發(fā)布時間：2018-04-18 09:32

  本文選題：聚(雙取代乙炔) + 聚合后修飾��； 參考：《浙江大學(xué)》2017年博士論文

【摘要】：在自然界中,每一個物種都是經(jīng)過進(jìn)化且適應(yīng)新的環(huán)境而存在的。在物種進(jìn)化的過程中,遺傳物質(zhì)(DNA和RNA,少許蛋白質(zhì))決定了其外在性狀的表達(dá)。生物教科書告訴我們,在基因的重組或變異只關(guān)乎堿基對的增、減和序列的改變,而無關(guān)其主鏈結(jié)構(gòu)。盡管熱力學(xué)上最終狀態(tài)是穩(wěn)定的,但是由小分子聚合成大分子需要消耗高能量,同時由小分子連接成高分子量聚合物帶來的熵減小效應(yīng)也與自發(fā)過程違和。于是,自然界演化出用相對單一的主鏈結(jié)構(gòu)通過多種側(cè)基組合來改變和豐富大分子功能的策略。目前,熒光聚合物材料在電致發(fā)光與太陽電池器件、化學(xué)傳感、生物成像等領(lǐng)域備受關(guān)注,而光電功能高分子的合成均采取通過改變單體結(jié)構(gòu)來調(diào)控聚合物功能的策略。換言之,每當(dāng)我們想調(diào)節(jié)一種共軛聚合物的結(jié)構(gòu)和功能,都需要從頭合成,這和自然選擇的策略大相徑庭。本論文工作結(jié)合課題組在聚炔領(lǐng)域的前期工作基礎(chǔ),師法自然,考慮到聚(二苯基乙炔)和聚(對苯乙炔撐)的衍生物具有良好的發(fā)光性能,以這兩類熒光聚合物為前驅(qū)體,通過引入活性反應(yīng)中心,從而實現(xiàn)對聚合物進(jìn)行后修飾和功能化的目的。我們首先將含有五氟苯酯的雙取代炔烴單體在WCl6和Ph4Sn的催化作用下聚合得到聚合物前驅(qū)體。五氟苯的拉電子效應(yīng)活化了酯基,使其在溫和條件下與伯胺/仲胺親核試劑進(jìn)行反應(yīng)。聚合物前驅(qū)體與炔丙胺反應(yīng)得到含有端炔的次級聚合物前驅(qū)體。進(jìn)而采用疊氮小分子與次級聚合物前驅(qū)體進(jìn)行點擊反應(yīng),最終得到了側(cè)基含有三唑的雙取代聚炔。兩步后修飾反應(yīng)均具有反應(yīng)溫和、高效、完全的特點。此外,得到的聚合物均具有黃綠色的熒光和較高的量子效率。其次,繼續(xù)以含活性酯的雙取代聚炔為前驅(qū)體,成功地制備了雙取代聚炔側(cè)鏈含有伯胺、叔胺的二級聚合物前驅(qū)體。在此基礎(chǔ)之上,具有功能化的氧化石墨烯/雙取代聚炔雜化體成功制備,具有調(diào)控聚合物及雜化體熒光發(fā)射波長的特點,我們將這一現(xiàn)象解釋為共平面誘導(dǎo)發(fā)射紅移;含有叔胺的雙取代聚炔一方面由于質(zhì)子化作用,表現(xiàn)出pH的響應(yīng)行為,另一方面可以繼續(xù)衍生得到含有兩性離子的雙取代聚炔,表現(xiàn)出一定的水溶性。在制備的含兩性離子雙取代聚炔具有水溶性后,我們接著又利用后修飾策略分別制備了含陽離子、陰離子的兩種二苯基聚乙炔的衍生物,分別比較了三種含離子型的雙取代聚炔的水分散情況,其水分散能力為:含兩性離子的雙取代聚炔含陰離子的雙取代聚炔含陽離子的雙取代聚炔。我們進(jìn)一步研究了三種離子型聚炔的熒光強度與濃度的關(guān)系。在較低濃度時,三種的聚合物熒光強度與濃度保持線性關(guān)系;而濃度過高時,出現(xiàn)熒光強度增加變緩和熒光下降情況兩種情況。綜合分析,鏈內(nèi)激子的形成是兩性離子型雙取代聚炔高濃度下熒光猝滅的主要原因。偶氮苯是具有光學(xué)活性的官能團(tuán),我們利用活性酯策略成功制備了含有偶氮苯衍生物的雙取代聚炔,并與之前報道的單取代偶氮苯聚炔的性質(zhì)進(jìn)行比較。研究發(fā)現(xiàn),二者在紫外燈的照射下均表現(xiàn)出光致異構(gòu)化的行為,且光致異構(gòu)化行為與聚合物的主鏈位阻效應(yīng)有著聯(lián)系。利用更高能量的紫外光(254nm)可以實現(xiàn)偶氮苯從順式到反式的回復(fù)。除此之外,含偶氮苯的雙取代聚炔其聚集熒光行為與母體聚合物有著截然相反的效果,前驅(qū)體聚炔表現(xiàn)為聚集增強熒光(AEE),而修飾后的雙取代聚炔表現(xiàn)為聚集猝滅熒光(ACQ),偶氮苯具有熒光淬滅的效果,這也為熒光行為調(diào)控提供了簡便的方法。手性側(cè)基將手性傳遞到雙取代聚炔的主鏈已取得成功,以往的研究關(guān)注的是含有對映異構(gòu)體的手性側(cè)基在圓二色譜上會呈現(xiàn)對應(yīng)的康頓信號和手性聚炔表現(xiàn)出偏振熒光發(fā)射。我們通過活性酯路線修飾了含較大手性側(cè)基后發(fā)現(xiàn),除圓二色譜外,對映異構(gòu)體修飾的聚合物在反應(yīng)現(xiàn)象、反應(yīng)程度、溶解性等方面都有較大差異,理論模擬優(yōu)化的結(jié)構(gòu)顯示L型的空間結(jié)構(gòu)滿足形成分子內(nèi)氫鍵的要求,而D型不可以,結(jié)構(gòu)上的差異導(dǎo)致了后續(xù)性能的區(qū)別。最后,采用Sonogashira偶聯(lián)聚合得到活性酯修飾的對苯乙炔與四苯基乙烯(TPE)的交替共聚合物。聚合物具有聚顯著的AEE行為,且在不同的混合溶劑體系中熒光增強閾值也不同。通過引入手性分子,手性可以實現(xiàn)傳導(dǎo)至主鏈,并使聚合物表現(xiàn)出“手性放大”效應(yīng);PEG分子鏈的引入則可以實現(xiàn)聚合物的親疏水性調(diào)控,將接PEG前后的聚合物在接觸角和掃描電鏡的測試中均有明顯的區(qū)別。此外,這類熒光聚合物在爆炸物的超放大檢測中有著優(yōu)異的效果。
[Abstract]:In nature, each species is evolved and adapted to the new environment and exist. In the process of the evolution of species, genetic material (DNA and RNA, a protein) determines its traits. The expression of biological textbooks tell us, in genetic recombination or mutation only about base pairs, reduction and sequence changes, regardless of its backbone structure. Although thermodynamically final state is stable, but by small molecules aggregated into large molecules need to consume high energy, at the same time by small molecules connected into a high molecular weight polymer has effects of reducing the entropy and spontaneous process molimen. Then evolved with the backbone structure is relatively simple through a variety of side groups combined to change and enrich the molecular function strategy. At present, the fluorescent polymer electroluminescent and solar cell devices in electrical, chemical sensing, biological imaging and other areas of concern, and the light Synthesis of functional polymer electric were taken by changing the monomer structure to control polymer functional strategies. In other words, when we want to adjust the structure and function of a conjugated polymer, which requires de novo synthesis, and natural selection strategy. This thesis be quite different with the nature of work based on our previous work, polyacetylene in the field, taking into account the poly (two phenyl acetylene) and poly (phenylene ethynylene) derivatives have good luminescent properties, the two kinds of fluorescent polymers as precursors by introducing active reaction center, so as to achieve the purpose of modification and functionalization of the polymer. We will contain five fluoro ester disubstituted alkyne monomer in the catalysis of WCl6 and Ph4Sn under the polymerization of polymer precursor. Five - electron withdrawing ester activation effect, make it under mild conditions with primary amine / secondary amine nucleophiles The reaction. The polymeric precursor and propargylamines reaction of secondary polymer precursor containing alkyne azide. Then the small molecules and secondary polymer precursors were click reaction, finally got the double side group containing three triazole substituted polyacetylenes. The two step after the modification reaction has mild reaction, efficient, complete. In addition, the quantum efficiency of the polymers obtained have high fluorescence and the yellow green. Secondly, to substituted polyacetylenes as precursor containing active ester, the successful preparation of disubstituted polyacetylenes containing side chain amine was prepared. The two stage polymerization precursors of tertiary amines. On this basis, with functionalized graphene oxide / disubstituted polyacetylenes hybrid was prepared successfully, and has the characteristics of control of polymer hybrid fluorescence emission wavelength, we explained the phenomenon as a co planar induced emission redshift; containing tertiary amine bis substituted polyacetylenes On the one hand, due to protonation, showed the response behavior of pH, on the other hand can be derived containing zwitterionic disubstituted polyacetylenes, exhibit certain water solubility. In preparation containing amphoteric disubstituted polyacetylenes with water soluble, we then use after modification strategies respectively the preparation of cation containing two phenyl, two anionic polyacetylene derivatives were compared respectively containing three kinds of ionic disubstituted polyacetylenes dispersed in water, the water dispersion ability: containing zwitterionic disubstituted polyacetylenes containing anionic disubstituted polyacetylenes containing cationic double substituted polyacetylenes. The relationship between fluorescence intensity and concentration we further study the three kinds of ionic polyacetylene. At low concentration, a linear relationship between the three kinds of polymer fluorescence intensity and concentration; and the concentration is too high, the fluorescence intensity increases moderate fluorescence appeared decrease situation two Cases. Comprehensive analysis, formation of intrachain exciton is the main reason of amphoteric disubstituted polyacetylenes in high concentrations. The fluorescence quenching of azobenzene groups is optically active, we use the active ester strategy was successfully prepared containing azobenzene derivatives disubstituted polyacetylenes, and compared with previously reported single substituted azobenzene polyacetylene properties. The study found that the two under the irradiation of UV lamp showed the photoisomerization behavior and the photoisomerization behavior and polymer backbone steric effect associated with higher energy. Using ultraviolet light (254nm) can be achieved from cis to trans azobenzene in reply. In addition, the azobenzene containing double substituted polyacetylenes and their aggregation behavior of fluorescence matrix polymer has the opposite effect, the precursor of polyacetylene exhibits aggregation enhanced fluorescence (AEE), and modified disubstituted polyacetylenes as poly In the fluorescence quenching (ACQ), azobenzene with fluorescence quenching effect, which is fluorescent behavior control provides a simple and convenient method. Chiral side group transferred to the chiral disubstituted polyacetylenes backbone has been successful, the previous study is concerned with the chiral side group enantiomer will appear in the corresponding circle two the Condon chromatographic signal and chiral polyacetylene exhibits polarization fluorescence emission. We modified with larger chiral side groups by active ester route after the discovery, in addition to round two chromatography, enantiomeric modification of the polymer in the reaction, the reaction degree, solubility and other aspects have great differences, the structure of the simulation optimization theory the display space structure of L type of intramolecular hydrogen bonding, while type D can not, structural differences lead to different follow-up performance. Finally, polymerization active ester modified 1,4-phenylenevinylene with Sonogashira coupling Four phenyl ethylene (TPE) alternating copolymer. Polymers with poly AEE behavior significantly, and in the mixed solvent system in different fluorescence enhancement threshold is different. Through the introduction of chiral molecules and chiral can transfer to the main chain, and the polymer showed "chiral amplification effect"; the introduction of PEG molecular chain can be achieved hydrophobicity control of polymer, polymer before and after PEG will pick both in the contact angle and the scanning electron microscope test significant difference. In addition, this kind of fluorescent polymers have excellent efficacy in ultra zoom explosive detection.

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O631
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本文編號：1767796