螺吡喃羟丙基纤维素的合成及其性能研究
发布时间：2018-08-27 13:02
【摘要】：自然界中产量最丰富的可再生资源天然高分子纤维素,取之不尽,用之不竭。由于其具有价格低廉、储存稳定、生物降解性及生物相容性好、无毒和无免疫原性等很多优点,纤维素这一绿色资源得到了人们的广泛关注。本文将具有光响应性的螺吡喃化合物通过酯化反应接枝到羟丙基纤维素上,制备了螺吡喃功能化的羟丙基纤维素SP-HPC,并对接枝聚合物的结构及性能进行了表征和测试,主要研究内容如下：1.以四氢呋喃(THF)为溶剂,N,N'-二环己基碳二亚胺/4-二甲氨基吡啶DCC/DMAP)为催化体系,通过1’-(3-羧乙基)-3',3'-二甲基-6-硝基螺[吲哚啉-2,2[2H]吲哚啉苯并吡喃](SPCOOH)和羟丙基纤维素(HPC)的酯化反应合成了螺吡喃功能化羟丙基纤维素SP-HPC。考察了不同的投料比对取代度的影响。采用1H-NMR、FT-IR、TGA等方法对聚合物进行了表征；通过UV-Vis测试SP-HPC的四氢呋喃(THF)溶液的光致变色性能。结果表明,SP-HPC的THF溶液呈现可逆的快速光响应性。交替的紫外光辐射和黑暗条件的存放,使得SP-HPC溶液呈现无色和紫色两种状态的可逆转变。2.采用选择性水溶剂透析方法制备了胶束溶液。通过动态光散射、透射电镜和扫描电镜表征了自组装所形成的胶束的尺寸和形态。结果表明,SP-HPC在水中组装成了球形胶束,紫外光照射后,胶束内部疏水闭环形式的SP能够异构化为开环部花菁形式(MC),产生更紧密地堆叠作用,促使球形胶束收缩,粒径分布变窄,显示了光响应性。随着聚合物胶束水溶液浓度的增加和聚合物中螺吡喃取代度的增加,胶束的粒径也相应随之增大。3.利用旋涂方法制备了SP-HPC固体膜。通过UV-Vis测试了SP-HPC固体膜的光致变色性能,采用接触角测量仪考察了聚合物固体膜表面润湿性的变化。结果表明,SP-HPC固体膜具有良好的光刺激响应性,紫外光照射后再置于黑暗条件下,SP-HPC固体膜中开环的MC转变为SP的光响应性较慢,其表面接触角随着螺吡喃基团开环与闭环构型的改变而发生改变；SP-HPC固体膜表面接触角随着聚合物取代度的增加而变小,紫外光照前后接触角变化幅度随螺吡喃取代度的增加而变小。
[Abstract]:Natural polymer cellulose, the most abundant renewable resource in nature, is inexhaustible. Because of its advantages of low cost, stable storage, good biodegradability and biocompatibility, nontoxic and non-immunogenicity, cellulose as a green resource has been paid more and more attention. In this paper, the spiropyran compounds with photoresponse were grafted onto hydroxypropyl cellulose by esterification reaction. The SP-HPC, functionalized hydroxypropyl cellulose was prepared, and the structure and properties of the grafted polymers were characterized and tested. The main research contents are as follows: 1. In this paper, tetrahydrofuran (THF) was used as the solvent for the catalytic system. The catalytic system consisted of N _ (N) N _ (-) -dicyclohexyl carbodiimide / 4-dimethylaminopyridine (DCC/DMAP). The functional hydroxyl propyl cellulose SP-HPC. was synthesized by the esterification of 1 (3-carboxyethyl) -3oxy 3- dimethyl-6-nitrospiroid [indoline -2azopyran] (SPCOOH) and hydroxypropyl cellulose (HPC) (HPC) by the esterification reaction of 1- (3-carboxyethyl) -3- (3-) -trimethylidene 3-nitropiro [indoline -2azopyran] (SPCOOH) and hydroxypropyl cellulose (HPC) The influence of different feed ratio on the degree of substitution was investigated. The polymer was characterized by 1H-NMR-FT-IRGA, and the photochromic property of SP-HPC tetrahydrofuran (THF) solution was tested by UV-Vis. The results show that the THF solution of SP-HPC exhibits a reversible fast photoresponse. The alternating ultraviolet radiation and the storage of dark conditions make the SP-HPC solution appear the reversible transition of colorless and purple state. 2. Micelle solution was prepared by selective water solvent dialysis. The size and morphology of the self-assembled micelles were characterized by dynamic light scattering, transmission electron microscopy and scanning electron microscopy. The results showed that SP-HPC was assembled into spherical micelles in water. After UV irradiation, SP in the hydrophobic closed loop form of the micelles could be isomerized into (MC), in the form of open ring cyanine, resulting in the contraction of the spherical micelles and the narrowing of the particle size distribution. The optical response is shown. With the increase of the concentration of polymer micelle aqueous solution and the degree of substitution of spiropyran in polymer, the particle size of micelle increases accordingly. SP-HPC solid film was prepared by spin coating method. The photochromic properties of SP-HPC solid films were measured by UV-Vis and the changes of surface wettability of polymer solid films were investigated by contact angle measuring instrument. The results showed that the SP-HPC solid film had a good photo-stimulative response, and the photoresponse of the open-loop MC in the SP-HPC solid film changed to that of SP slowly after UV irradiation. The surface contact angle of SP-HPC film decreases with the increase of the degree of substitution of the polymer, and the surface contact angle changes with the change of the open-loop and closed-loop configuration of the spiropyran group, and the surface contact angle of the SP-HPC solid film decreases with the increase of the degree of substitution of the polymer. The range of contact angle before and after UV irradiation decreases with the increase of the degree of substitution of spiropyran.
【学位授予单位】：广西大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O636.1
本文编号：2207374
[Abstract]:Natural polymer cellulose, the most abundant renewable resource in nature, is inexhaustible. Because of its advantages of low cost, stable storage, good biodegradability and biocompatibility, nontoxic and non-immunogenicity, cellulose as a green resource has been paid more and more attention. In this paper, the spiropyran compounds with photoresponse were grafted onto hydroxypropyl cellulose by esterification reaction. The SP-HPC, functionalized hydroxypropyl cellulose was prepared, and the structure and properties of the grafted polymers were characterized and tested. The main research contents are as follows: 1. In this paper, tetrahydrofuran (THF) was used as the solvent for the catalytic system. The catalytic system consisted of N _ (N) N _ (-) -dicyclohexyl carbodiimide / 4-dimethylaminopyridine (DCC/DMAP). The functional hydroxyl propyl cellulose SP-HPC. was synthesized by the esterification of 1 (3-carboxyethyl) -3oxy 3- dimethyl-6-nitrospiroid [indoline -2azopyran] (SPCOOH) and hydroxypropyl cellulose (HPC) (HPC) by the esterification reaction of 1- (3-carboxyethyl) -3- (3-) -trimethylidene 3-nitropiro [indoline -2azopyran] (SPCOOH) and hydroxypropyl cellulose (HPC) The influence of different feed ratio on the degree of substitution was investigated. The polymer was characterized by 1H-NMR-FT-IRGA, and the photochromic property of SP-HPC tetrahydrofuran (THF) solution was tested by UV-Vis. The results show that the THF solution of SP-HPC exhibits a reversible fast photoresponse. The alternating ultraviolet radiation and the storage of dark conditions make the SP-HPC solution appear the reversible transition of colorless and purple state. 2. Micelle solution was prepared by selective water solvent dialysis. The size and morphology of the self-assembled micelles were characterized by dynamic light scattering, transmission electron microscopy and scanning electron microscopy. The results showed that SP-HPC was assembled into spherical micelles in water. After UV irradiation, SP in the hydrophobic closed loop form of the micelles could be isomerized into (MC), in the form of open ring cyanine, resulting in the contraction of the spherical micelles and the narrowing of the particle size distribution. The optical response is shown. With the increase of the concentration of polymer micelle aqueous solution and the degree of substitution of spiropyran in polymer, the particle size of micelle increases accordingly. SP-HPC solid film was prepared by spin coating method. The photochromic properties of SP-HPC solid films were measured by UV-Vis and the changes of surface wettability of polymer solid films were investigated by contact angle measuring instrument. The results showed that the SP-HPC solid film had a good photo-stimulative response, and the photoresponse of the open-loop MC in the SP-HPC solid film changed to that of SP slowly after UV irradiation. The surface contact angle of SP-HPC film decreases with the increase of the degree of substitution of the polymer, and the surface contact angle changes with the change of the open-loop and closed-loop configuration of the spiropyran group, and the surface contact angle of the SP-HPC solid film decreases with the increase of the degree of substitution of the polymer. The range of contact angle before and after UV irradiation decreases with the increase of the degree of substitution of spiropyran.
【学位授予单位】：广西大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O636.1
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