两亲性聚氨酯接枝共聚物的制备及其乳液应用研究
发布时间：2018-11-13 08:09
【摘要】：接枝共聚物是指支链通过共价键或非共价键形式接枝在主链上形成的一种支化结构的聚合物。接枝共聚物的接支链数量、长度及种类均可调。与线型聚合物相比,具有支化结构的接枝共聚物在药物包覆、药物控制释放等领域展现出更加优异的性能。本论文提出组合聚加成反应和可控自由基聚合反应合成两种不同结构的两亲性聚氨酯接枝共聚物。接枝聚合物主链为亲油的聚氨酯聚合物,支链为亲水的聚N,N-二甲基丙烯酰胺聚合物。支链以共价键或可逆共价键形式接枝在主链上。对两亲性聚氨酯接枝共聚物的结构进行了表征,并将聚合物用于稳定乳液。本论文的研究工作主要包括以下两个部分:(1)两亲性聚氨酯接枝聚N,N-二甲基丙烯酰胺(PU-g-PDMA)接枝共聚物的合成。首先合成了含双羟基的三硫酯的化合物2,2-双(羟甲基)-2-(((乙硫基)硫代甲酰基)硫)-2-甲基丙酸酯(BEMP)。然后以BEMP,六亚甲基二异氰酸酯(HDI)、1,4-丁二醇(BDO)为原料,通过聚加成反应合成了一种侧基含有三硫酯基团的功能性聚氨酯(fPU)。以fPU做为大分子链转移剂,偶氮二异丁腈(AIBN)为引发剂,在N,N-二甲基乙酰胺(DMAc)中进行N,N-二甲基丙烯酰胺(DMA)单体的RAFT聚合反应,得到两亲性聚氨酯接枝共聚物PU-g-PDMA。对DMA单体RAFT聚合反应动力学进行了研究,并对接枝共聚物的结构进行了表征。研究结果显示:fPU引发DMA单体RAFT聚合反应具有可控自由基聚合的特征。两亲性PU-g-PDMA在水中能组装成球形胶束。该球形胶束能用作粒子乳化剂形成Pickering乳液。(2)两亲性聚氨酯接枝聚N,N-二甲基丙烯酰胺(PU-g-PDMA)超分子接枝共聚物的合成及稳定乳液应用。首先采用多步化学反应合成了一种同时含双羟基、二硫键、三硫酯的化合物2-(乙基三硫代碳酸酯基)-2-甲基丙酸-2-二硫-(2,2-二羟甲基丁酯)乙酯(BOMP)。然后以BOMP,二苯基甲烷二异氰酸酯(MDI)、1,4-丁二醇(BDO)为原料,通过聚加成反应合成了一种侧基同时含有二硫键、三硫酯基团的功能性聚氨酯(fPU)。以fPU作大分子链转移剂,偶氮二异丁腈(AIBN)为引发剂,在N,N-二甲基乙酰胺(DMAc)中进行N,N-二甲基丙烯酰胺(DMA)单体的RAFT聚合反应,得到两亲性PU-g-PDMA超分子接枝共聚物。以PU-g-PDMA自组装的胶束为乳化剂制备O/W型乳液,考察了乳化剂含量和水油比对乳液制备的影响,研究了乳液的氧化还原响应去乳化特性。
[Abstract]:Graft copolymers are branched polymers that are grafted on the main chain by covalent or non-covalent bonds. The number, length and type of the graft chain can be adjusted. Compared with linear polymers, grafted copolymers with branched structure showed better performance in drug coating and drug controlled release. In this paper, two kinds of amphiphilic polyurethane grafted copolymers with different structures were synthesized by combined polymerization and controlled radical polymerization. The main chain of grafted polymer is an oil-lipophilic polyurethane polymer, and the branched chain is a hydrophilic polyN- N-dimethylacrylamide polymer. Branched chains are grafted on the main chain in the form of covalent or reversible covalent bonds. The structure of the amphiphilic polyurethane graft copolymer was characterized and the polymer was used to stabilize the emulsion. The main work of this thesis includes the following two parts: (1) the synthesis of grafted copolymer of amphiphilic polyurethane (APC) with N- dimethylacrylamide (PU-g-PDMA). First of all, a compound containing bis (hydroxymethyl) -2- (ethylthioyl) thioyl) -2-methylpropionate (BEMP).) was synthesized. Then, using BEMP, hexamethylenediisocyanate (HDI), 1) -4-butanediol (BDO) as raw material, a kind of functional polyurethane (fPU). With side group containing trithioester group was synthesized by poly-addition reaction. Using fPU as macromolecular chain transfer agent and azodiisobutyronitrile (AIBN) as initiator, the RAFT polymerization of N- dimethylacrylamide (DMA) monomer was carried out in NN- dimethylacetamide (DMAc). Amphiphilic Polyurethane Graft Copolymer PU-g-PDMA. The kinetics of DMA monomer RAFT polymerization was studied and the structure of graft copolymer was characterized. The results show that the DMA monomer RAFT polymerization initiated by fPU has the characteristics of controllable radical polymerization. Amphiphilic PU-g-PDMA can be assembled into spherical micelles in water. The spherical micelles can be used as particle emulsifiers to form Pickering emulsions. (2) the synthesis and stable emulsion application of amphiphilic polyurethane graft copolymerization of N-dimethylacrylamide (PU-g-PDMA) supramolecular graft copolymers. Firstly, a compound 2- (ethyl trithiocarbamate) -2-methylpropionic acid-2-dithio-(2o 2-dihydroxymethyl butyl ester) ethyl ester (BOMP). Was synthesized by multistep chemical reaction. Then, using BOMP, diphenyl methane diisocyanate (MDI), 1 and 4 butanediol (BDO) as raw material, a kind of functional polyurethane (fPU). With side group and disulfide group was synthesized by poly-addition reaction. Using fPU as macromolecular chain transfer agent and azodiisobutyronitrile (AIBN) as initiator, the RAFT polymerization of N- dimethylacrylamide (DMA) monomer was carried out in NN- dimethylacetamide (DMAc). Amphiphilic PU-g-PDMA supramolecular graft copolymers were obtained. O / W emulsion was prepared by using PU-g-PDMA self-assembled micelle as emulsifier. The effects of emulsifier content and water-oil ratio on emulsion preparation were investigated. The redox response of the emulsion was studied.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631
本文编号：2328517
[Abstract]:Graft copolymers are branched polymers that are grafted on the main chain by covalent or non-covalent bonds. The number, length and type of the graft chain can be adjusted. Compared with linear polymers, grafted copolymers with branched structure showed better performance in drug coating and drug controlled release. In this paper, two kinds of amphiphilic polyurethane grafted copolymers with different structures were synthesized by combined polymerization and controlled radical polymerization. The main chain of grafted polymer is an oil-lipophilic polyurethane polymer, and the branched chain is a hydrophilic polyN- N-dimethylacrylamide polymer. Branched chains are grafted on the main chain in the form of covalent or reversible covalent bonds. The structure of the amphiphilic polyurethane graft copolymer was characterized and the polymer was used to stabilize the emulsion. The main work of this thesis includes the following two parts: (1) the synthesis of grafted copolymer of amphiphilic polyurethane (APC) with N- dimethylacrylamide (PU-g-PDMA). First of all, a compound containing bis (hydroxymethyl) -2- (ethylthioyl) thioyl) -2-methylpropionate (BEMP).) was synthesized. Then, using BEMP, hexamethylenediisocyanate (HDI), 1) -4-butanediol (BDO) as raw material, a kind of functional polyurethane (fPU). With side group containing trithioester group was synthesized by poly-addition reaction. Using fPU as macromolecular chain transfer agent and azodiisobutyronitrile (AIBN) as initiator, the RAFT polymerization of N- dimethylacrylamide (DMA) monomer was carried out in NN- dimethylacetamide (DMAc). Amphiphilic Polyurethane Graft Copolymer PU-g-PDMA. The kinetics of DMA monomer RAFT polymerization was studied and the structure of graft copolymer was characterized. The results show that the DMA monomer RAFT polymerization initiated by fPU has the characteristics of controllable radical polymerization. Amphiphilic PU-g-PDMA can be assembled into spherical micelles in water. The spherical micelles can be used as particle emulsifiers to form Pickering emulsions. (2) the synthesis and stable emulsion application of amphiphilic polyurethane graft copolymerization of N-dimethylacrylamide (PU-g-PDMA) supramolecular graft copolymers. Firstly, a compound 2- (ethyl trithiocarbamate) -2-methylpropionic acid-2-dithio-(2o 2-dihydroxymethyl butyl ester) ethyl ester (BOMP). Was synthesized by multistep chemical reaction. Then, using BOMP, diphenyl methane diisocyanate (MDI), 1 and 4 butanediol (BDO) as raw material, a kind of functional polyurethane (fPU). With side group and disulfide group was synthesized by poly-addition reaction. Using fPU as macromolecular chain transfer agent and azodiisobutyronitrile (AIBN) as initiator, the RAFT polymerization of N- dimethylacrylamide (DMA) monomer was carried out in NN- dimethylacetamide (DMAc). Amphiphilic PU-g-PDMA supramolecular graft copolymers were obtained. O / W emulsion was prepared by using PU-g-PDMA self-assembled micelle as emulsifier. The effects of emulsifier content and water-oil ratio on emulsion preparation were investigated. The redox response of the emulsion was studied.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631
【参考文献】
相关硕士学位论文 前1条
1 龙时宇;基于巯基点击化学制备环形高分子的研究[D];武汉纺织大学;2014年
，本文编号：2328517
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