腰果酚生物基自愈合微胶囊的高效制备工艺研究

doi:10.11949/0438-1157.20230320

化工学报 ›› 2023, Vol. 74 ›› Issue (7): 3103-3115.DOI: 10.11949/0438-1157.20230320

• 材料化学工程与纳米技术 • 上一篇下一篇

腰果酚生物基自愈合微胶囊的高效制备工艺研究

吴文涛¹(), 褚良永¹(), 张玲洁², 谭伟民³, 沈丽明¹, 暴宁钟¹()

^1.南京工业大学化工学院，材料化学工程国家重点实验室，江苏南京 211816
^2.浙江大学材料科学与工程学院，浙江杭州 310027
^3.中海油常州涂料化工研究院有限公司，江苏常州 213016

收稿日期:2023-04-04 修回日期:2023-07-05 出版日期:2023-07-05 发布日期:2023-08-31
通讯作者: 褚良永,暴宁钟
作者简介:吴文涛（1997—），男，硕士研究生，202061104097@njtech.edu.cn
基金资助:
国家重点研发计划项目(2020YFE0100100)

High-efficient preparation of cardanol-based self-healing microcapsules

Wentao WU¹(), Liangyong CHU¹(), Lingjie ZHANG², Weimin TAN³, Liming SHEN¹, Ningzhong BAO¹()

^1.College of Chemical Engineering, State Key Laboratory of Material-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^2.College of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^3.CNOOC Changzhou Paint and Coatings Industry Research Institute Co. , Ltd. , Changzhou 213016, Jiangsu, China

Received:2023-04-04 Revised:2023-07-05 Online:2023-07-05 Published:2023-08-31
Contact: Liangyong CHU, Ningzhong BAO

摘要/Abstract

摘要：

生物基微胶囊的高效制备，对于生物基自愈合涂层的发展意义重大。针对传统石油基表面活性剂无法有效封装腰果酚基树脂及固化剂等愈合剂的难题，报道了以腰果酚基表面活性剂为乳化剂，通过溶剂蒸发法，高效制备聚甲基丙烯酸甲酯为外壳的生物基微胶囊的方法。结合溶剂蒸发法机理，提出了假说解释腰果酚基乳化剂的高效封装机制。通过SEM、TGA、粒径分析等表征方法研究了乳化剂浓度、芯壁比、转速、温度等工艺参数对微胶囊形貌、尺寸、稳定性的影响，确立粒径可控、单分散和规则球形的微胶囊制备工艺。研究表明蒸发温度40℃、芯壁比1∶1时制备的微胶囊具有较好的表面形貌，乳化剂浓度、转速与平均粒径之间存在规律性影响，并且埋植20%（质量）生物基微胶囊的自愈合涂层的愈合效率达到61.25%。报道的基于腰果酚基表面活性剂的生物基微胶囊的高效制备，对于生物基自愈合涂层的开发，推动生物基涂层对石油基的取代，具有指导意义。

关键词: 腰果酚, 微胶囊, 自愈合, 制备, 优化, 生物质

Abstract:

The efficient preparation of bio-based microcapsules is of great significance for the development of bio-based self-healing coatings. To solve the issue that traditional petroleum-based surfactants cannot effectively encapsulate biological healing agents such as cardanol-based epoxy resins and curing agents, it is reported that cardanol-based surfactants can be used as an emulsifier in the preparation of microcapsules. Using the solvent evaporation method, bio-based microcapsules with polymethyl methacrylate as the shell have been efficiently prepared. Based on the solvent volatilization mechanism, a hypothesis has been proposed to explain the efficient packaging of cardanol-based emulsifiers. The morphology of the microcapsules was analyzed by scanning electron microscopy, and the stability and size distribution of the microcapsules were analyzed by thermogravimetry and laser particle size analyzer. By systematic optimization of process parameters such as emulsifier concentration, the ratio of core to the wall, stirring speed, and temperature, bio-based microcapsules with controllable particle size, mono dispersibility, and spherical structure were prepared. The results show that the microcapsules prepared at evaporation temperature of 40℃ and core-wall ratio of 1∶1 have better surface morphology, and there are regular effects between emulsifier concentration, stirring speed and average particle size. Moreover, the healing efficiency of the self-healing coating embedded with 20%(mass) bio-based microcapsules reaches 61.25%. The application of bio-based surfactants in the high-efficient preparation of bio-based microcapsules may guide the development of bio-based self-healing coatings and contribute to the replacement of petroleum-based materials with bio-based materials in the coating field.

Key words: cardanol, microcapsule, self-healing, preparation, optimization, biomass

中图分类号:

TQ 323.5

吴文涛, 褚良永, 张玲洁, 谭伟民, 沈丽明, 暴宁钟. 腰果酚生物基自愈合微胶囊的高效制备工艺研究[J]. 化工学报, 2023, 74(7): 3103-3115.

Wentao WU, Liangyong CHU, Lingjie ZHANG, Weimin TAN, Liming SHEN, Ningzhong BAO. High-efficient preparation of cardanol-based self-healing microcapsules[J]. CIESC Journal, 2023, 74(7): 3103-3115.

图/表 17

图1 生物基微胶囊E-capsule和Ami-capsule的合成工艺和结构示意图

Fig.1 Schematic diagram of the synthesis process and structure of bio-based microcapsules E-capsule and Ami-capsule

表1 乳化剂性质

Table 1 The properties of the emulsifier

乳化剂	原材料类型	HLB值	pH
聚乙烯醇（PVA）	石油基	12.3	5.0~7.0
十二烷基硫酸钠（SDS）	石油基	15	6.0~9.0
腰果酚基表面活性剂NSF3007C	生物基	10.8	4.0~7.0

图2 分别以PVA、SDS和NSF3007C作为乳化剂制备的E-capsule的SEM图像

Fig.2 SEM images of E-capsule prepared with PVA, SDS, and NSF3007C as emulsifiers

图3 分别以PVA、SDS和NSF3007C作为乳化剂制备的Ami-capsule的SEM图像

Fig.3 SEM images of Ami-capsule prepared with PVA, SDS, and NSF3007C as emulsifiers

图4 溶剂挥发过程中采用不同乳化剂的芯材分子的状态示意图

Fig.4 Schematic diagram of state of core material molecules using different emulsifiers during solvent evaporation

图5 不同水油体积比下乳液的溶液状态照片和Zeta电位曲线

Fig.5 Solution state digital images and Zeta potential curve of emulsion with different water-oil volume ratio

图6 不同乳化时间下乳液的溶液状态照片和Zeta电位曲线

Fig.6 Solution state digital images and Zeta potential curves of emulsion with different emulsification time

表2 影响微胶囊制备的工艺参数

Table 2 Process parameters affecting the preparation of microcapsules

序号	工艺参数	基础水平	最终水平
1	蒸发温度/℃	20	80
2	乳化剂浓度/%（质量）	1	5
3	转速/(r/min)	2000	3500
4	芯壁比	1∶2	3∶1

图7 不同蒸发温度下制备的E-capsule和Ami-capsule的SEM图像

Fig.7 SEM images of E-capsule and Ami-capsule prepared at different evaporation temperatures

图8 不同浓度下以NSF3007C作为乳化剂制备的微胶囊的粒径分布

Fig.8 Particle size distribution of microcapsules prepared with NSF3007C as emulsifier at different concentrations

图9 不同搅拌速度下以NSF3007C为乳化剂制备的微胶囊的粒径分布

Fig.9 Particle size distribution of microcapsules prepared with NSF3007C as emulsifier at different stirring speeds

图10 具有不同芯壁比的E-capsule和Ami-capsule的SEM图像

Fig.10 SEM images of E-capsule and Ami-capsule with different ratios of core to wall

图11 壳材、微胶囊和愈合剂的FTIR光谱

Fig.11 FTIR spectra of shell materials, microcapsules, and core materials

图12 壳材、芯材和微胶囊的TGA曲线

Fig.12 TGA curves of shell materials, core materials, and microcapsules

表3 溶剂蒸发温度为40℃时不同工艺条件下制备的E-capsule储存12 h的质量损失

Table 3 Mass loss of E-capsule prepared under different process conditions at a solvent evaporation temperature of 40℃ after storage for 12 h

温度/℃	质量损失/%
	芯壁比				转速/(r/min)				乳化剂浓度/%（质量）
	1∶2	1∶1	2∶1	3∶1	2000	2500	3000	3500	1	2	3	4	5
60	1.7	0.8	1.4	0.6	1.1	0.8	0.4	1.7	1.4	0.8	0.8	6	0.7
80	1.8	1.3	2.2	4.6	1.6	1.3	4.1	2.2	1.5	1.3	1.0	11	0.9
100	2	1.9	4.7	5.4	3	1.9	4.9	3.4	2.4	1.9	1.4	12	1
120	4.5	5.7	5.6	7.1	5.3	5.7	5.8	7.3	5.7	2.8	2.1	14	5

表4 溶剂蒸发温度为40℃时不同工艺条件下制备的Ami-capsule储存12 h的质量损失

Table 4 Mass loss of Ami-capsule prepared under different process conditions at a solvent evaporation temperature of 40℃ after storage for 12 h

温度/℃	质量损失/%
	芯壁比				转速/（r/min）				乳化剂浓度/%（质量）
	1∶2	1∶1	2∶1	3∶1	2000	2500	3000	3500	1	2	3	4	5
60	1.3	1.5	0.6	0.9	0.9	1.3	4.2	0.8	1.1	1.3	0.5	3.2	1.6
80	1.3	1.7	0.7	2.4	0.9	1.3	5	1	1.4	1.3	1	4.2	2.2
100	1.4	1.7	1.2	2.6	1.3	1.4	7.1	1.8	1.9	1.4	1.5	5.6	2.2
120	1.5	2	5.	5.7	1.4	1.5	9	2.2	5.2	1.5	3	9.7	4

图13 （a）埋植生物基微胶囊的原始和愈合TDCB涂层样品的应力-应变曲线；（b）表面具有“X”划痕的自愈合涂层在3.5%（质量） NaCl溶液下浸泡的Bode曲线；（c）表面被划伤的自愈合涂层的SEM图；（d）表面被划伤的自愈合涂层愈合后的SEM图

Fig.13 (a) Stress-strain curves of original and healed TDCB coating samples embedded with bio-based microcapsules; (b) Bode curves of self-healing coating with “X” scratch on the surface immersed in 3.5%(mass) NaCl solution; (c) SEM image of self-healing coatings with scratched surface; (d) SEM image of the scratched self-healing coating after healing

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腰果酚生物基自愈合微胶囊的高效制备工艺研究

High-efficient preparation of cardanol-based self-healing microcapsules

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