超支化聚缩水甘油甲基丙烯酸酯作为O/W型乳状液的破乳剂

doi:10.16085/j.issn.1000-6613.2020-2546

化工进展 ›› 2021, Vol. 40 ›› Issue (6): 3434-3443.DOI: 10.16085/j.issn.1000-6613.2020-2546

超支化聚缩水甘油甲基丙烯酸酯作为O/W型乳状液的破乳剂

张丽锋¹^,²(), 詹宁宁³, 秦立娟², 赵新星², 周立山², 滕厚开²^,⁴, 方文军⁵

^1.天津大学化工学院，天津 300072
^2.中海油天津化工研究设计院有限公司，天津 300131
^3.中海油能源发展股份有限公司工程技术分公司，天津 300450
^4.河北工业大学化工学院，天津 300132
^5.浙江大学化学系，浙江杭州 310058

收稿日期:2020-12-22 修回日期:2021-02-08 出版日期:2021-06-06 发布日期:2021-06-22
通讯作者: 张丽锋
作者简介:张丽锋（1987—），男，博士，工程师。主要从事超支化聚合物研究。E-mail：zlifeng@zju.edu.cn。
基金资助:
中国博士后科学基金(2019M661034)

Methacrylated hyperbranched polyglycerol demulsifier for O/W emulsion

ZHANG Lifeng¹^,²(), ZHAN Ningning³, QIN Lijuan², ZHAO Xinxing², ZHOU Lishan², TENG Houkai²^,⁴, FANG Wenjun⁵

^1.School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, China
^2.CNOOC Tianjin Chemical Research and Design Institute Company Limited, Tianjin 300131, China
^3.CNOOC Energy Technology & Service Limited-Drilling & Production Co. , Tianjin 300450, China
^4.School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300132, China
^5.Department of Chemistry, Zhejiang University, Hangzhou 310058, Zhejiang, China

Received:2020-12-22 Revised:2021-02-08 Online:2021-06-06 Published:2021-06-22
Contact: ZHANG Lifeng

摘要/Abstract

摘要：

以超支化聚缩水甘油（HPG）和甲基丙烯酸缩水甘油酯（GMA）进行酯交换反应，得到一系列超支化聚缩水甘油甲基丙烯酸酯（HPG-MA）破乳剂，考察了添加量、破乳温度、沉降时间及相对分子质量对破乳性能的影响，并探究动态界面张力和破乳过程中油滴的破裂速率常数的变化，分析其破乳机理。结果表明，在60℃、沉降时间为40min、破乳剂的添加量为2000mg/L时，其脱油率达到90%。与商用破乳剂相比，超支化聚缩水甘油甲基丙烯酸酯因具有独特的超支化多位点结构，用作破乳剂时界面活性高、沉降时间短。

关键词: 超支化聚合物, 多位点结构, 破乳机理, 破乳剂

Abstract:

In this work, a series of methacrylated hyperbranched polyglycerol (HPG-MA) were synthesized through the transesterifivation reaction of polyglycerol (HPG) and GMA. The effects of demulsifier concentration, temperature, settling time and molecular weight on the performance of demulsifier were investigated, and the research of dynamic interfacial tension and rupture rate constant of oil droplets in the demulsification were also studied to analyze its demulsification mechanism. The results indicated that the oil removal rate reached 90% with the condition of 2000mg/L, 30min and 60℃. Compared with traditional demulsifiers, it exhibited high interfacial activity and short settling time because of the unique hyperbranched and multi-point structure.

Key words: hyperbranched polymer, multi-point structure, demulsification mechanism, demulsifier

中图分类号:

TE39

张丽锋, 詹宁宁, 秦立娟, 赵新星, 周立山, 滕厚开, 方文军. 超支化聚缩水甘油甲基丙烯酸酯作为O/W型乳状液的破乳剂[J]. 化工进展, 2021, 40(6): 3434-3443.

ZHANG Lifeng, ZHAN Ningning, QIN Lijuan, ZHAO Xinxing, ZHOU Lishan, TENG Houkai, FANG Wenjun. Methacrylated hyperbranched polyglycerol demulsifier for O/W emulsion[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3434-3443.

图/表 18

图1 超支化聚缩水甘油（HPG）分子结构示意图

图2 超支化聚缩水甘油（HPG）合成示意图

图3 采用酯交换反应合成HPG-MA的示意图

图4 单滴法实验装置示意图

图5 HPG-1与HPG-1-MA-2的1H NMR谱图及其归属

图6 HPG-1和HPG-1-MA-2的红外谱图

表1 HPG样品相关物性参数

聚合物	TMP /g	CH₃OK /g	1，4-二氧六环 /mL	缩水甘油 /mL	$M n ˉ$ ^①	产率 /%	PDI	R_h^② /nm
HPG-1	1.68	0.184	—	30	2100	96.7	1.15	3.10
HPG-2	1.68	0.184	—	50	4100	96.1	1.18	3.30
HPG-3	1.68	0.184	10	50	13500	95.9	1.21	11.20
HPG-4	1.68	0.184	15	50	23000	95.7	1.25	15.50
HPG-5	1.68	0.184	20	50	41700	95.5	1.30	21.10

表1 HPG样品相关物性参数

聚合物	TMP /g	CH₃OK /g	1，4-二氧六环 /mL	缩水甘油 /mL	$M n ˉ$ ^①	产率 /%	PDI	R_h^② /nm
HPG-1	1.68	0.184	—	30	2100	96.7	1.15	3.10
HPG-2	1.68	0.184	—	50	4100	96.1	1.18	3.30
HPG-3	1.68	0.184	10	50	13500	95.9	1.21	11.20
HPG-4	1.68	0.184	15	50	23000	95.7	1.25	15.50
HPG-5	1.68	0.184	20	50	41700	95.5	1.30	21.10

表2 HPG-MA样品的物理参数

聚合物	V_GMA∶m_HPG	$M n ˉ$ ^①	产率/%	R_h^②/nm	DS^②/%
HPG-1-MA-1	1∶1	2280	97.6	3.20	12.30
HPG-1-MA-2	2∶1	2300	97.5	3.30	22.50
HPG-1-MA-3	2.5∶1	2350	97.7	3.40	28.10
HPG-3-MA-1	3∶1	13800	96.9	11.90	12.80
HPG-3-MA-2	1.5∶1	14000	96.8	12.00	19.30
HPG-3-MA-3	3∶2.5	14300	96.6	12.20	23.80
HPG-5-MA-1	1.5∶1	42200	95.7	21.60	11.50
HPG-5-MA-2	3∶2.5	42600	95.6	21.80	21.00
HPG-5-MA-3	1∶1	44100	95.3	21.90	24.20

表2 HPG-MA样品的物理参数

聚合物	V_GMA∶m_HPG	$M n ˉ$ ^①	产率/%	R_h^②/nm	DS^②/%
HPG-1-MA-1	1∶1	2280	97.6	3.20	12.30
HPG-1-MA-2	2∶1	2300	97.5	3.30	22.50
HPG-1-MA-3	2.5∶1	2350	97.7	3.40	28.10
HPG-3-MA-1	3∶1	13800	96.9	11.90	12.80
HPG-3-MA-2	1.5∶1	14000	96.8	12.00	19.30
HPG-3-MA-3	3∶2.5	14300	96.6	12.20	23.80
HPG-5-MA-1	1.5∶1	42200	95.7	21.60	11.50
HPG-5-MA-2	3∶2.5	42600	95.6	21.80	21.00
HPG-5-MA-3	1∶1	44100	95.3	21.90	24.20

图7 不同系列HPG/HPG-MA破乳剂的破乳性能（沉降时间40min，温度60℃）

图8 HPG-1-MA-2添加量对脱油率的影响

图9 温度对HPG-3-MA-2脱油率的影响

图10 沉降时间对HPG-5-MA-2脱油率的影响

图11 相对分子质量对HPG-MA-2脱油率的影响

图12 添加系列HPG-MA-2破乳剂后油水界面的动态界面张力

图13 HPG-MA破乳示意图

图14 HPG-MA对液滴液膜破裂速率常数的影响

图15 HPG-MA对液膜半衰期的影响

图16 不同类型破乳剂的脱油率（沉降时间60min，温度45℃）

参考文献 14

1	SUNDER A, MULHAUP R, HAAG R, et al. Hyperbranched polyether polyols: a modular approach to complex polymer architectures[J]. Advanced Materials, 2000, 12: 235-239.
2	CHEN S, XU Z, ZHANG D. Synthesis and application of epoxy-ended hyperbranched polymers[J]. Chemical Engineering Journal, 2018, 343: 283-302.
3	TENG H K, CHEN C T, YAN S, et al. Modified hyperbranched polyethylenimine as a novel demulsifier for oil-in-water emulsions[J]. Energy Fuels, 2019, 33: 10108-10114.
4	XU Z J, ZHANG Y, HU Q, et al. Biocompatible hyperbranched polyglycerol modified beta-cyclodextrin derivatives for docetaxel delivery[J]. Materials Science & Engineering C-Materials for Biological Applications, 2017, 71: 965-972.
5	MORADI L G, SARI M G, RAMEZANZADEH B. Polyester-amide hyperbranched polymer as an interfacial modifier for graphene oxide nanosheets: mechanistic approach in an epoxy nanocomposite coating[J]. Progress in Organic Coatings Volume, 2020, 142: 105573.
6	DU C G, LI S D, GUAN Q N. Cold preservation with hyperbranched polyglycerol-based solution improves kidney functional recovery with less injury at reperfusion in rats[J]. American Journal of Translational Research, 2017, 9: 429-441.
7	YANG L, SUN H, LIU Y, et al. Self-assembled aptamer-grafted hyperbranched polymer nanocarrier for targeted and photoresponsive drug delivery[J]. Angewandte Chemie: International Edition, 2018, 57: 17048-17052.
8	ZHANG L F, HE G J, YING H, et al. Methacrylated hyperbranched polyglycerol as a high-efficiency demulsifier for oil-in-water emulsions[J]. Energy Fuels, 2016, 30: 9939-9946.
9	XU B. Fast and Energy-efficient demulsification for crude oil emulsions using pulsed electric field[J]. International Journal of Electrochemical Science, 2017, 12: 9242-9249.
10	PENG J X, LIU Q X, XU Z H, et al. Synthesis of interfacially active and magnetically responsive nanoparticles for multiphase separation applications[J]. Advanced Functional Materials, 2012, 22: 1732-1740.
11	ZHANG L F, YING H, YAN S, et al. Hyperbranched poly(amido amine) as an effective demulsifier for oilin-water emulsions of microdroplets[J]. Fuel, 2018, 211: 197-205.
12	LI S, LI N, YANG S, et al. The synthesis of a novel magnetic demulsifier and its application for the demulsification of oil-charged industrial wastewaters[J]. Journal of Materials Chemistry A, 2014, 2: 94-99.
13	ELMOBARAK W, ALMOMANI F, SAAD M A H, et al. Utilizing environmentally friendly hyperbranched polyglycerol polymers to separate gasoline from deionized water[J]. Greenhouse Gases: Science and Technology, 2020, 10: 759-770.
14	COCKBAIN E G, MCROBERTS T S. The stability of elementary emulsion drops and emulsions[J]. Journal of Colloid Science, 1953, 8: 440-451.

[1]	吴亚, 赵丹, 方荣苗, 李婧瑶, 常娜娜, 杜春保, 王文珍, 史俊. 用于复杂原油乳液的高效破乳剂开发及应用研究进展[J]. 化工进展, 2023, 42(8): 4398-4413.
[2]	李松涛, 赵谨, 张丽锋. 超支化聚酰胺-胺的合成及其在O/W型乳状液的破乳应用[J]. 化工进展, 2023, 42(1): 401-408.
[3]	郭睿, 高弯弯, 刘雪艳, 霍文生, 冯文佩, 李秀环. NPEAA与AEPH共改性苯基含氢硅油的制备及其破乳性能[J]. 化工进展, 2019, 38(06): 2922-2932.
[4]	都伟超, 孙金声, 蒲晓林, 张洁, 陈刚. 国内外黏土水化抑制剂研究现状与发展趋势[J]. 化工进展, 2018, 37(10): 4013-4021.
[5]	石斌龙，张谋真，程蝉，刘启瑞. TA162824原油破乳剂的复配[J]. 化工进展, 2013, 32(03): 678-680.
[6]	强涛涛，张国国，王学川. 两亲性超支化聚合物研究进展[J]. 化工进展, 2013, 32(03): 666-670.
[7]	王宁，火跃芳，卞庆亚，仇凡，蒋立英. ABn型α-环糊精单体及其超支化聚合物的合成及表征[J]. 化工进展, 2011, 30(12): 2679-.
[8]	姜岩，吴迪，任南琪，耿大军. 生物技术在油田地面处理系统中的应用研究进展 [J]. 化工进展, 2009, 28(9): 1489-.
[9]	张道洪，周子鹄，贾德民，张爱清. 超支化不饱和树脂的制备与应用研究进展 [J]. 化工进展, 2009, 28(7): 1187-.
[10]	肖文清，胡剑青，涂伟萍. 超支化聚合物合成方法与应用研究进展 [J]. 化工进展, 2007, 26(9): 1253-.

超支化聚缩水甘油甲基丙烯酸酯作为O/W型乳状液的破乳剂

Methacrylated hyperbranched polyglycerol demulsifier for O/W emulsion

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 18

参考文献 14

相关文章 10

编辑推荐

Metrics

本文评价