颗粒型聚醚：一类新型的非水基泡沫消泡剂

doi:10.3969/j.issn.2097-2806.2025.06.003

摘要/Abstract

摘要：

以聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物和柠檬酸为原料，利用高温缩合-碳化工艺，制备了纳米碳交联的超支化/交联型聚醚。以三乙醇胺单油酸酯/对二甲苯混合物为模型体系，发现所制备的新型聚醚对非水泡沫具有优异的消除能力，30 min消泡率可达86%，消泡速度较无消泡剂体系提高2 000余倍。利用二氧化碳加压，对孤岛采油厂所产原油进行发泡，发现新型聚醚对原油泡沫亦具有良好的消泡能力。该研究为纳米碳混杂的聚醚消泡剂的研发提供了一条新的思路，有望应用于难以大量应用有机硅消泡剂的领域，如石油开采中因大量助剂的使用而形成的泡沫油。

关键词: 颗粒型, 聚醚, 非水基, 泡沫, 消泡剂

Abstract:

Using triblock copolymer poly（ethylene oxide）-poly（propylene oxide）-poly（ethylene oxide） and citric acid as raw materials, a novel polyether was synthesized through condensation-carbonization under high temperature, which had a hyperbranched structure using nanocarbon as the core, or crosslinked morphology connected by nanocarbon. The mixture of triethanolamine monooleate/p-xylene was selected as a model system to produce nonaqueous foam. It was found that the synthesized polyether had a high defoaming efficiency up to 86% within 30 min, demonstrating a defoaming rate over 2 000 times that of the defoamer-free system. Furthermore, the crude oil from Gudao oil production plant was foamed under high pressure of CO₂. The polyether also showed good defoaming efficiency to this foam of crude oil. Our work might provide a new strategy to synthesize nanocarbon-hybridized polyether, which could find applications in cases where defoamers based on organosilicone could hardly be used on a large scale, e.g., the foamed oil produced by the oilfield auxiliary chemicals that are intensively used during oil exploitation.

Key words: particulate, polyether, nonaqueous, foam, defoamer

中图分类号:

TQ423

王玉江, 汤龙皓, 刘晓倩, 冯宁, 李洪光. 颗粒型聚醚：一类新型的非水基泡沫消泡剂[J]. 日用化学工业（中英文）, 2025, 55(6): 700-708.

Yujiang Wang, Longhao Tang, Xiaoqian Liu, Ning Feng, Hongguang Li. Particulated polyether: A novel defoamer for nonaqueous foams[J]. China Surfactant Detergent & Cosmetics, 2025, 55(6): 700-708.

图/表 6

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参考文献 30

[1]	Chandran Suja V, Kar A, Cates W, et al. Foam stability in filtered lubricants containing antifoams[J]. Journal of Colloid and Interface Science, 2020, 567: 1-9.
[2]	林雪松. 某区块泡沫油形成机理及分布规律研究[D]. 大庆: 东北石油大学, 2018.
[3]	Lombardi Lombardi, Roig Sanchez Soledad, Bapat Amar, et al. Nonaqueous foam stabilization mechanisms in the presence of volatile solvents[J]. Journal of Colloid and Interface Science, 2023, 648: 46-55. doi: 10.1016/j.jcis.2023.05.156 pmid: 37295369
[4]	Fameau Anne Laure, Saint Jalmes Arnaud. Non-aqueous foams: Current understanding on the formation and stability mechanisms[J]. Advances in Colloid and Interface Science, 2017, 247: 454-464. doi: S0001-8686(16)30383-9 pmid: 28245904
[5]	胡楠, 胡明明, 李志鑫, 等. 消泡剂的研究进展与展望[J]. 盐科学与化工, 2021, 50: 10-16.
[6]	王敏, 郭睿, 张凯峰, 等. 有机硅消泡剂的合成与应用[J]. 精细化工, 2017, 34: 274-278.
[7]	窦尹辰. 不同结构聚醚改性硅油的制备与消泡性能研究[D]. 西安: 陕西科技大学, 2014.
[8]	J·J·托曼, D·J·奥里尔, G·南斯基维尔, 等. 低起泡蒸馏物燃料调合物: CN200680025838.X[P]. 2008-10-01.
[9]	Cevada Enrique, Fuentes Jessica V, Zamora Edgar Benedicto, et al. Effect of the chemical structure of alkyl acrylates on their defoaming activity in crude oil: experimental and theoretical studies[J]. Energy & Fuels, 2021, 35 (10) : 9047-9058.
[10]	Fraga Assis K, Souza Luiz F I, Magalhães Jeniffer Rayane, et al. Development and evaluation of oil in water nanoemulsions based on polyether silicone as demulsifier and antifoam agents for petroleum[J]. Journal of Applied Polymer Science, 2014, 131 (20) : 40889.
[11]	Xin Xia, Xu Guiying, Zhao Taotao, et al. Dispersing carbon nanotubes in aqueous solutions by a starlike block copolymer[J]. Journal of Physical Chemistry C, 2008, 112: 16377-16384.
[12]	Xin Xia, Xu Guiying, Zhang Zhiqing, et al. Aggregation behavior of star-like PEO-PPO-PEO block copolymer in aqueous solution[J]. European Polymer Journal, 2007, 43: 3106-3111.
[13]	Yang Shan, Zhang Zhiqing, Wang Fang, et al. Surface properties and aggregation behaviors of amphiphilic highly-branched block polyethers in aqueous solution[J]. Journal of Polymer Research, 2013, 20: 205.
[14]	史松, 燕永利, 奚琪, 等. 三乙醇胺油酸酯/对二甲苯溶致液晶的泡沫性能研究[J]. 应用化工, 2022, 51 (5) : 1248-1251, 1255.
[15]	中国石化集团胜利石油管理局. 原油消泡剂通用技术条件: Q/SH1020 2194—2013[S]. 东营: 中国石化集团胜利石油管理局, 2013: 7.
[16]	Kasprzyk Wiktor, Świergosz Wiktor, Romanczyk Piotr P, et al. The role of molecular fluorophores in the photoluminescence of carbon dots derived from citric acid: current state-of-the-art and future perspectives[J]. Nanoscale, 2022, 14 (39) : 14368-14384.
[17]	Georgakopoulos C G, Statheropoulos M, Montaudo G. Pyrolysis pathways of polyethers and a method for the interpretation of the pyrolysis mass spectra of polyethers[J]. Polymer Degradation and Stability, 1998, 61 (3) : 481-491.
[18]	Danil W Boukhvalov, Vladimir Yu Osipov, Danatbek Murzalinov, et al. A comprehensive model of carbon nanodots with 0.21 nm lattice fringes patterns[J]. Carbon, 2024, 225: 119101.
[19]	Ludmerczki Robert, Malfatti Luca, Stagi Luigi, et al. Polymerization-driven photoluminescence in alkanolamine-basedc-dots[J]. Chemistry-A European Journal, 2021, 27: 2543-2551. doi: 10.1002/chem.202004465 pmid: 33196126
[20]	Mondjinou Yawo A, Loren Bradley P, Collins Christopher J, et al. Gd³⁺: DOTa-modified 2-hydroxypropyl-β-cyclodextrin/4-sulfobutyl ether-β-cyclodextrin-based polyrotaxanes as long circulating high relaxivity mri contrast agents[J]. Bioconjugate Chemistry, 2018, 29 (11) : 3550-3560. doi: 10.1021/acs.bioconjchem.8b00525 pmid: 30403467
[21]	Zhang Qing, Wang Ruoyu, Feng Bowen, et al. Photoluminescence mechanism of carbon dots: triggering high-color-purity red fluorescence emission through edge amino protonation[J]. Nature Communication, 2021, 12: 6856-6869.
[22]	Li Jun, Ni Xiping, Zhou Zhihan, et al. Preparation and characterization of polypseudorotaxanes based on block-selected inclusion complexation between poly(propylene oxide) -poly(ethylene oxide) -poly(propylene oxide) triblock copolymers and α-cyclodextrin [J]. Journal of the American Chemical Society, 2003, 125 (7) : 1788-1795.
[23]	Mai Yiyong, Zhou Yongfeng, Yan Deyue, et al. Quantitative dependence of crystallinity on degree of branching for hyperbranched poly[3-ethyl-3- (hydroxymethyl) oxetane][J]. New Journal of Physics, 2005, 7: 42.
[24]	Zhu Xinyuan, Zhou Yongfeng, Yan Deyue. Influence of branching architecture on polymer properties[J]. Journal of Polymer Science Part B-Polymer Physics, 2011, 49 (18) : 1277-1286.
[25]	Magnusson Helene, Malmström Eva, Hult Anders, et al. The effect of degree of branching on the rheological and thermal properties of hyperbranched aliphatic polyethers[J]. Polymer, 2002, 43 (2) : 301-306.
[26]	Alexandridis Paschalis, Alan T Hatton. Poly(ethylene oxide)-poly(propylene oxide) -poly (ethylene oxide) block copolymer surfactants in aqueous solutions and at interfaces: thermodynamics, structure, dynamics, and modeling[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1995, 96: 1-46.
[27]	Friberg S E, Wohn C S, Greene B, et al. A nonaqueous foam with excellent stability[J]. Journal of Colloid and Interface Science, 1984, 101 (2) : 593-595.
[28]	王莉娟, 张高勇, 董金凤, 等. 泡沫性能的测试和评价方法进展[J]. 日用化学工业, 2005, 35 (3) : 171-173, 191.
[29]	Heymans Robbe, Tavernier Iris, Dewettinck Koen, et al. Crystal stabilization of edible oil foams[J]. Trends in Food Science & Technology, 2017, 69: 13-24.
[30]	Zhang Qi, Zuo Lili, Wu Changchun, et al. The evolution and influence factors of CO₂ flooding crude oil defoaming behavior after depressurization[J]. Journal of Petroleum Science and Engineering, 2021, 206: 108996.