Dye/pigment encapsulation technology and evaluation method
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摘要: 近年来,彩色微球(CMS)的开发和应用越来越受到关注,它是一种微纳米级高分子聚合物,具有粒径小、比表面积大、单分散、稳定和色泽明亮等特点,在环保、医药、电子、农业、食品、化妆品等制造业领域具有广泛的应用。目前,关于影响CMS封装效果关键因素的综合分析尚属空白。同时,我国CMS的种类和应用与国外相比还有较大差距。因此加强CMS的基础研究和技术攻关成为重中之重。染料/颜料(D/P)的封装在CMS的合成过程中是非常重要的环节,除了考虑CMS的稳定性和色泽亮度的基本性能外,还需要对D/P的封装效果进行科学的评价。本文介绍了D/P在溶液中的聚集机制及排列形式,D/P与微球(MS)基材相互作用对封装的影响及作用机制,重点从聚合方法、D/P结构、MS基材等方面综合阐述了CMS合成过程中影响封装的关键因素及机制,并总结了目前较为成熟的D/P封装效果评价方法。最后,预测了CMS的D/P封装技术的未来研究方向。Abstract: The color microsphere(CMS) is micro and nano polymers with small particle size, large specific surface area, monodispersity, stable and bright color, etc., which are widely used in the fields of environmental protection, medical, electronics, agriculture, food, cosmetics, and so on. Currently, the comprehensive analysis of the key factors affecting the encapsulation effect of the CMS is lacking. Meanwhile, there is still a wide gap between the types and applications of the CMS in China and abroad. Thus, strengthening the basic research and technical research of the CMS is one of the top priorities. Dyes/pigments (D/P) encapsulation is a very important part in the synthesis of the CMS. In addition to considering the basic properties of stability and color brightness of the CMS, it is also necessary to scientifically evaluate the encapsulation effect of the D/P. This paper introduces the aggregation mechanism and arrangement form of the D/P in solution, the influence of the interaction between the D/P and microsphere (MS) substrates on encapsulation and the mechanism of action. Focuses on the key factors and mechanisms of the encapsulation in the synthesis of the CMS comprehensively from the aspects of polymerization method, the D/P structure and MS substrate. Then, the evaluation methods of the D/P encapsulation effect, which are more mature at present, are summarized. Finally, the future research direction of the D/P encapsulation technology for the CMS is predicted.
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图 2 (a)激子理论-吸收波长位移示意图[133];(b)激子-激子湮灭过程的能级示意图[18];(c)聚集体与单分子动态平衡示意图[134]
Figure 2. (a) Exciton Theory-Schematic diagram of absorption wavelength shift[133]; (b) Schematic diagram of the energy level of the exciton-exciton annihilation process [18]; (c) Schematic diagram of the dynamic equilibrium of aggregates and single molecules [134]
图 5 (a)静置沉降示意图;(b)浓硫酸稀释颜色变化示意图[72];(c)超离心沉降示意图[72] ;(d)彩色微球的TEM示意图
Figure 5. (a)Schematic diagram of static settlement; (b)Schematic diagram of dilution color change of concentrated sulfuric acid (b)[72]; (c)Schematic diagram of ultracentrifugal sedimentation[72]; (d)Schematic diagram of TEM of colored microspheres
表 1 彩色微球的封装方法及特点
Table 1. Encapsulation methods and characteristics of colored polymers
Polymerization method Performance characteristics Name of dye/pigment References Miniemulsion polymerization High encapsulation rate;
Good repeatability;
Gentle reaction rate;
Highly tunable microsphere
size and structure;Sudan black B [47] Solvent red;solvent blue;solvent yellow [82] PB15:3 [53] PB15:3;styrene-based dyes [14] Disperse yellow 201;oil yellow 129 [62] Solvent red;yellow; blue;green [55] Solvent yellow43 [73] Perylene orange [119] Carbon black [46] Disperse red 60 [120] Pigment yellow 13 [72] Fluorescein [118] PB15:3 [107] PB15:3 [121] C.I. 60752 ;
Disperse yellow 211;
Disperse blue183;
[122]PB15:3 [9] Fluorescent yellow R [90] Pigment yellow 74;
Pigment violet 19;
PB15:3;
[61]PB15:3 [84] Emulsion polymerization High encapsulation rate;
Good encapsulation pattern;
Good dispersion stability;
Low system viscosity;
Short reaction period;
Uniform particle size;Basic red 9 [67][123] Double-bonded anthraquinone dyes [124-125] [127] Carbon black [89] PB15:3 [126] Pigment red 112; [72] Emulsifier free emulsion
polymerizationEmulsifier free;
Clean product ;
Good monodispersity;Carbon black [41] Disperse red 60;
Disperse blue 60;
Disperse yellow 114;
Disperse black;[75] Disperse red 60;
Disperse blue 60;
Disperse yellow 114;[112] Disperse red 60 [4] Disperse red 343 [117] Reactive red 24;
Reactive blue 49;
Reactive yellow 95;
Reactive black 5;[128] Sudan red 7 B [10] Seeding polymerization High encapsulation rate;
Uniform particle size distribution;8301 blue FFG[129]
In-situ polymerizationGood stability;
Strong controllability;
Excellent performance;Carbon black [130] Notes:PB15:3 is the ceresbluebhr. 表 2 染料/颜料用量对封装过程的影响
Table 2. Effect of dye dosage on the encapsulation process
Dye/pigment amount Mechanisms of influence References
Excessive
amoutIncreased proportion of nitrogen and thinning of the PS; [47] Enhanced intermolecular interactions and hydrophobicity of D/P promote phase separation; [82] D/P cannot be dispersed uniformly and precipitation occurs during polymerization. [131] Excessive D/P kernel, thinning of PS thickness; [72] Increase in the number of D/P molecules leads to an increase in entropy and an increase in the
chances of intermolecular collisions, which enhances D/P aggregation;[49] Lesser amount The distance between molecules is far, the intermolecular force is weak, and the monomer
polymerization rate is fast, thus it is difficult to realize phase separation between PS and D/P;[82] CMS color is too low; [120] Easily appear blank irregular MS; [42] CMS yield is too low. [132] Notes:The PS is a polymer layer; D/P is the dye/pigment; CMS is the color microsphere;MS is the microsphere. -
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