【摘要】：接枝共聚物是指支鏈通過(guò)共價(jià)鍵或非共價(jià)鍵形式接枝在主鏈上形成的一種支化結(jié)構(gòu)的聚合物。接枝共聚物的接支鏈數(shù)量、長(zhǎng)度及種類(lèi)均可調(diào)。與線型聚合物相比,具有支化結(jié)構(gòu)的接枝共聚物在藥物包覆、藥物控制釋放等領(lǐng)域展現(xiàn)出更加優(yōu)異的性能。本論文提出組合聚加成反應(yīng)和可控自由基聚合反應(yīng)合成兩種不同結(jié)構(gòu)的兩親性聚氨酯接枝共聚物。接枝聚合物主鏈為親油的聚氨酯聚合物,支鏈為親水的聚N,N-二甲基丙烯酰胺聚合物。支鏈以共價(jià)鍵或可逆共價(jià)鍵形式接枝在主鏈上。對(duì)兩親性聚氨酯接枝共聚物的結(jié)構(gòu)進(jìn)行了表征,并將聚合物用于穩(wěn)定乳液。本論文的研究工作主要包括以下兩個(gè)部分:(1)兩親性聚氨酯接枝聚N,N-二甲基丙烯酰胺(PU-g-PDMA)接枝共聚物的合成。首先合成了含雙羥基的三硫酯的化合物2,2-雙(羥甲基)-2-(((乙硫基)硫代甲酰基)硫)-2-甲基丙酸酯(BEMP)。然后以BEMP,六亞甲基二異氰酸酯(HDI)、1,4-丁二醇(BDO)為原料,通過(guò)聚加成反應(yīng)合成了一種側(cè)基含有三硫酯基團(tuán)的功能性聚氨酯(fPU)。以fPU做為大分子鏈轉(zhuǎn)移劑,偶氮二異丁腈(AIBN)為引發(fā)劑,在N,N-二甲基乙酰胺(DMAc)中進(jìn)行N,N-二甲基丙烯酰胺(DMA)單體的RAFT聚合反應(yīng),得到兩親性聚氨酯接枝共聚物PU-g-PDMA。對(duì)DMA單體RAFT聚合反應(yīng)動(dòng)力學(xué)進(jìn)行了研究,并對(duì)接枝共聚物的結(jié)構(gòu)進(jìn)行了表征。研究結(jié)果顯示:fPU引發(fā)DMA單體RAFT聚合反應(yīng)具有可控自由基聚合的特征。兩親性PU-g-PDMA在水中能組裝成球形膠束。該球形膠束能用作粒子乳化劑形成Pickering乳液。(2)兩親性聚氨酯接枝聚N,N-二甲基丙烯酰胺(PU-g-PDMA)超分子接枝共聚物的合成及穩(wěn)定乳液應(yīng)用。首先采用多步化學(xué)反應(yīng)合成了一種同時(shí)含雙羥基、二硫鍵、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-(2,2-二羥甲基丁酯)乙酯(BOMP)。然后以BOMP,二苯基甲烷二異氰酸酯(MDI)、1,4-丁二醇(BDO)為原料,通過(guò)聚加成反應(yīng)合成了一種側(cè)基同時(shí)含有二硫鍵、三硫酯基團(tuán)的功能性聚氨酯(fPU)。以fPU作大分子鏈轉(zhuǎn)移劑,偶氮二異丁腈(AIBN)為引發(fā)劑,在N,N-二甲基乙酰胺(DMAc)中進(jìn)行N,N-二甲基丙烯酰胺(DMA)單體的RAFT聚合反應(yīng),得到兩親性PU-g-PDMA超分子接枝共聚物。以PU-g-PDMA自組裝的膠束為乳化劑制備O/W型乳液,考察了乳化劑含量和水油比對(duì)乳液制備的影響,研究了乳液的氧化還原響應(yīng)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.
【學(xué)位授予單位】：湘潭大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O631

【參考文獻(xiàn)】

相關(guān)碩士學(xué)位論文 前1條

1 龍時(shí)宇;基于巰基點(diǎn)擊化學(xué)制備環(huán)形高分子的研究[D];武漢紡織大學(xué);2014年

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本文編號(hào)：2328517