基于單電子轉(zhuǎn)移活性自由基聚合技術(shù)的環(huán)境響應(yīng)性光電功能聚合物的設(shè)計(jì)、合成與自組裝行為
發(fā)布時(shí)間：2019-04-09 16:29
【摘要】：單電子轉(zhuǎn)移活性自由基聚合(Single electron transfer-living radical polymerization,SET-LRP)是一種在原子轉(zhuǎn)移活性自由基聚合(Atom transfer radical polymerization,ATRP)基礎(chǔ)上發(fā)展而來(lái)的新的聚合方法。在SET-LRP聚合反應(yīng)中,單質(zhì)Cu(0)通過(guò)非均相外層電子轉(zhuǎn)移使引發(fā)劑中結(jié)合較弱的碳-鹵鍵在多相體系溶液中異裂產(chǎn)生自由基來(lái)激活休眠種,并形成自由基鈍化-活化平衡來(lái)有效控制自由基的濃度,從而達(dá)到可控“活性自由基聚合”的目的。該聚合方法能夠很好控制聚合物的相對(duì)分子質(zhì)量、相對(duì)分子質(zhì)量分布,并且還很容易改變聚合物的化學(xué)組分,設(shè)計(jì)合成具有復(fù)雜拓?fù)浣Y(jié)構(gòu)以及具有很高鏈端功能團(tuán)含量功能高分子材料。本課題中我們主要以SET-LRP聚合技術(shù)并結(jié)合ATRP制備了一系列聚合物光電功能分子,并詳細(xì)研究了不同環(huán)境因子對(duì)聚合物的聚合動(dòng)力學(xué)、光電性能和自組裝行為的影響。首先我們以成熟的室溫下丙烯酸甲酯(Methyl acrylate,MA)在二甲基亞砜(Dimethyl sulfoxide,DMSO)中的SET-LRP聚合動(dòng)力學(xué)作為研究對(duì)象。通過(guò)在反應(yīng)中添加不同摩爾濃度的無(wú)水FeCl3,詳細(xì)研究了其對(duì)MA的SET-LRP聚合動(dòng)力學(xué)的影響。實(shí)驗(yàn)結(jié)果表明,加入Fe(III)以后,聚合反應(yīng)仍然表現(xiàn)為活性自由基聚合,引發(fā)劑效率比較高,鏈端功能團(tuán)被較為完美的保留,含量均在85%以上。此外,在加入一定量鐵鹽后所得聚合物的多分散性指數(shù)變大(1.19~1.14),但是和不加Fe(III)相比,影響不大。并且隨著三價(jià)鐵離子量Fe(III)含量的增加,其鏈增長(zhǎng)速率常數(shù)下降,并且出現(xiàn)誘導(dǎo)期延長(zhǎng)的現(xiàn)象,說(shuō)明三價(jià)鐵離子參與了SET-LRP的聚合動(dòng)力學(xué)過(guò)程,它和在同樣實(shí)驗(yàn)條件下二價(jià)銅所起的作用截然不同,顯著變長(zhǎng)。表明添加具有減活作用的無(wú)水FeCl3能夠有效調(diào)節(jié)SET-LRP的聚合動(dòng)力學(xué)。聚(N-異丙基丙烯酰胺)(Poly(N-isopropylacrylamide),PNIPAM)是一種兩親性環(huán)境敏感的高分子材料。該聚合物中含有親水性酰胺基和疏水性異丙基,當(dāng)外界溫度發(fā)生變化時(shí),通過(guò)分子間的相互作用其自身會(huì)發(fā)生可逆性的相變化。我們利用具有易于合成,可高效進(jìn)行化學(xué)修飾、量子產(chǎn)率高等優(yōu)點(diǎn)的四苯基乙烯(Tetraphenylethene,TPE)類分子作為引發(fā)劑。通過(guò)N-異丙基丙烯酰胺的SET-LRP聚合反應(yīng),制備了具有AIE(Aggregation-induced emission,AIE)效應(yīng)的大分子引發(fā)劑PNIPAM-Br,然后以苯乙烯為單體,通過(guò)ATRP聚合制備兩親性嵌段聚合物PNIPAM-b-PSt,并詳細(xì)研究了具有AIE效應(yīng)的引發(fā)劑和兩親性嵌段聚合物在不同溫度和濃度下光物理性質(zhì)和自組裝行為的變化情況。研究發(fā)現(xiàn)相同濃度條件下,隨著溫度的升高AIE效應(yīng)引發(fā)劑熒光強(qiáng)度不斷下降,而嵌段聚合物的熒光強(qiáng)度先上升。當(dāng)溫度超過(guò)到37 oC后,嵌段聚合物的熒光強(qiáng)度不斷下降。同樣的,通過(guò)依次改變AIE效應(yīng)引發(fā)劑和嵌段聚合物在四氫呋喃和水混合溶劑中的濃度發(fā)現(xiàn),隨著濃度的減小,AIE效應(yīng)引發(fā)劑的熒光強(qiáng)度不斷下降,改變濃度時(shí)嵌段聚合物熒光強(qiáng)度的變化規(guī)律和改變溫度時(shí)熒光強(qiáng)度的變化趨勢(shì)相似,說(shuō)明在雙親性嵌段聚合物末端掛接AIE效應(yīng)的TPE分子是可以表征其聚集態(tài)結(jié)構(gòu)的變化。最后我們又進(jìn)一步研究了不同濃度混合溶劑中嵌段聚合物的自組裝行為,隨著分散液濃度的降低,組裝體的尺寸變小,并經(jīng)歷從片狀到球狀再到無(wú)規(guī)則形狀的演化過(guò)程,說(shuō)明改變分散液的濃度可以大范圍調(diào)節(jié)所得組裝體的大小和形狀。
[Abstract]:Single electron transfer-polymerization (SET-LRP) is a new method of polymerization developed on the basis of atom transfer active radical polymerization (ATRP). in that SET-LRP polymerization reaction, the simple substance Cu (0) generate free radicals in the multi-phase system solution by the heterogeneous outer layer electron transfer to generate free radicals in the multi-phase system solution to activate the dormant species, and form a free radical passivation-activation balance to effectively control the concentration of the free radicals, So as to achieve the purpose of controllable "active free radical polymerization". The polymerization method can well control the relative molecular mass and relative molecular weight distribution of the polymer, and also can easily change the chemical components of the polymer, and is designed and synthesized to have a complex topological structure and a high-chain end functional group content functional high molecular material. In this paper, a series of polymer photo-functional molecules were prepared by SET-LRP and ATRP, and the effects of different environmental factors on the polymerization kinetics, photoelectricity and self-assembly behavior of the polymer were studied in detail. The kinetics of SET-LRP polymerization of methyl acrylate (MA) in Dimethylacrylate (DMSO) at room temperature was first studied. The effect of its SET-LRP polymerization kinetics on MA was studied in detail by adding anhydrous FeCl3 with different molar concentrations in the reaction. The experimental results show that after the addition of Fe (III), the polymerization still shows that the polymerization of the active free radical, the initiator efficiency is high, the chain end functional group is preserved perfectly, and the content is above 85%. In addition, the polydispersity index of the polymer obtained after the addition of a certain amount of iron salt was increased (1.19 to 1.14), but the effect was not large compared with the addition of Fe (III). In addition, with the increase of the content of Fe (III) in the ferric ion, the rate of chain growth is decreased and the induction period is prolonged. It is indicated that the ferric ion is involved in the process of the polymerization of SET-LRP, which is very different from the action of the divalent copper under the same experimental conditions, and it becomes longer. It is shown that the addition of anhydrous FeCl3 with deactivation effect can effectively adjust the polymerization kinetics of SET-LRP. Poly (N-isopropylidenamine) (PNIPAM) is an amphiphilic environment-sensitive polymer material. The polymer contains a hydrophilic polar amine group and a hydrophobic isopropyl group, and when the external temperature is changed, the reversible phase change can occur through the interaction between the molecules. Tetraphenylethylene (TPE) molecules with the advantages of easy synthesis, high efficiency for chemical modification, high quantum yield and the like can be used as the initiator. A macromolecular initiator PNIPAM-Br with AIE (AIE) effect was prepared by using a SET-LRP polymerization of N-isopropylamide and then the amphipathic block polymer PNIPAM-b-PSt was prepared by ATRP polymerization using styrene as a monomer. The changes of light physical properties and self-assembly behavior of initiator and amphipathic block polymer with AIE effect at different temperatures and concentrations were studied in detail. The fluorescence intensity of the block polymer was first increased with the increase of the temperature and the increase of the fluorescence intensity of the AIE effect. When the temperature exceeds 37 oC, the fluorescence intensity of the block polymer decreases. In the same way, by sequentially changing the concentration of the AIE effect initiator and the block polymer in the tetrahydrogen peroxide and the water mixed solvent, as the concentration is reduced, the fluorescence intensity of the AIE effect initiator is continuously reduced, The change of the fluorescence intensity of the block polymer when the concentration is changed and the change tendency of the fluorescence intensity at the time of the change are similar, and the change of the structure of the aggregation state can be characterized by the AIE effect on the end of the amphiphilic block polymer. In that end, we further study the self-assembly behavior of the block polymer in the mixed solvent of different concentration, with the decrease of the concentration of the dispersion liquid, the size of the assembly becomes small, and the evolution process from the sheet-like to the non-regular shape is experience. The size and shape of the resulting assembly can be adjusted in a large range by changing the concentration of the dispersion.
【學(xué)位授予單位】：南京郵電大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.5
本文編號(hào)：2455336
[Abstract]:Single electron transfer-polymerization (SET-LRP) is a new method of polymerization developed on the basis of atom transfer active radical polymerization (ATRP). in that SET-LRP polymerization reaction, the simple substance Cu (0) generate free radicals in the multi-phase system solution by the heterogeneous outer layer electron transfer to generate free radicals in the multi-phase system solution to activate the dormant species, and form a free radical passivation-activation balance to effectively control the concentration of the free radicals, So as to achieve the purpose of controllable "active free radical polymerization". The polymerization method can well control the relative molecular mass and relative molecular weight distribution of the polymer, and also can easily change the chemical components of the polymer, and is designed and synthesized to have a complex topological structure and a high-chain end functional group content functional high molecular material. In this paper, a series of polymer photo-functional molecules were prepared by SET-LRP and ATRP, and the effects of different environmental factors on the polymerization kinetics, photoelectricity and self-assembly behavior of the polymer were studied in detail. The kinetics of SET-LRP polymerization of methyl acrylate (MA) in Dimethylacrylate (DMSO) at room temperature was first studied. The effect of its SET-LRP polymerization kinetics on MA was studied in detail by adding anhydrous FeCl3 with different molar concentrations in the reaction. The experimental results show that after the addition of Fe (III), the polymerization still shows that the polymerization of the active free radical, the initiator efficiency is high, the chain end functional group is preserved perfectly, and the content is above 85%. In addition, the polydispersity index of the polymer obtained after the addition of a certain amount of iron salt was increased (1.19 to 1.14), but the effect was not large compared with the addition of Fe (III). In addition, with the increase of the content of Fe (III) in the ferric ion, the rate of chain growth is decreased and the induction period is prolonged. It is indicated that the ferric ion is involved in the process of the polymerization of SET-LRP, which is very different from the action of the divalent copper under the same experimental conditions, and it becomes longer. It is shown that the addition of anhydrous FeCl3 with deactivation effect can effectively adjust the polymerization kinetics of SET-LRP. Poly (N-isopropylidenamine) (PNIPAM) is an amphiphilic environment-sensitive polymer material. The polymer contains a hydrophilic polar amine group and a hydrophobic isopropyl group, and when the external temperature is changed, the reversible phase change can occur through the interaction between the molecules. Tetraphenylethylene (TPE) molecules with the advantages of easy synthesis, high efficiency for chemical modification, high quantum yield and the like can be used as the initiator. A macromolecular initiator PNIPAM-Br with AIE (AIE) effect was prepared by using a SET-LRP polymerization of N-isopropylamide and then the amphipathic block polymer PNIPAM-b-PSt was prepared by ATRP polymerization using styrene as a monomer. The changes of light physical properties and self-assembly behavior of initiator and amphipathic block polymer with AIE effect at different temperatures and concentrations were studied in detail. The fluorescence intensity of the block polymer was first increased with the increase of the temperature and the increase of the fluorescence intensity of the AIE effect. When the temperature exceeds 37 oC, the fluorescence intensity of the block polymer decreases. In the same way, by sequentially changing the concentration of the AIE effect initiator and the block polymer in the tetrahydrogen peroxide and the water mixed solvent, as the concentration is reduced, the fluorescence intensity of the AIE effect initiator is continuously reduced, The change of the fluorescence intensity of the block polymer when the concentration is changed and the change tendency of the fluorescence intensity at the time of the change are similar, and the change of the structure of the aggregation state can be characterized by the AIE effect on the end of the amphiphilic block polymer. In that end, we further study the self-assembly behavior of the block polymer in the mixed solvent of different concentration, with the decrease of the concentration of the dispersion liquid, the size of the assembly becomes small, and the evolution process from the sheet-like to the non-regular shape is experience. The size and shape of the resulting assembly can be adjusted in a large range by changing the concentration of the dispersion.
【學(xué)位授予單位】：南京郵電大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.5
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 袁偉;袁媛;陳于藍(lán);;機(jī)械力誘導(dǎo)發(fā)光高分子材料[J];高分子學(xué)報(bào);2016年11期
，本文編號(hào)：2455336
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2455336.html
最近更新
教材專著
