高温可逆热致变色材料的微胶囊化研究
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摘要
目前，可逆热致变色示温材料已成为国内、外研究的热点，并具有重要的使用价值。本文针对高温变色示温材料普遍存在的可逆性差、温度适用范围小的缺点，利用微胶囊技术，将水溶性无机变色材料进行微胶囊化，以提高可逆热致变色材料的变色可逆性，拓宽可逆热致变色材料的适用范围。
本研究采用油相相分离法，以无机变色颜料NLHN为芯材，乙基纤维素(EC)为壳材，环己烷(HC)为溶剂，Span-80为乳化剂，聚异丁烯(PIB)为相稳定剂，制备了S／O型NLHN-RTM微胶囊。试验研究了核-壳比、乳化剂用量、溶剂用量、相稳定剂用量、表面张力和搅拌速率等六个关键因素对S／O型NLHN-RTM微胶囊的粒度及其包裹率的影响，探讨了芯材性能、囊壁厚度、搅拌速率和冷却速率与S／O型NLHN-RTM微胶囊变色性能之间的关系。利用生物显微镜(BM)、扫描电子显微镜(SEM)、热重分析仪(TGA)、X-射线衍射仪(XRD)和红外光谱分析仪(IR)对S／O型NLHN-RTM微胶囊进行了结构表征与性能研究，分析了S／O型NLHN-RTM微胶囊的粒度、囊壁厚度、包裹率、热稳定性、化学稳定性、机械强度和环境适应性等，探讨了S／O型NLHN-RTM微胶囊结构与性能之间的关系。此外，将S／O型NLHN-RTM微胶囊以颜料的形式应用在PVA基础涂料、醇酸清漆基涂料和水性乳胶漆基涂料中，研究了S／O型NLHN-RTM微胶囊在油性和水性涂料中的应用。
研究表明，当核-壳比为2：3、溶剂环己烷用量为70ml、搅拌速率为1000r／min、乳化剂Span-80用量为5％，乳化时间为40min，相稳定剂量聚异丁烯用量为3％时，制备的S／O型NLHN-RTM微胶囊变色温度T_c为109.5℃，变色时间t_c为60s，复色温度T_f为108℃，复色时间t_f为120s，变色灵敏度K为0.315，其颜色在绿色和紫色之间发生可逆变化。结果表明，S／O型NLHN-RTM微胶提高了高温热致变色材料的可逆性、改善了变色灵敏性、扩宽了温度适用范围，具有良好的性能和广阔的应用前景。
Presently, the reversible thermochomic materials have become a hotspot of researching, and have high practical valued. Water-solubility inorganic thermal materials were wrapped by microencapsulation method in this paper, which in order to enhance the reversibility and extend the using area of different temperature.
In this thesis, using inorganic pigment (NLHN), ethyl cellulose (EC), cyclohexane (HC), Span-80 and poly-isobutylene (PIB) to prepare S/O type NLHN-RTM microcapsule by oil phase separation method in which NLHN EC, HC, Span-80 and PIB are used as core materials, shell materials, solvent, emulsifier respectively and phase stabilizer. The roles which act on the particle size and embedding efficiency of the S/O type NLHN-RTM microcapsule played by six factors: the ratio of core and shell, emulsifier concentration, solvent content, stabilizer content, surface tension, and the rate of stiring. The relation between the different factors and the thermochromism performance of S/O type NLHN-RTM microcapsule are discussed, which considered the performance of core, the thickness of shell, the rate of stiring and the rate of cooling. Microstructure and thermochromism performance of the S/O type NLHN-RTM microcapsule are characterized by Biomicroscope, Scanning Electron Microscopy, Thermal Gravimetric Analysis and Fourier Transform Infrared spectroscopy, and the particle size, thickness of shell, embedding efficiency, heat resistance, chemical stability, mechanism resistance and environment resistance, of the S/O type NLHN-RTM microcapsule are investigated, and the structure and performance of the NLHN-RTM microcapsule are discussed. Then the effects on thermochromism and project performance of the S/O type NLHN-RTM microcapsule in PVA elements coating, alkyd varnish coating and latex paint are discussed.
The results have shown that: the best choice is that the ratio of core and shell is 2 : 3, the mass of solvent is 70ml, the mass of emulsifier is 5wt%, emulsified time is 40min, the rate of stirring is 1000r/min, and the mass of phase stabilizer is 3wt%. The temperature of color changing of the S/O type NLHN-RTM microcapsule is 109.5℃, while the time of color changing is 60s, and the temperature and the time of color fading are 108℃ and 120s, and the sensitivity of color changing is 0.315 respectively. And it's color changes reversibly from green to purple. As a conclusion, the reversibility and sensitive are improved by microencapsulation, and high performances and prospected applications.
本研究采用油相相分离法，以无机变色颜料NLHN为芯材，乙基纤维素(EC)为壳材，环己烷(HC)为溶剂，Span-80为乳化剂，聚异丁烯(PIB)为相稳定剂，制备了S／O型NLHN-RTM微胶囊。试验研究了核-壳比、乳化剂用量、溶剂用量、相稳定剂用量、表面张力和搅拌速率等六个关键因素对S／O型NLHN-RTM微胶囊的粒度及其包裹率的影响，探讨了芯材性能、囊壁厚度、搅拌速率和冷却速率与S／O型NLHN-RTM微胶囊变色性能之间的关系。利用生物显微镜(BM)、扫描电子显微镜(SEM)、热重分析仪(TGA)、X-射线衍射仪(XRD)和红外光谱分析仪(IR)对S／O型NLHN-RTM微胶囊进行了结构表征与性能研究，分析了S／O型NLHN-RTM微胶囊的粒度、囊壁厚度、包裹率、热稳定性、化学稳定性、机械强度和环境适应性等，探讨了S／O型NLHN-RTM微胶囊结构与性能之间的关系。此外，将S／O型NLHN-RTM微胶囊以颜料的形式应用在PVA基础涂料、醇酸清漆基涂料和水性乳胶漆基涂料中，研究了S／O型NLHN-RTM微胶囊在油性和水性涂料中的应用。
研究表明，当核-壳比为2：3、溶剂环己烷用量为70ml、搅拌速率为1000r／min、乳化剂Span-80用量为5％，乳化时间为40min，相稳定剂量聚异丁烯用量为3％时，制备的S／O型NLHN-RTM微胶囊变色温度T_c为109.5℃，变色时间t_c为60s，复色温度T_f为108℃，复色时间t_f为120s，变色灵敏度K为0.315，其颜色在绿色和紫色之间发生可逆变化。结果表明，S／O型NLHN-RTM微胶提高了高温热致变色材料的可逆性、改善了变色灵敏性、扩宽了温度适用范围，具有良好的性能和广阔的应用前景。
Presently, the reversible thermochomic materials have become a hotspot of researching, and have high practical valued. Water-solubility inorganic thermal materials were wrapped by microencapsulation method in this paper, which in order to enhance the reversibility and extend the using area of different temperature.
In this thesis, using inorganic pigment (NLHN), ethyl cellulose (EC), cyclohexane (HC), Span-80 and poly-isobutylene (PIB) to prepare S/O type NLHN-RTM microcapsule by oil phase separation method in which NLHN EC, HC, Span-80 and PIB are used as core materials, shell materials, solvent, emulsifier respectively and phase stabilizer. The roles which act on the particle size and embedding efficiency of the S/O type NLHN-RTM microcapsule played by six factors: the ratio of core and shell, emulsifier concentration, solvent content, stabilizer content, surface tension, and the rate of stiring. The relation between the different factors and the thermochromism performance of S/O type NLHN-RTM microcapsule are discussed, which considered the performance of core, the thickness of shell, the rate of stiring and the rate of cooling. Microstructure and thermochromism performance of the S/O type NLHN-RTM microcapsule are characterized by Biomicroscope, Scanning Electron Microscopy, Thermal Gravimetric Analysis and Fourier Transform Infrared spectroscopy, and the particle size, thickness of shell, embedding efficiency, heat resistance, chemical stability, mechanism resistance and environment resistance, of the S/O type NLHN-RTM microcapsule are investigated, and the structure and performance of the NLHN-RTM microcapsule are discussed. Then the effects on thermochromism and project performance of the S/O type NLHN-RTM microcapsule in PVA elements coating, alkyd varnish coating and latex paint are discussed.
The results have shown that: the best choice is that the ratio of core and shell is 2 : 3, the mass of solvent is 70ml, the mass of emulsifier is 5wt%, emulsified time is 40min, the rate of stirring is 1000r/min, and the mass of phase stabilizer is 3wt%. The temperature of color changing of the S/O type NLHN-RTM microcapsule is 109.5℃, while the time of color changing is 60s, and the temperature and the time of color fading are 108℃ and 120s, and the sensitivity of color changing is 0.315 respectively. And it's color changes reversibly from green to purple. As a conclusion, the reversibility and sensitive are improved by microencapsulation, and high performances and prospected applications.
引文
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