基于分子动力学的环氧树脂与固化剂及地层矿物间的作用模拟

董浩安; 李志勇; 张金波; 金星宇; 岑昊天; 徐瑞星

doi:10.12358/j.issn.1001-5620.2025.03.001

基于分子动力学的环氧树脂与固化剂及地层矿物间的作用模拟

doi: 10.12358/j.issn.1001-5620.2025.03.001

1.
中国石油大学(北京)石油工程学院, 北京 102249
2.
中国石油集团长城钻探工程有限公司, 北京 100012

基金项目: 中石油集团重大科技专项《油田用化工新材料产品开发》子课题三“油田井筒工作液关键化学材料的开发与应用”（2020E−2803）。

详细信息

作者简介:
董浩安，1994年生，在读博士，主要从事钻井液优化设计、储层保护和钻井废弃物处理等研究。E-mail：496498778@qq.com

通讯作者:
李志勇，博士生导师，从事钻井液优化设计、储层保护和钻井废弃物处理等研究。E-mail：lzyktz2198@163.com。

中图分类号: TE254.4
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出版历程
- 收稿日期: 2024-12-11
- 修回日期: 2025-01-26
- 刊出日期: 2025-06-12

Simulation of Action between Epoxy Resin and Solidifier/Formation Minerals Based on Molecular Dynamics

1.
School of Petroleum Engineering, China University of Petroleum, Beijing 102249
2.
CNPC Great Wall Drilling Engineering Co., Ltd., Beijing 100012

摘要

摘要: 研究环氧树脂材料的固化过程以及其与地层矿物之间的相互作用，对于其在石油领域的应用具有重要的理论意义。然而，以往的研究主要集中于环氧树脂材料自身的性质，忽视了其与地层的相互作用。为了深入探讨环氧树脂材料的固化过程及其与地层矿物之间的相互作用，该研究基于分子模拟方法，以E51环氧树脂分子和不同种固化剂为研究对象，计算了其分子间的静电势、作用能以及固化产物与地层矿物之间的相互作用能。研究结果表明，环氧树脂分子中的环氧基团具有明显的负静电势，数值为−0.060 Hartree/e，而固化剂分子中的活泼氢原子则具有明显的正电势，数值在0.053～0.126 Hartree/e之间。此外，环氧树脂与不同固化剂分子间存在相互吸引作用，其相互作用能范围为−0.446～−29.306 kcal/mol；交联后，分子间的相互作用能下降至−80.987～−110.844 kcal/mol之间。最后，环氧树脂交联产物与地层矿物之间也存在显著的相互吸引作用，其中单个树脂分子与方解石矿物的相互作用能在−49.795～−173.187 kcal/mol之间，与白云石矿物的相互作用能在−44.604～−147.307 kcal/mol之间。该研究的结果为环氧树脂在石油天然气工业中的应用提供了理论基础，所采用的研究方法也可用于优化环氧树脂类添加剂的设计。
- 分子模拟 /
- 环氧树脂 /
- 地层矿物 /
- 静电势 /
- 相互作用能
Abstract: Studying on the hardening process of epoxy resin and the interaction between epoxy and formation minerals has important theoretical significance for their application in petroleum industry. Studies on epoxy in the past mainly focused on the properties of epoxy resin itself, with its interaction with formations being ignored. To extensively investigate the hardening process of epoxy and the interaction between epoxy and formation minerals, molecular simulation method was used to study the molecules of E51 epoxy resin and several hardening agents. The electrostatic potential and interaction energy between the molecules of epoxy and the molecules of the hardening agents, as well as the interaction energy between the products of the hardening process and the formation minerals, were calculated. It was found that the epoxy groups in the epoxy resin molecules have a significant negative potential, which is −0.060 Hartree/e, while the active hydrogen atoms in the molecules of the hardening agents have significant positive potential, ranging from 0.053 Hartree/e to 0.126 Hartree/e. Moreover, mutual attraction exists between the molecules of the epoxy resin and the molecules of the hardening agents, the energy of the attraction ranges from −0.446 kcal/mol to −29.306 kcal/mol. After crosslinking, the interaction energy between the molecules was reduced to −80.987 kcal/mol to −110.844 kcal/mol. Finally, significant mutual attraction also exists between the crosslinking product of the epoxy resin and formation minerals; the interaction energy between a single epoxy molecule and the calcite mineral in the formation ranges from −49.795 kcal/mol to −173.187 kcal/mol, while the interaction energy between a single epoxy molecule and the dolomite mineral in the formation ranges from −44.604 kcal/mol to −147.307 kcal/mol. These research achievements have provided a theoretical base for the application of epoxy resin in oil and natural gas industry, and the research method adopted can be used in optimizing the design of epoxy resin additives.
- Molecular simulation /
- Epoxy resin /
- Formation mineral /
- Electrostatic potential /
- Interaction energy

HTML全文

图 1 环氧树脂、不同固化剂分子建模及静电势计算

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图 2 胺类固化剂与环氧树脂相互作用示意图

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图 3 交联后的环氧树脂分子与地层矿物间相互作用模拟

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表 1 环氧树脂及固化剂分子静电势计算

名称	静电势/（Hartree·e⁻¹）
名称	最大	最小
环氧树脂E51	0.039 035	−0.060 107
双氰胺（DICY）	0.126 240	−0.087 255
4,4'-二氨基二苯基甲烷（DDM）	0.071 624	−0.057 469
3,3'-二乙基-4,4'- 二氨基二苯甲烷（DEDDM）	0.068 772	−0.059 088
3,3'-二氨基二苯砜（3,3DDS）	0.083 658	−0.068 687
4,4'-二氨基二苯砜（4,4DDS）	0.089 912	−0.074 753
3-二乙胺基丙胺（DEAPA）	0.053 483	−0.076 348
二亚乙基三胺	0.055 256	−0.079 466

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表 2 交联前环氧树脂与各固化剂间分子作用能

固化剂	E_AB/Hartree	E_A/Hartree	E_B/Hartree	作用能/（kcal·mol⁻¹）	单个树脂分子作用能/（kcal·mol⁻¹）
双氰胺	−2526.14	−2228.80	−297.34	−0.89	−0.45
DDM	−2841.49	−2228.80	−612.69	−2.78	−1.39
DEDDM	−2998.56	−2228.80	−769.75	−2.81	−1.41
3,3DDS	−3350.68	−2228.80	−1121.79	−57.14	−28.57
4,4DDS	−3350.69	−2228.80	−1121.80	−58.61	−29.31
DEAPA	−2615.42	−2228.80	−386.62	−3.51	−1.75
二亚乙基三胺	−2552.94	−2228.80	−324.13	−5.88	−2.94

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表 3 交联后环氧树脂与各固化剂间分子作用能

固化剂	E_AB/Hartree	E_A/Hartree	E_B/Hartree	作用能/（kcal·mol⁻¹）	单个树脂分子作用能/（kcal·mol⁻¹）
双氰胺	−2526.24	−2229.90	−296.00	−211.16	−105.58
DDM	−2841.57	−2229.94	−611.37	−161.97	−80.99
DEDDM	−2998.63	−2229.96	−768.43	−155.35	−77.67
3,3DDS	−3350.84	−2229.96	−1120.52	−219.17	−109.58
4,4DDS	−3350.75	−2229.92	−1120.48	−221.69	−110.84
DEAPA	−2615.49	−2229.93	−385.28	−176.59	−88.30
二亚乙基三胺	−2553.05	−2229.97	−322.79	−178.51	−89.26

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表 4 交联后环氧树脂-方解石分子间作用能

固化剂	E_AB/Hartree	E_A/Hartree	E_B/Hartree	作用能/（kcal·mol⁻¹）	单个树脂分子作用能/（kcal·mol⁻¹）
双氰胺	−367 961.44	−364 495.69	2706.21	−6171.97	−61.72
DDM	−369 891.37	−365 585.24	673.38	−4979.51	−49.80
DEDDM	−367 049.70	−364 839.98	3005.20	−5214.92	−52.15
3,3DDS	−368 504.58	−364 888.47	2574.26	−6190.37	−61.90
4,4DDS	−368 221.60	−363 507.82	4180.85	−8894.63	−88.95
DEAPA	−336 115.01	−359 373.68	40 577.39	−17318.71	−173.19
二亚乙基三胺	−365 579.78	−365 212.85	5243.81	−5610.74	−56.11

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表 5 交联后环氧树脂-白云石分子间作用能

固化剂	E_AB/Hartree	E_A/Hartree	E_B/Hartree	作用能/（kcal·mol⁻¹）	单个树脂分子作用能/（kcal·mol⁻¹）
双氰胺	−392 645.53	−389 742.54	2531.26	−5434.26	−54.34
DDM	−394 792.62	−390 534.88	432.30	−4690.04	−46.90
DEDDM	−391 613.49	−389 788.12	2864.97	−4690.34	−46.90
3,3DDS	−393 370.18	−390 746.30	2285.05	−4908.93	−49.09
4,4DDS	−391 789.88	−388 670.10	4051.63	−7171.40	−71.71
DEAPA	−359 170.31	−383 661.55	39222.01	−14730.77	−147.31
二亚乙基三胺	−389 627.68	−390 196.08	5028.79	−4460.39	−44.60

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