本文關(guān)鍵詞：基于巰基“點擊”反應(yīng)合成有機(jī)硅熒光材料及性能研究　出處：《山東大學(xué)》2017年博士論文　論文類型：學(xué)位論文

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【摘要】："點擊"反應(yīng)是一種迅速高效,并且具有很高選擇性的新型的化學(xué)方法。點擊反應(yīng)具有反應(yīng)原料選擇范圍廣,所得產(chǎn)物無需復(fù)雜的分離提出過程等優(yōu)點。因此,點擊反應(yīng)的概念在諾獎得主Sharpless提出后有著長足的發(fā)展及廣泛的應(yīng)用。而巰基-烯/炔基反應(yīng)作為點擊反應(yīng)的一種,也同樣具有反應(yīng)速率高,選擇性好,反應(yīng)條件溫和等許多特點。目前,該反應(yīng)已被廣泛應(yīng)用于高聚物的合成和后功能化、納米壓印材料制備、材料表面改性、聚合物微球的制備、涂層以及凝膠的合成等。有機(jī)硅材料(如硅油、硅樹脂、硅橡膠等)具有極好的耐高低溫、耐老化、良好的電氣絕緣性以及優(yōu)越的生理惰性等獨特性能。這些都為其他種類的高分子材料所不能替代,因此有機(jī)硅材料被廣泛應(yīng)用于電子電氣、航空航天、化工輕工、機(jī)械紡織、交通、建筑、能源、醫(yī)療、農(nóng)業(yè)等方面。然而,如今功能化有機(jī)硅化合物及材料的方法主要為硅氫加成反應(yīng)。然而,硅氫加成反應(yīng)通過重金屬催化劑催化存在著諸多缺點,如:催化劑的殘留會影響材料在醫(yī)學(xué)方面的應(yīng)用;反應(yīng)時間較長且反應(yīng)條件苛刻;官能化基團(tuán)的存在會引發(fā)催化劑的中毒,從而影響催化劑的催化效果。此外,賦予現(xiàn)有的有機(jī)硅材料優(yōu)越的熒光性能會擴(kuò)展有機(jī)硅產(chǎn)品的應(yīng)用范圍。因而,尋找一種迅速高效,無重金屬催化劑的新反應(yīng)來制備新型有機(jī)硅熒光材料將具有重要的研究意義。本論文從以下六個方面出發(fā),主要采用巰基"點擊"反應(yīng)設(shè)計合成有機(jī)硅化合物,特別是有機(jī)硅熒光材料,并對其性能進(jìn)行研究,同時探索這種反應(yīng)方式作為一種得到功能型有機(jī)硅材料的新方法。1.從小分子單體出發(fā),通過巰基-炔基"點擊"反應(yīng)合成了一系列功能化硅烷。與常用的"硅氫加成"的合成方法相比,采用的方法具有反應(yīng)條件溫和(一般在室溫即可反應(yīng)),產(chǎn)率高,副反應(yīng)少;反應(yīng)速度快,立體選擇性高;空氣、水分以及活性基團(tuán)的存在不會影響反應(yīng)的進(jìn)行;有充足的商品化的巰基和雙鍵化合物(反應(yīng)成本低)可選用;反應(yīng)過程不需要重金屬催化劑等特點。這將大大降低功能化硅烷的合成成本。此外,制備的烷氧基硅烷成功地應(yīng)用于硅片表面改性,亦顯示出其在無機(jī)材料表面改性方面的潛在應(yīng)用價值。此外,合成的以硫為橋的官能化烷氧基硅烷在紫外光下有著優(yōu)良的熒光性能。2.利用巰基-雙鍵"點擊"反應(yīng)設(shè)計合成一系列以硫醚鍵為橋的聚硅氧烷,通過控制巰基與雙鍵的摩爾比調(diào)控所得聚合物的分子量。此外,保持雙鍵過量得到一系列不同分子量的以雙鍵封端的聚硅氧烷。并進(jìn)一步通過巰基-雙鍵反應(yīng)對雙鍵封端聚硅氧烷進(jìn)行后功能化,分別得到以酯基,羧基,硅烷氧基修飾的新型功能化聚硅氧烷。最后采用酯基功能化聚硅氧烷與稀土離子銪(Eu),以及鋱(Tb)配位,得到一系列紫外光下發(fā)出強(qiáng)烈熒光的熒光材料。這些新型熒光材料將在OLED顯示方面有著潛在應(yīng)用前景。3.用Oxone氧化以硫醚鍵為橋的聚硅氧烷的研究發(fā)現(xiàn),硫醚鍵的氧化會伴隨硅氧硅鍵的斷裂重排反應(yīng)。更有趣的是,使用這種方法我們意外地得到了新型含砜基環(huán)硅氧烷及其單晶結(jié)構(gòu)。這是一種有機(jī)硅環(huán)體合成的新方法,可作為制備有機(jī)硅環(huán)體傳統(tǒng)方法的有效補(bǔ)充。而得到的新型含砜基環(huán)硅氧烷能進(jìn)一步開環(huán)聚合用于構(gòu)筑聚硅氧烷新穎結(jié)構(gòu)。隨著氧化反應(yīng)的進(jìn)行,基于硅硫配鍵所產(chǎn)生的熒光消失。4.經(jīng)巰基-雙鍵反應(yīng)合成了功能化聚硅氧烷,然后通過稀土配位的方式將銪、鋱等稀土離子引入聚硅氧烷體系,并進(jìn)一步通過巰烯反應(yīng)交聯(lián)發(fā)光聚硅氧烷,得到一系列有著良好發(fā)光純度的有機(jī)硅彈性體。若同時引入稀土鋱離子及羅丹明,則可得到激發(fā)光波長響應(yīng)的可變色有機(jī)硅彈性體。將固化前的混合溶液涂在市售的UV-LED燈珠表面,經(jīng)過"原位"交聯(lián)后,可以得到激發(fā)波長響應(yīng)的熒光發(fā)射UV-LED燈,在器件制造方面顯示出廣泛的用途。5.利用太陽光引發(fā)的巰基-雙鍵"點擊"反應(yīng)制備了一系列基于聚硅氧烷的發(fā)光薄膜。即首先合成側(cè)鏈巰丙基的聚硅氧烷,然后在側(cè)基上經(jīng)巰基-雙鍵反應(yīng)引入羅丹明-B熒光基團(tuán),得到羅丹明-B功能化的聚硅氧烷;再利用側(cè)鏈上剩余的巰基與天然分子D-檸檬烯于太陽光下進(jìn)行光固化交聯(lián)反應(yīng),便得到發(fā)光薄膜。此外,將聚醚鏈段引入巰丙基聚硅氧烷,發(fā)現(xiàn)可以調(diào)控所得薄膜的親疏水性。最后,將固化前的混合溶液涂在市售的UV-LED燈珠表面,經(jīng)過"原位"交聯(lián)后,采用一種簡便的方式得到了具有實用價值、發(fā)彩色熒光的UV-LED燈。6.經(jīng)巰基-雙鍵反應(yīng)將硼酸酯鍵引入聚硅氧烷體系,利用硼酸酯鍵斷裂-生成的可逆反應(yīng),得到了可自愈的有機(jī)硅彈性體。這是經(jīng)簡單的巰基-雙鍵反應(yīng)得到可自愈有機(jī)硅彈性體的首次報道。此外,通過引入雙交聯(lián)體系及熒光單體分子,成功地實現(xiàn)了對彈性體的力學(xué)和熒光性能的有效調(diào)控。
[Abstract]:"Click" reaction is a kind of new chemical methods quickly and efficiently, and has very high selectivity. Click reaction has a wide range of raw materials, the products without complicated separation process is proposed and other advantages. Therefore, the concept of click reaction in Nobel Prize winner Sharpless has made great progress and extensive the application and thiol ene / alkyne reaction as a click reaction, also has high reaction rate, good selectivity, mild reaction conditions and many other characteristics. At present, the function of synthesis and after the reaction has been widely used in polymers, nano imprint material preparation, surface modification, polymer microspheres the preparation of coating and gel synthesis. Silicone materials (such as silicone oil, silicone resin, silicone rubber) has excellent high and low temperature resistance, aging resistance, electrical insulation and excellent physical inert unique properties such as good. These are substitutes for other types of polymer materials can therefore, silicone material has been widely used in electrical and electronic, aerospace, chemical industry, textile machinery, transportation, construction, energy, health, agriculture and so on. However, now the method of functional organosilicon compounds and materials for hydrosilylation reaction. However, the hydrosilylation reaction catalyzed by heavy metals has many shortcomings, such as: the application of the catalyst residue will influence material in medicine; a longer reaction time and harsh reaction conditions; functional groups exist will cause catalyst poisoning, thus affecting the catalytic effect of catalysts. In addition, the scope of application to fluorescence properties of silicone materials available the superior extension of silicone products. Therefore, looking for a new reaction quickly and efficiently, without heavy metal catalysts for the preparation of a new type of organic fluorescent materials will be The research has important significance. This paper from the following six aspects, mainly by using silicone synthetic thiol "click" reaction design compounds, especially organic fluorescent materials, and to study its properties, and explore this response as a way to get.1. new method of functional silicone materials from the monomer of the thiol alkyne click reaction of a series of functionalized silanes. With the commonly used "hydrosilylation" synthesis method compared the method with mild reaction conditions (general reaction at room temperature can), high yield, less side reaction; reaction speed, high stereoselectivity; air and water. The existence of the active groups will not affect the reaction; a thiol and double bond compound sufficient commercial (low reaction cost) can be selected; the reaction process does not need heavy metal catalyst and so on. This will be greatly reduced Low cost synthesis of functionalized silane. In addition, alkoxy silane was prepared successfully applied to silicon surface modification, also showed in the surface modification of inorganic materials and potential application value. In addition, the synthesis of using sulfur functionalized alkoxysilane bridge has excellent fluorescent properties of.2. double click the sulfhydryl reaction design and synthesis of a series of thioether bridged polysiloxane under ultraviolet light, through the molecular regulation of the polymer molar ratio control and double the amount of thiol. In addition, keep a series of different double bond excess molecular weight with polysiloxane doublebond terminated. And further through the function of double seal mercapto terminated polysiloxanes double after the reaction, the ester, carboxyl groups were obtained. The new functional polysiloxane modified silyloxy. Finally using ester functionalized polysiloxane with rare earth ions europium (Eu), to And terbium (Tb) ligand, fluorescent material to obtain a series of UV light emitted strong fluorescence. The fluorescence of these new materials will be shown in OLED has a potential application prospect in.3. research by the thioether bond as bridge polysiloxane by Oxone oxidation, oxidation of thioether bond will be accompanied by rearrangement of Si-O-Si bond fracture the more interesting is that using this method we accidentally got new sulfonyl containing siloxane ring and single crystal structure. It is a new method of synthesis of silicone ring, can be used as an effective complement for preparation of silicone ring. The traditional method and the new type of sulfonyl containing cyclosiloxane can further open loop to construct a novel structure. The polymerization of polysiloxane with the oxidation reaction, the fluorescence produced by silicon sulfur coordination bond based on the disappearance of.4. by a thiol functionalized polysiloxane was synthesized by reaction of double bond, and then through the rare earth coordination way of europium, Terbium ions into the polysiloxane system, and further through thiol ene reaction of crosslinked light-emitting polysiloxane, then a series of a silicone elastomer with good luminescence purity. If the introduction of terbium ion and Luo Danming, can get the excitation wavelength response can change color of silicone elastomer before curing. The mixed solution on the market UV-LED lamp surface, after in situ crosslinking, can get fluorescence excitation wavelength response of UV-LED light emission, showing a wide range of uses of.5. thiol light induced double bond "click" reaction to prepare a series of luminescent films. Using the sun in polysiloxane based on devices that first synthesis of side chain polysiloxane mercaptopropyl. Then, based on the side reaction by a thiol bond by introducing Luo Danming -B fluorophores, by Luo Danming -B functionalized polysiloxane; using thiol side chain residues Light curing reaction and natural molecular D- limonene in the sun, we get the luminescent films. In addition, the introduction of mercaptopropyl polyether polysiloxane, found the hydrophilicity can be controlled in the films. Finally, the mixed before curing solution on a commercially available UV-LED lamp bead surface, after in situ crosslinking after using a simple way to get the practical value, hair color fluorescent lamp.6. UV-LED by a thiol Bond Reaction of boric acid ester bond was introduced into the polysiloxane system, using the reversible reaction of the borate ester bonding fault generated by the obtained silicone elastomer can be self-healing. This is the simple reaction of thiol bonds obtained for the first time reported self-healing silicone elastomer. In addition, through the introduction of double crosslinking system and fluorescent monomer molecules, successfully realized the effective regulation of the mechanical and fluorescence properties of the elastomer.

【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ422
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本文編號：1386165