物）。Cr3+ -PRP/HPAM体系发生多重复合反应，首先是Cr3+ -PRP络合物中的部分Cr3+ 与HPAM产生交联反应，随后是络合物中的剩余Cr3+ 和全部的PRP与聚合物同时发生交联反应，而且Cr3+ /羧基的交联反应与PRP/酰胺基团的交联反应会相互影响。实验结果促进了对Cr3+ -PRP/HPAM体系的交联本质的认识，为其高效应用奠定了一定的理论基础。

Based on the respective characteristics of gel conformance control systems of HPAM/Cr3+ and HPAM/phenolic resin prepolymer，the chromic acetate and phenolic resin prepolymer（PRP）composite can not only improve the thermal stability of HPAM/Cr3+ gel，but also promote the better application of HPAM/PRP gel in low-medium temperature oil reservoirs. Besides，it can improve the mechanical properties of the HPAM gel. However，the mechanism of the composite cross-linking reaction between Cr3+ -PRP and HPAM is still unclear. Therefore，by characterizing the performance differences between Cr3+ -PRP solution and PRP solution，the chemical reaction process between Cr3+ and PRP was studied. Thus，by comparing the reaction differences between Cr3+ -PRP/HPAM and Cr3+ /HPAM，PRP/HPAM，the mechanism of the composite crosslinking reaction of Cr3+ -PRP/HPAM was revealed. In a Cr3+ -PRP solution，because the hydroxymethyl and phenolic hydroxyl groups on the benzene ring of PRP are more active than acetate，a new polynuclear hydroxyl bridge complex ion（Cr3+ -PRP complex）was formed. The cross-linking reaction between the Cr3+ -PRP complex and HPAM was a multiple complex reaction. At first，part of Cr3+ from the Cr3+ -PRP complex reacted with HPAM，and then the remaining Cr3+ and all PRP in the complex reacted with the polymer at the same time. The cross-linking reaction of Cr3+ and carboxy group could affect the cross-linking reaction of PRP and amide group. The reaction process of Cr3+ -PRP complex with HPAM was different from the superposition of the reaction of Cr3+ /HPAM and PRP/HPAM. The experimental results promoted the understanding of the crosslinking mechanism of Cr3+ -PRP/HPAM system，which could lay a certain theoretical foundation for its efficient application.

10.19346/j.cnki.1000-4092.2022.02.019