石蜡Pickering乳液及其微胶囊相变非织造材料的制备与性能

doi:10.13475/j.fzxb.20230604601

Abstract

Abstract:

Objective Pickering emulsion uses solid-particles as emulsifier instead of small-molecule surfactants, in which solid particles are embedded on the surface of emulsion droplets, and thus its interfacial adsorption energy is far greater than the thermodynamic energy of the solid particle Brown motion. Consequently, it is difficult for the solid particles to escape from the oil-water interface, providing the emulsion with excellent storage stability. Pickering solid emulsifier in the paraffin emulsion does not cut down the paraffin crystalline temperature, and eliminates the subcool phenomenon, and improves its phase-change energy storage performance. Unfortunately, very few Pickering emulsifiers have existed, such as nano-silica, graphene oxide, nano-cellulose crystals, more often being applied with organic polymer co-emulsifier.

Methods Soap-free emulsion polymerization was carried out with styrene (St) and methacryloxyethyl-trimethylammonium chloride (DMC) as monomers, divinyl benzene (DVB) as crosslinker, ethanol as auxiliary solvent. Cationic copolymer particles characterized with monodispersity, clean surface, and designed size were obtained. The paraffin Pickering emulsions and paraffin droplets on viscose fabric phase change materials (Vis-PCM) were prepared by using the resultant copolymer nanoparticles (P(St-co-DMC)). The microstructure and properties, monomer conversion, nanoparticle size, Zeta potential and contact angles of P(St-co-DMC) particles as well as Vis-PCM were investigated by Fourier transform infrared spectrometry, scanning electron microscopy, thermogravimetry, differential scanning calorimetry, and contact angle goniometry.

Results The influences of DMC and initiator dosages, and ethanol contents on the monomer conversion and the nanoparticle size, as well as of DMC dosages on the contact angle and Zeta potential of the nanoparticles were studied. The results showed that cationic P(St-co-DMC) copolymer nanoparticles were successfully prepared, and the two major monomers were merged into the copolymer chain. The resulted polymers were shown to withstand the thermal shock during emulsification process, as well as phase change energy storage and heat release recycling processes. The monomer conversion presented bell-shape behavior, whereas the particle size and its dispersion index showed reversed bell tendency with the increases of DMC, initiator and ethanol. However, the Zeta potential of the copolymer particles initially soared up and then tended to be constant, whereas the hydrophilicity was improved with the increase of DMC dosage. When the amounts of DMC, KPS and ethanol were fixed at 25%, 2.5% and 15%, respectively, the monomer conversion reached 83%, the size, the Zeta potential, and the surface contact angle of the resultant copolymer particles were 114 nm, 47.2 mV, and 58°, respectively. The over three-month shelf life, oil-in-water paraffin Pickering emulsion at the oil-to-water volume ratio of 3∶1 and at the droplet size of (4.4±0.5) μm was eventually obtained. The phase change latent heat of Vis-PCM, which was obtained by impregnating spunlaced viscose nonwoven fabric into the Pickering emulsion, reached up to 139.3 J/g, and the paraffin leakage rate of Vis-PCM was only 0.6% after 20 thermal cycls.

Conclusion Copolymer particles with controllable surface features such as water contact angle, particle size and electricity, instead of the small molecule surfactant, can be adsorbed firmly at the oil-water interface to obtain a long shelf life Pickering emulsion. P(St-co-DMC) emulsifier copes with the paraffin subcool phenomenon due to small molecule surfactant plasticizer based on heterogeneous nucleation mechanism. Also it is emulsion droplets rather than de-emulsified paraffin bulk that adhere to the nonwoven surface, which ensures the paraffin-microencapsulated fabric acting as reusable phase change energy storage materials. All the results confirm that P(St-co-DMC) possesses excellent emulsifying ability, and Vis-PCM has good heat storage and heat release properties.

Key words: methacryloyloxyethyl trimethylammonium chloride, soap-free emulsion polymerization, paraffin, Pickering emulsion, viscose nonwoven, phase change material

CLC Number:

TS195.2

KE Wentao, CHEN Ming, ZHENG Chuntian, SHI Xiaoli, ZHU Xinsheng. Preparation and properties of paraffin Pickering emulsion and its microcapsule phase change nonwoven materials[J].Journal of Textile Research, 2024, 45(07): 130-139.

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URL: http://www.fzxb.org.cn/EN/10.13475/j.fzxb.20230604601

http://www.fzxb.org.cn/EN/Y2024/V45/I07/130

Figures/Tables 13

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References 29

[1]	茹绍青, 武亚飞, 车黎明. 低过冷度石蜡Pickering乳液的制备和表征[J]. 化工学报, 2021, 72(4): 2309-2316. doi: 10.11949/0438-1157.20201053
	RU Shaoqing, WU Yafei, CHE Liming. Preparation and characterization of paraffin Pickering emulsion without subcooling phenomenon[J]. CIESC Journal, 2021, 72(4): 2309-2316.
[2]	BINKS B P, LUMSDON S O. Influence of particle wettability on the type and stability of surfactant-free emulsions[J]. Langmuir, 2000, 16(23): 8622-8631.
[3]	陈玉, 曹金珍. 蒙脱土稳定石蜡基Pickering乳液处理木材的性能研究[J]. 林业工程学报, 2017, 2(5): 36-40.
	CHEN Yu, CAO Jinzhen. Effect of dicumyl pero-xide(DCP) on properties of paraffin wax based Pickering emulsion stabilized by montmorillonite[J]. Journal of Forestry Engineering, 2017, 2(5): 36-40.
[4]	杨隽阁, 高成乾, 李博鑫, 等. 改性氧化石墨烯稳定Pickering乳液法制备高导热相变整体材料[J]. 高等学校化学学报, 2022, 43(2): 183-190.
	YANG Junge, GAO Chengqian, LI Boxin, et al. Preparation of high thermal conductivity phase change monolithic materials based on Pickering emulsion stabilized by surface modified graphene oxide[J]. Chemical Research in Chinese Universities, 2022, 43(2): 183-190.
[5]	MIKHAYLOV V I, TORLOPOV M A, VASENEVA I N, et al. Magnetically controlled liquid paraffin oil-in-water Pickering emulsion stabilized by magnetite/cellulose nanocrystals: Formation and Cr (VI) adsorption[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021. DOI: 10.1016/j.colsurfa.2021.126634.
[6]	唐新, 沈一丁, 李培枝. 阳离子型全氟丙烯酸酯无皂乳液的合成及性能[J]. 涂料工业, 2010, 40(3): 57-60.
	TANG Xin, SHEN Yiding, LI Peizhi. Synthesis and properties of cationic perfluoroacrylate emusifier-free emulsion[J]. Paint & Coatings Industry, 2010, 40(3): 57-60.
[7]	张高文, 叶莹, 杨侃, 等. 无皂乳液聚合法合成阴离子PS微球及粒径控制[J]. 高分子通报, 2013 (5): 60-64.
	ZHANG Gaowen, YE Ying, YANG Kan, et al. The preparation of anionic polystyrene microspheres via emulsifier-free emulsion polymerization and diameter control[J]. Polymer Bulletin, 2013 (5): 60-64.
[8]	TANG J, QUINLAN P J, TAM K C. Stimuli-responsive Pickering emulsions: recent advances and potential applications[J]. Soft Matter, 2015, 11(18): 3512-3529. doi: 10.1039/c5sm00247h pmid: 25864383
[9]	ZHANG B, ZHANG Z, KAPAR S, et al. Microencapsulation of phase change materials with polystyrene/cellulose nanocrystal hybrid shell via Pickering emulsion polymerization[J]. ACS Sustainable Chemistry & Engineering, 2019, 7: 17756-17767.
[10]	SONG M, JIANG J, ZHU J, et al. Lightweight, strong, and form-stable cellulose nanofibrils phase change aerogel with high latent heat[J]. Carbohydrate Polymers, 2021. DOI:.1016/j.carbpol.2021.118460.
[11]	COLLETTE FM, LORENTZ C, GEBEL G, et al. Hygrothermal aging of Nafion[J]. Journal of Membrane Science, 2009, 330: 21-29.
[12]	TAO R, GAO D, SHI X, et al. The relationship between the pH value of dilute effluent streams and system durability in the separate bed electrodeionization process[J]. Separation and Purification Technology, 2020. DOI:10.1016/j.seppur.2020.116980.
[13]	石小丽. 紫外照射功能化接枝聚合改性丙纶织物及其微观结构性能与应用[D]. 苏州: 苏州大学, 2014: 19-48.
	SHI Xiaoli. Ultraviolet-irradiated graft polymerization modification, microstructure, properties and applications of polypropylene fabrics[D]. Suzhou: Soochow University, 2014:19-48.
[14]	艾丽. 紫外引发阴离子单体接枝改性丙纶非织造布与应用研究[D]. 苏州: 苏州大学, 2014:38-53.
	AI li. Grafting copolymerization of polypropylene fabric with anionic monomers under UV irradiation and its adsorption behavior[D]. Suzhou: Soochow University, 2014:38-53.
[15]	徐继红, 李庄, 苏瑞文. 无皂乳液聚合制备MMA/BA/MAA三元共聚物乳胶粒及表征[J]. 化工新型材料, 2009, 37(6): 58-60.
	XU Jihong, LI Zhuang, SU Ruiwen. Preparation of MMA/BA/MAA copolymer latexes by nonsoap emulsion polymerization[J]. New Chemical Materials, 2009, 37(6): 58-60.
[16]	李小玉, 何桂荣, 胡雯燕. 无皂乳液聚合法制备丙烯酸改性聚醋酸乙烯酯乳液的研究[J]. 中国胶粘剂, 2018, 27(1): 28-32.
	LI Xiaoyu, HE Guirong, HU Wenyan. Study on acrylic acid modified polyvinyl acetate emulsion prepared by surfactant-free emulsion polymerization[J]. China Adhesives, 2018, 27(1): 28-32.
[17]	钟瑞英, 付长清, 申亮. 细乳液聚合最新研究进展[J]. 涂料工业, 2019, 49(8): 81-87.
	ZHONG Ruiying, FU Changqing, SHEN Liang. Recent progress in mini-emulsion polymerization[J]. Paint & Coatings Industry, 2019, 49(8): 81-87.
[18]	陈鑫, 陈志民, 崔占臣, 等. 表面富集季胺盐的交联聚苯乙烯微球合成与表征及其溶胀行为研究[J]. 高分子学报, 2003 (2): 293-297.
	CHEN Xin, CHEN Zhimin, CUI Zhanchen, et al. Synthsis and characterizations of cross-linked polystyrene microspheres with quarternary ammonium on the surface and studies on their swelling behavior[J]. Acta Polymerica Sinica, 2003(2): 293-297.
[19]	青晨, 徐建军, 叶光斗, 等. VAc/MA/AA三元无皂乳液共聚的研究[J]. 中国胶粘剂, 2006, 15(4): 1-5.
	QING Chen, XU Jianjun, YE Guangdou, et al. Study on emulsifier-free emulsion polymerization of VAc/MA/AA[J]. China Adhesives, 2006, 15(4): 1-5.
[20]	王旭, 隋智慧, 郭制安, 等. 聚丙烯酸酯无皂乳液的性能及其应用[J]. 印染, 2020, 46(5): 51-55.
	WANG Xu, SUI Zhihui, GUO Zhian, et al. Properties and application of polyacrylate soap free emulsion[J]. China Dyeing & Finishing, 2020, 46(5): 51-55.
[21]	ZHOU X, SHAO H, LIU H. Preparation and characterization of film-forming raspberry-like polymer/silica nanocomposites via soap-free emulsion polymerization and the sol-gel process[J]. Colloid and Polymer Science, 2013, 291: 1181-1890.
[22]	SMOLUCHOWSKI M V. Versuch zur mathematischen theorie der koagulationskinetik kolloider losungen[J]. Zeitschrift fur Physikalische Chemie, 1918, 92: 129-138.
[23]	梁励芬. 电泳迁移率的简便计算方法[J]. 大学物理, 1996(5): 5-6,34.
	LIANG Lifen. A brief calculation method of electrophoresis mobility[J]. College Physics, 1996(5): 5-6,34.
[24]	薛中衡, 任钦益, 刘海涓, 等. 聚苯乙烯纳米粒子及其石蜡乳液的制备与应用[J]. 合成纤维工业, 2022, 45(3): 59-64.
	XUE Zhongheng, REN qinyi, LIU Haijuan, et al. Preparation and application of polystyrene nanoparticles and paraffin emulsions[J]. China Synthetic Fiber Industry, 2022, 45(3): 59-64.
[25]	程凤珍, 李友明. 机械浆磨浆过程中纤维分离与分丝帚化研究进展[J]. 纸与造纸, 2014, 33(8): 14-17.
	CHENG Fengzhen, LI Youming. Review of fiber separation and development in mechanical pulp refining process[J]. Paper and Paper Making, 2014, 33(8): 14-17.
[26]	LINDLEY K S, ROWSON N A. Charging mechanisms for particles prior to electrostatic separation[J]. Magnetic and Electrical Separation, 1997, 8: 101-113.
[27]	张秋香, 陈建华, 陆洪彬, 等. 纳米二氧化硅改性石蜡微胶囊相变储能材料的研究[J]. 高分子学报, 2015 (6): 692-698.
	ZHANG Qiuxiang, CHEN Jianhua, LU Hongbin, et al. Studies on nanosilica modified paraffin microcapsule phase change energy storage materials[J]. Acta Polymerica Sinica, 2015(6): 692-698.
[28]	王安明, 吴华强, 王俊恩, 等. 溶剂热法制备小粒径无皂均聚物纳米胶乳粒子[J]. 功能高分子学报, 2003, 16(4): 517-520.
	WNAG Anming, WU Huaqiang, WANG Junen, et al. Preparation of emulsifier-free macromolecule nanoparticle latex with solvothermal method[J]. Journal of Functional Polymers, 2003, 16(4): 517-520.
[29]	陈琳, 武亚飞, 车黎明. 一种测量石蜡相变乳液过冷度的新方法: 平衡态比容法[J]. 化工学报, 2019, 70(9): 3370-3376. doi: 10.11949/0438-1157.20190293
	CHEN Lin, WU Yafei, CHE Liming. A new approach to determine the degree of subcooling in phase-change paraffin emulsion: equilibrium volumetry[J]. CIESC Journal, 2019, 70(9): 3370-3376.

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KPS质量分数/%	粒径/nm	PDI值	转化率/%
0.5	230	0.35	77
1.0	161	0.19	79
1.5	122	0.12	80
2.0	119	0.07	81
2.5	114	0.01	83
3.0	116	0.14	79
3.5	119	0.24	76
4.0	121	0.25	73
4.5	123	0.29	69
5.0	126	0.36	66

乙醇体积分数/%	粒径/nm	PDI值	转化率/%
5	157	0.37	76
10	138	0.12	79
15	114	0.01	83
20	123	0.10	78
25	126	0.18	75
30	133	0.18	74
35	135	0.17	72
40	142	0.18	71
45	155	0.31	71

样品编号	P(St-co-DMC) 质量分数/%	油水体积比	负载率/%	泄漏率/%	过冷度/℃
Vis-PCM1	3	1∶1	133.8	8.7	4.71
Vis-PCM2	3	3∶1	179.3	10.1	6.36
Vis-PCM3	6	3∶1	291.5	0.6	5.20

试样	负载率/%	熔融焓/(J·g^-1)
纯石蜡	—	151.1
Vis-PCM1	133.8	131.3
Vis-PCM2	179.3	130.9
Vis-PCM3	291.5	139.3

Preparation and properties of paraffin Pickering emulsion and its microcapsule phase change nonwoven materials

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Figures/Tables 13

References 29

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DMC质量分数/%	粒径/nm	PDI值	转化率/%
15	130	0.10	74
20	129	0.08	80
25	114	0.01	83
30	117	0.05	78
35	123	0.09	73
40	142	0.11	72
45	173	0.22	72

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