基于巯基“点击”反应合成有机硅荧光材料及性能研究

发布时间：2018-01-06 03:43

  本文关键词：基于巯基“点击”反应合成有机硅荧光材料及性能研究　出处：《山东大学》2017年博士论文　论文类型：学位论文

  更多相关文章： 巯基-点击反应 有机硅高分子 发光弹性体 可自愈 紫外光

【摘要】："点击"反应是一种迅速高效,并且具有很高选择性的新型的化学方法。点击反应具有反应原料选择范围广,所得产物无需复杂的分离提出过程等优点。因此,点击反应的概念在诺奖得主Sharpless提出后有着长足的发展及广泛的应用。而巯基-烯/炔基反应作为点击反应的一种,也同样具有反应速率高,选择性好,反应条件温和等许多特点。目前,该反应已被广泛应用于高聚物的合成和后功能化、纳米压印材料制备、材料表面改性、聚合物微球的制备、涂层以及凝胶的合成等。有机硅材料(如硅油、硅树脂、硅橡胶等)具有极好的耐高低温、耐老化、良好的电气绝缘性以及优越的生理惰性等独特性能。这些都为其他种类的高分子材料所不能替代,因此有机硅材料被广泛应用于电子电气、航空航天、化工轻工、机械纺织、交通、建筑、能源、医疗、农业等方面。然而,如今功能化有机硅化合物及材料的方法主要为硅氢加成反应。然而,硅氢加成反应通过重金属催化剂催化存在着诸多缺点,如:催化剂的残留会影响材料在医学方面的应用;反应时间较长且反应条件苛刻;官能化基团的存在会引发催化剂的中毒,从而影响催化剂的催化效果。此外,赋予现有的有机硅材料优越的荧光性能会扩展有机硅产品的应用范围。因而,寻找一种迅速高效,无重金属催化剂的新反应来制备新型有机硅荧光材料将具有重要的研究意义。本论文从以下六个方面出发,主要采用巯基"点击"反应设计合成有机硅化合物,特别是有机硅荧光材料,并对其性能进行研究,同时探索这种反应方式作为一种得到功能型有机硅材料的新方法。1.从小分子单体出发,通过巯基-炔基"点击"反应合成了一系列功能化硅烷。与常用的"硅氢加成"的合成方法相比,采用的方法具有反应条件温和(一般在室温即可反应),产率高,副反应少;反应速度快,立体选择性高;空气、水分以及活性基团的存在不会影响反应的进行;有充足的商品化的巯基和双键化合物(反应成本低)可选用;反应过程不需要重金属催化剂等特点。这将大大降低功能化硅烷的合成成本。此外,制备的烷氧基硅烷成功地应用于硅片表面改性,亦显示出其在无机材料表面改性方面的潜在应用价值。此外,合成的以硫为桥的官能化烷氧基硅烷在紫外光下有着优良的荧光性能。2.利用巯基-双键"点击"反应设计合成一系列以硫醚键为桥的聚硅氧烷,通过控制巯基与双键的摩尔比调控所得聚合物的分子量。此外,保持双键过量得到一系列不同分子量的以双键封端的聚硅氧烷。并进一步通过巯基-双键反应对双键封端聚硅氧烷进行后功能化,分别得到以酯基,羧基,硅烷氧基修饰的新型功能化聚硅氧烷。最后采用酯基功能化聚硅氧烷与稀土离子铕(Eu),以及铽(Tb)配位,得到一系列紫外光下发出强烈荧光的荧光材料。这些新型荧光材料将在OLED显示方面有着潜在应用前景。3.用Oxone氧化以硫醚键为桥的聚硅氧烷的研究发现,硫醚键的氧化会伴随硅氧硅键的断裂重排反应。更有趣的是,使用这种方法我们意外地得到了新型含砜基环硅氧烷及其单晶结构。这是一种有机硅环体合成的新方法,可作为制备有机硅环体传统方法的有效补充。而得到的新型含砜基环硅氧烷能进一步开环聚合用于构筑聚硅氧烷新颖结构。随着氧化反应的进行,基于硅硫配键所产生的荧光消失。4.经巯基-双键反应合成了功能化聚硅氧烷,然后通过稀土配位的方式将铕、铽等稀土离子引入聚硅氧烷体系,并进一步通过巯烯反应交联发光聚硅氧烷,得到一系列有着良好发光纯度的有机硅弹性体。若同时引入稀土铽离子及罗丹明,则可得到激发光波长响应的可变色有机硅弹性体。将固化前的混合溶液涂在市售的UV-LED灯珠表面,经过"原位"交联后,可以得到激发波长响应的荧光发射UV-LED灯,在器件制造方面显示出广泛的用途。5.利用太阳光引发的巯基-双键"点击"反应制备了一系列基于聚硅氧烷的发光薄膜。即首先合成侧链巯丙基的聚硅氧烷,然后在侧基上经巯基-双键反应引入罗丹明-B荧光基团,得到罗丹明-B功能化的聚硅氧烷;再利用侧链上剩余的巯基与天然分子D-柠檬烯于太阳光下进行光固化交联反应,便得到发光薄膜。此外,将聚醚链段引入巯丙基聚硅氧烷,发现可以调控所得薄膜的亲疏水性。最后,将固化前的混合溶液涂在市售的UV-LED灯珠表面,经过"原位"交联后,采用一种简便的方式得到了具有实用价值、发彩色荧光的UV-LED灯。6.经巯基-双键反应将硼酸酯键引入聚硅氧烷体系,利用硼酸酯键断裂-生成的可逆反应,得到了可自愈的有机硅弹性体。这是经简单的巯基-双键反应得到可自愈有机硅弹性体的首次报道。此外,通过引入双交联体系及荧光单体分子,成功地实现了对弹性体的力学和荧光性能的有效调控。
[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.

【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ422
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本文编号：1386165