本文選題：受限 + 高分子　； 參考：《南京大學(xué)》2017年博士論文

【摘要】：處在納米尺度的高分子的結(jié)晶動(dòng)力學(xué)、粘度、玻璃化轉(zhuǎn)變溫度、物理老化速率都表現(xiàn)出與本體的巨大差別。自1994年人們開始研究受限態(tài)高分子的玻璃化轉(zhuǎn)變以來(lái),受限態(tài)物質(zhì)的性質(zhì)受到大家的持續(xù)關(guān)注,雖然在這個(gè)方面國(guó)際上已經(jīng)開展了許許多多的研究,但是大部分研究的關(guān)注點(diǎn)在于表觀物理性質(zhì)的改變,很少有人去關(guān)注受限態(tài)高分子的微觀結(jié)構(gòu)。這主要?dú)w因于研究手段的相對(duì)缺乏,處在納米受限態(tài)的高分子含量極少,樣品與背景的信號(hào)不易區(qū)分。在本論文的工作中,我們用熒光無(wú)輻射能量轉(zhuǎn)移法(FRET)表征高分子的結(jié)構(gòu),結(jié)合量熱學(xué)的手段研究受限態(tài)高分子的玻璃化轉(zhuǎn)變行為。基于FRET在高分子物理中的應(yīng)用現(xiàn)狀,我們發(fā)現(xiàn)無(wú)規(guī)標(biāo)記的樣品很難應(yīng)用于定量分析,所以我們利用可控自由基聚合的方法制備染料標(biāo)記位點(diǎn)明確的高分子。首先,我們探索了鏈末端標(biāo)記熒光基團(tuán)高分子的合成方法,從而我們可以表征高分子的鏈內(nèi)距離。我們合成了一種全新的鏈轉(zhuǎn)移劑,它是一種同時(shí)包含咔唑和蒽的雙硫酯結(jié)構(gòu),我們利用可逆加成斷裂鏈轉(zhuǎn)移(RAFT)聚合的方法制備了聚苯乙烯(PS),聚甲基丙烯酸甲酯(PMMA),聚甲基丙烯酸丁酯(PBMA),分子量從幾千到幾萬(wàn)可調(diào),產(chǎn)物分散性窄。我們以PBMA為例,證實(shí)了反應(yīng)動(dòng)力學(xué)符合活性聚合特征。此外,我們又探索了利用位點(diǎn)指定的原子轉(zhuǎn)移自由基聚合(ATRP)結(jié)合點(diǎn)擊化學(xué)的后改性方法同樣制備了這種鏈末端標(biāo)記不同熒光基團(tuán)的遙爪聚合物。我們制備了熒光受體接枝的ATRP引發(fā)劑,通過(guò)ATRP使得受體被定位在鏈的α端,將ω端的溴基改性為疊氮基,再與咔唑改性的炔進(jìn)行點(diǎn)擊化學(xué)反應(yīng),即可制備這種鏈末端標(biāo)記不同熒光基團(tuán)的遙爪聚合物PS和PMMA。通過(guò)控制反應(yīng)轉(zhuǎn)化率,我們制備了數(shù)均分子量為5500的PS,末端熒光基團(tuán)的含量均在90%以上,反映了定量標(biāo)記的特征。對(duì)于PMMA而言,α端受體的標(biāo)記產(chǎn)率近100%,但因聚合反應(yīng)單體轉(zhuǎn)化率較高造成了 ω端給體的標(biāo)記產(chǎn)率只有58.2%。我們結(jié)合熒光光譜的分析證實(shí)了合成的高分子的末端距分布函數(shù)與理論值一樣,說(shuō)明了這兩種合成的結(jié)構(gòu)能夠定量應(yīng)用于FRET的研究,這得益于這種特殊的合成方法學(xué)可以保證有咔唑的鏈的另一端一定有蒽基,這就可以保證這種結(jié)構(gòu)可以用于FRET的定量研究,也使得這種聚合方法可以輕松實(shí)現(xiàn)定量FRET研究而不需要特別考慮反應(yīng)的轉(zhuǎn)化率以及ω端功能性的缺失。其次,在完成了鏈內(nèi)FRET的定量計(jì)算后,我們考慮鏈間FRET的定量研究,這需要我們確保每根鏈上有且只有一個(gè)熒光基團(tuán)。我們制備了四種全新的雙功能的ATRP引發(fā)劑,引發(fā)劑的結(jié)構(gòu)中分別標(biāo)記了咔唑基和蒽基,然后通過(guò)本體聚合制備了分子量從幾千到幾萬(wàn)的PS,PMMA和PBMA,通過(guò)紫外光譜,我們確證了每根鏈上標(biāo)記產(chǎn)率均在90%以上,這種近乎定量的標(biāo)記產(chǎn)率為我們定量進(jìn)行鏈間距離的計(jì)算提供了強(qiáng)有力的保證。我們基于熒光光譜法,檢測(cè)了不同分子量、高分子種類的聚合物的鏈間距離,計(jì)算結(jié)果與理論值一致,這表明我們聚合的產(chǎn)物能夠有效地應(yīng)用于定量分析。接下來(lái),我們探索鏈中心標(biāo)記熒光基團(tuán)的高分子在超薄膜結(jié)構(gòu)表征中的應(yīng)用�；跓晒鈮勖鼫y(cè)試,我們可以通過(guò)擬合得到熒光基團(tuán)在空間中的維度分布信息。因?yàn)槊扛溕嫌星抑挥幸粋�(gè)熒光基團(tuán),熒光基團(tuán)的空間分布可以反映高分子鏈的排布狀態(tài),當(dāng)熒光基團(tuán)呈平面分布時(shí),說(shuō)明高分子線團(tuán)的排列狀態(tài)是單分子層堆積。以PMMA為例,我們通過(guò)分析得到當(dāng)膜厚降低至1.5Rg時(shí),薄膜中的高分子線團(tuán)呈單分子層排列。這種特殊結(jié)構(gòu)的高分子結(jié)合壽命擬合分析可以幫助我們獲得單層堆積的高分子膜。通過(guò)濃度分析我們看到了因受限效應(yīng),導(dǎo)致高分子鏈的壓縮鏈間解纏結(jié)的現(xiàn)象。我們結(jié)合超靈敏差分交流芯片量熱儀(AC-chip)研究了基底支撐的PMMA薄膜的玻璃化行為,發(fā)現(xiàn)隨著膜厚的降低,玻璃化轉(zhuǎn)變溫度(rg)呈現(xiàn)升高現(xiàn)象。最后,除了高分子薄膜以外,我們拓展了受限維度的研究范圍,成功實(shí)現(xiàn)了從一維薄膜的研究到二維納米管道受限態(tài)的研究。我們研究了 PBMA受限在陽(yáng)極氧化鋁AAO中的玻璃化轉(zhuǎn)變行為以及鏈結(jié)構(gòu),發(fā)現(xiàn)慢速降溫受限態(tài)熔體將得到兩個(gè)rg,一個(gè)高于本體的rg,hi對(duì)應(yīng)界面層;一個(gè)等于本體的T_g,low對(duì)應(yīng)中間層。形成界面吸附層的關(guān)鍵在于高分子應(yīng)發(fā)生吸附轉(zhuǎn)變,制樣過(guò)程需達(dá)到吸附轉(zhuǎn)變溫度的閾值,證實(shí)了界面層的鏈間鄰近度比本體更加靠近。對(duì)于高分子量的PBMA來(lái)說(shuō),300 nm孔徑的AAO中的PBMA易形成兩個(gè)rg,小于等于100 nm孔徑AAO中的PBMA納米線只能形成一個(gè)T_g。通過(guò)界面改性的方法,可以抑制大分子量聚合物在AAO中界面層的形成,但不能抑制寡聚物界面層的形成。這說(shuō)明針對(duì)不同分子量的高分子來(lái)說(shuō),界面改性對(duì)形成界面吸附層的影響機(jī)理可能不同。
[Abstract]:The crystallization kinetics, viscosity, vitrification temperature and physical aging rate of nanoscale polymers show great differences with the body. Since the glass transition of restricted polymers has been studied in 1994, the properties of restricted materials have been paid more and more attention, although in this respect have been carried out internationally There are a lot of studies, but most of the attention is on the change of apparent physical properties. Few people pay attention to the microstructure of confined polymers. This is mainly due to the relative lack of research means, the low polymer content in the nano limited state, and the difficult to distinguish between the sample and the background signal. We use the fluorescence free energy transfer (FRET) to characterize the structure of polymer and study the glass transition behavior of confined polymers by means of calorimetry. Based on the current application of FRET in polymer physics, we find that the random labeled samples are difficult to apply to the fixed quantity analysis, so we use the controlled free radical polymerization. First, we have explored the synthesis method of the chain terminal labeled fluorescent group polymer, thus we can characterize the intra chain distance of the polymer. We have synthesized a new chain transfer agent, which is a double disulfide structure containing both carbazole and anthracene. We use reversible addition break. Polystyrene (PS), polymethylmethacrylate (PMMA) and polybutyl methacrylate (PBMA) are prepared by RAFT polymerization. The molecular weight is adjustable from several thousand to tens of thousands, and the dispersivity of the products is narrow. In the case of PBMA, we confirm that the reaction kinetics conforms to the characteristics of the active polymerization. In addition, we also explored the atomic transfer specified by the site. The free radical polymerization (ATRP) combined with clicking chemistry was also used to prepare the teleconnelling polymer with different fluorescent groups at the end of the chain. We prepared the ATRP initiator grafted by the fluorescent receptor. Through ATRP, the receptor was positioned at the alpha end of the chain, the bromyl group at the Omega end was modified to azido, and then the alkyne modified by carbazole was carried out. By chemical reaction, the teleconnelling polymer PS and PMMA. with different fluorescent groups at the end of the chain were prepared. By controlling the conversion rate of the reaction, we prepared a PS with a mean molecular weight of 5500. The content of the terminal fluorescent group was above 90%, reflecting the characteristics of the quantitative labeling. For PMMA, the labeling yield of alpha end receptor was nearly 100%, but because of the result, the factor of alpha end receptor was nearly 100%. The high conversion rate of polymerization monomer resulted in the labeling yield of Omega end donor only 58.2%.. We confirmed that the terminal distance distribution function of the synthesized polymer was the same as that of the theoretical value by the analysis of the fluorescence spectrum. It shows that the two synthetic structures can be used in the study of FRET. This is due to this special synthesis method. In order to ensure that the other end of carbazole chain must have anthracene, it can be guaranteed that this structure can be used for quantitative study of FRET, and that this polymerization method can easily realize quantitative FRET research without special consideration of the conversion rate and Omega function loss. We consider the quantitative study of interchain FRET, which requires us to ensure that there is only one fluorescent group on each chain. We have prepared four new dual functional ATRP initiators. The structure of the initiator is marked with carbazole and anthracene respectively in the structure of the initiator, and the molecular weight from several thousand to tens of thousands of PS, PMMA and PBMA is prepared through the bulk polymerization through the purple. In the external spectrum, we confirm that the yield of each chain is more than 90%. This nearly quantitative labeling yield provides a strong guarantee for the calculation of the interchain distance of the chain. Based on the fluorescence spectrum, the interchain distance of the polymers of different molecular weights and polymer types is detected, and the calculated results are in accordance with the theoretical values. It shows that our polymerized products can be effectively used in quantitative analysis. Next, we explore the application of polymer in chain center labeled fluorescent group in ultrathin membrane structure characterization. Based on the fluorescence lifetime test, we can get the dimensional distribution information of the fluorescent group in the space by fitting the fluorescent group. The spatial distribution of fluorescent groups and fluorescent groups can reflect the arrangement state of polymer chains. When the fluorescent groups are distributed in a plane, the arrangement state of the polymer wires is a single molecular layer. As an example, we have obtained that when the thickness of the membrane is reduced to 1.5Rg, the polymer lines in the film are arranged in a single molecular layer. The structural polymer lifetime fitting analysis can help us obtain the monolayer polymer membrane. Through the concentration analysis, we see the entanglement between the compression chains of the polymer chain due to the limited effect. We study the vitrification of the PMMA film supported by the substrate with the ultra sensitive differential AC chip calorimeter (AC-chip). Behavior, it is found that the glass transition temperature (RG) increases with the decrease of the thickness of the membrane. Finally, besides the polymer film, we expand the scope of the limited dimension, and successfully realized the study of the limited state of the two-dimensional nanotube from the one-dimensional thin film. We studied the vitrification of the PBMA limited in the anodic alumina AAO. The transition behavior and chain structure show that the slow cooling limited state will get two RG, a RG higher than the noumenon, hi corresponding to the interface layer; a T_g, low corresponding to the middle layer. The key to the formation of the interface adsorption layer is that the polymer should have adsorption transition, and the sample process needs to reach the threshold of adsorption transition temperature, and the interface layer is confirmed. The interchain proximity is closer than that of the noumenon. For the high molecular weight PBMA, the PBMA in the AAO of 300 nm aperture is easy to form two RG, and the PBMA nanowires in the AAO of less than 100 nm aperture can only form a T_g. through the interface modification method, which can inhibit the formation of the interface layer of the large molecular weight polymer in AAO, but can not inhibit the oligomer. The formation of interface layer indicates that the mechanism of interfacial modification on the interface adsorption layer is different for polymer with different molecular weights.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.1

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 陳介平;;高分子結(jié)構(gòu)對(duì)高分子化學(xué)反應(yīng)性的影響[J];化學(xué)通報(bào);1980年11期

2 安智珠;;高分子的污染與防治[J];四川環(huán)境;1987年02期

3 趙芳;;高分子:微觀世界的“巨人”[J];發(fā)明與創(chuàng)新(中學(xué)時(shí)代);2013年08期

4 黃發(fā)榮;降解高分子的設(shè)計(jì)及其材料[J];化學(xué)世界;2000年S1期

5 羅娟;王立堅(jiān);羅祥林;;磷脂高分子的研究進(jìn)展[J];高分子材料科學(xué)與工程;2006年02期

6 沈瑜;張朝云;章林溪;;受限于平行界面之間高分子鏈力學(xué)行為的研究[J];高分子學(xué)報(bào);2007年02期

7 李玲娜;;對(duì)高分子鏈模擬的數(shù)學(xué)研究[J];中國(guó)西部科技(學(xué)術(shù));2007年09期

8 溫曉會(huì);章林溪;;打結(jié)高分子鏈穿孔行為的研究[J];物理學(xué)報(bào);2010年10期

9 滕超;薛奇;;高分子鏈的去擁擠轉(zhuǎn)變及低溫流動(dòng)[J];高分子學(xué)報(bào);2011年09期

10 周宏偉;梁恩湘;鄭朝暉;丁小斌;彭宇行;;基于Belousov-Zhabotinsky自振蕩反應(yīng)的智能高分子[J];化學(xué)進(jìn)展;2011年11期

相關(guān)會(huì)議論文 前10條

1 王超;孫李真;羅孟波;;高分子鏈分離的模擬研究[A];2013年全國(guó)高分子學(xué)術(shù)論文報(bào)告會(huì)論文摘要集——主題B：高分子理論、計(jì)算與模擬[C];2013年

2 顧芳;王海軍;;高分子鏈通過(guò)薄膜上納米孔隙的理論研究[A];中國(guó)化學(xué)會(huì)第27屆學(xué)術(shù)年會(huì)第07分會(huì)場(chǎng)摘要集[C];2010年

3 羅孟波;;高分子鏈穿越相互作用的小孔的自由能輪廓和動(dòng)力學(xué)行為[A];中國(guó)化學(xué)會(huì)第27屆學(xué)術(shù)年會(huì)第07分會(huì)場(chǎng)摘要集[C];2010年

4 吉青;楊小震;;高分子鏈在溶液與熔體中的構(gòu)象態(tài)結(jié)構(gòu)與構(gòu)象態(tài)躍遷[A];2005年全國(guó)高分子學(xué)術(shù)論文報(bào)告會(huì)論文摘要集[C];2005年

5 雍懷松;羅開富;;高分子鏈穿越納米長(zhǎng)孔的輸運(yùn)動(dòng)力學(xué)[A];2011年全國(guó)高分子學(xué)術(shù)論文報(bào)告會(huì)論文摘要集[C];2011年

6 付翠柳;孫昭艷;安立佳;;高分子鏈靜態(tài)和動(dòng)態(tài)性質(zhì)的受限程度依賴性[A];2011年全國(guó)高分子學(xué)術(shù)論文報(bào)告會(huì)論文摘要集[C];2011年

7 付翠柳;孫昭艷;安立佳;;高分子鏈靜態(tài)和動(dòng)態(tài)性質(zhì)的受限程度依賴性[A];中國(guó)化學(xué)會(huì)第28屆學(xué)術(shù)年會(huì)第13分會(huì)場(chǎng)摘要集[C];2012年

8 安全福;錢錦文;王猛;程昒時(shí);;溶液中高分子鏈的疊加度[A];2009年全國(guó)高分子學(xué)術(shù)論文報(bào)告會(huì)論文摘要集（上冊(cè)）[C];2009年

9 楊小震;張竹青;;高分子鏈線團(tuán)互穿程度的力學(xué)響應(yīng)[A];2005年全國(guó)高分子學(xué)術(shù)論文報(bào)告會(huì)論文摘要集[C];2005年

10 盧宇源;安立佳;王十慶;王振綱;;啟動(dòng)形變下高分子鏈構(gòu)象與纏結(jié)點(diǎn)演化的動(dòng)力學(xué)研究[A];2013年全國(guó)高分子學(xué)術(shù)論文報(bào)告會(huì)論文摘要集——主題B：高分子理論、計(jì)算與模擬[C];2013年

相關(guān)重要報(bào)紙文章 前2條

1 本報(bào)記者 常麗君;向高分子“交通網(wǎng)”學(xué)如何治堵[N];科技日?qǐng)?bào);2013年

2 本報(bào)記者 馮海波;中國(guó)科學(xué)院院士程昒時(shí)在高分子材料世界“遨游”[N];廣東科技報(bào);2011年

相關(guān)博士學(xué)位論文 前10條

1 馬新;納米粒子表面接枝高分子共混刷體系的相行為研究[D];復(fù)旦大學(xué);2013年

2 栗娟;高分子鏈驅(qū)動(dòng)變形的計(jì)算機(jī)模擬研究[D];南京大學(xué);2014年

3 王超;高分子鏈通過(guò)管道輸運(yùn)的蒙特卡羅模擬[D];浙江大學(xué);2015年

4 李洪;基于Monte Carlo方法模擬自回避鏈的計(jì)算方法及并行優(yōu)化[D];山東大學(xué);2015年

5 王生;智能高分子脂質(zhì)囊泡納米系統(tǒng)在腫瘤診療中的初步應(yīng)用[D];天津大學(xué);2015年

6 蘇鳳梅;同步輻射技術(shù)原位研究高分子結(jié)晶前預(yù)有序[D];中國(guó)科學(xué)技術(shù)大學(xué);2016年

7 柴利國(guó);不同界面對(duì)高分子單晶熔融行為的影響[D];北京化工大學(xué);2016年

8 冒海燕;水性聚氨酯基高分子染料的合成及性能[D];江南大學(xué);2017年

9 羅仲龍;溶劑與側(cè)鏈對(duì)高分子單鏈彈性影響的單分子力譜研究[D];西南交通大學(xué);2016年

10 蒲明鋒;活性體系非平衡動(dòng)力學(xué)若干問(wèn)題的理論研究[D];中國(guó)科學(xué)技術(shù)大學(xué);2017年

相關(guān)碩士學(xué)位論文 前10條

1 錢宏;部分帶電高分子鏈通過(guò)小孔的模擬研究[D];浙江大學(xué);2012年

2 王利波;高分子鏈穿過(guò)納米孔的計(jì)算機(jī)模擬[D];浙江大學(xué);2012年

3 張春英;高分子鏈在狹窄管道內(nèi)構(gòu)象和擴(kuò)散的蒙特卡羅模擬[D];浙江大學(xué);2015年

4 王曉燕;探索計(jì)算機(jī)模擬在高分子的體積排除色譜表征中的應(yīng)用[D];蘇州大學(xué);2015年

5 趙陽(yáng);紫外光誘導(dǎo)疊氮—炔環(huán)加成反應(yīng)制備環(huán)狀高分子[D];武漢紡織大學(xué);2016年

6 周麗琴;受限于圓柱形納米通道中的半剛性高分子鏈的逃逸動(dòng)力學(xué)[D];中國(guó)科學(xué)技術(shù)大學(xué);2016年

7 胡婷婷;聚氧化乙烯與碘化鈉共混體系的流變和結(jié)晶行為研究[D];中國(guó)科學(xué)技術(shù)大學(xué);2016年

8 劉瑞清;含釓刺激響應(yīng)性高分子微粒的制備及作為多功能診療試劑的研究[D];湖北大學(xué);2016年

9 秦立云;線形高分子鏈共混熔體的結(jié)構(gòu)和動(dòng)力學(xué)性質(zhì)[D];伊犁師范學(xué)院;2016年

10 許佳麗;高分子稀土復(fù)合物界面復(fù)合成膜的研究[D];東華大學(xué);2016年

，

本文編號(hào)：2101027