【作者】 刘静；

【导师】 张光华；

【作者基本信息】 陕西科技大学 ， 应用化学， 2011， 博士

【摘要】 双三嗪氨基二苯乙烯荧光增白剂(简称FBs),是一种能够吸收近紫外波段光,发射出高强度蓝紫色荧光的特殊染料,因其能够减少织物黄色,增加白度及高性价比而广泛应用于造纸、纺织、皮革、涂料、洗涤剂等领域,是目前使用最多的一类荧光增白剂。由于其耐光性较差,降低了增白效果,不能满足强酸强碱条件下应用的要求,对环境影响大,因而应用受到限制。聚合型荧光增白剂(PFBs)中荧光单体发色团结构不变,仍保持原有的增白性能。发色团与高分子间以共价键相连,使其结构稳定性、耐光性等得到改善；同时增白性能和荧光量子产率显著提高所提高,且对环境影响小,是环保型高性能新产品。PFBs能够在强酸(碱)条件下使用,扩大了传统荧光增白剂在造纸和印染等方面的使用范围,具有较高的染色白度及上染率,不迁移,即使流失进入生物体,也很容易代谢,因而安全性高。近年来,聚合型荧光增白剂领域的研究热点是新型结构聚合物新品开发和性能的研究,在强酸碱条件下使用的荧光增白剂及不对称型荧光增白剂的研究及其应用等方面。国内此类研究鲜见报道。国外研究主要集中在DSD-三嗪环上引入烯丙氧基、丙烯酰胺基等不饱和基团,通过聚合把荧光单体固定在苯乙烯或丙烯腈长链上。PFBs可极大提高发色团的稳定性和荧光发射,具有很高白度。但合成的PFBs水溶性较差,合成产品单一,从而限制了其应用。研究工作分两部分：合成实验和性能测试实验。(1)对称结构聚合型双三嗪氨基二苯乙烯类荧光增白剂的合成。采用三种方法：①以N-甲基哌嗪替代DSD-CC荧光增白剂中一种氨基化合物,与丙烯基氯发生SN2取代反应,生成N-甲基哌嗪-亚胺烯丙基氯化铵荧光单体,与丙烯酰胺聚合合成系列聚-4,4’-双-(4-N’-甲基哌嗪-R-1,3,5-三嗪-2-氨基)-二苯乙烯-2,2’-二磺酸-亚胺丙烯基氯-丙烯酰胺荧光增白剂(简称PFBs)。与未聚合4,4’-双-(4-N’-甲基哌嗪-R-1,3,5-三嗪-2-氨基)-二苯乙烯-2,2’-二磺酸荧光小分子相比较,PFBs耐光和耐热性能提高,水溶性改善,增白效果好,与纤维结合强,具有抗硬水能力和耐洗牢度强等优点,可以提高纸张的白度和抗张强度,猝灭浓度大,适用pH范围变宽。②以N,N’-二甲基甲酰胺(DMF)为溶剂,醋酸酐为脱水剂,将传统三嗪氨基二苯乙烯荧光分子通过脱水闭环反应对马来酸酐改性,并与苯乙烯共聚,合成了系列聚-4,4’-双-(4-N-马来酰亚胺-R-1,3,5-三嗪-2-氨基)-二苯乙烯-2,2’-二磺酸-苯乙烯荧光增白剂。此N-三嗪马来酰亚胺聚合型荧光增白剂的发色团与高分子之间共价键使光学稳定性增强,增白性能和荧光量子产率显著提高；随着溶剂极性的降低,荧光量子产率增加,最大吸收波长和发射波长发生红移。三嗪环上取代基类型直接影响顺反式异构体的比例,对光吸收和荧光分配无显著影响。在水溶液中脂肪族取代基反式异构体浓度大,芳香族取代基顺式异构体占主导地位。③通过缩聚反应将三聚氯氰与4,4’-二氨基二苯乙烯-2,2’-二磺酸和氨基化合物缩合而得的荧光小分子,像葫芦一样一个一个地按一定间距悬挂到聚乙烯醇、壳聚糖多羟基高分子的碳链上,合成悬挂型聚乙烯醇和壳聚糖高分子荧光增白剂(PVA-FBs和CS-FBs)。此悬挂型高分子荧光增白剂与纸张纤维结合力强,涂布纸增白效果和纸张的抗张强度、耐破指数及耐光性得到提高,容易代谢,安全性高。(2)不对称结构高分子荧光增白剂的合成。以4-硝基-4’-氨基二苯乙烯-2,2’-二磺酸(ANSD)为原料,经过缩合发应和硫氢化钠的还原作用,与另外一个接枝了聚己二酰二乙烯三胺的三嗪氨基二苯乙烯化合物进行缩合,合成不对称结构高分子荧光增白剂。此产物稳定性提高,加之三嗪环上不同类型取代基各自的光谱性质加合增效作用,使得紫外吸收及染色性能明显提高,耐光性和耐热性能、水溶性得到改善。荧光猝灭浓度为5×104 mg/L(3)两性季铵盐型荧光增白剂的合成。以羟基、巯基、氨基替代其中一种氨基化合物,经过缩合反应和失水甘油基三甲基氯化铵(GTMAC)的开环反应,合成了两性季铵盐型荧光增白剂。此产物的吸收光谱和荧光光谱呈较好的镜像对称关系,对日光稳定,耐酸碱性能、紫外吸收性能提高；对纤维吸附能力强,提高耐洗性和摩擦牢度,耐光性能和增白效果好。在抄纸中的增白及物理抗张强度提高。使用范围扩大。但荧光发射性能略有降低。(4)结构表征与性能测试。对合成的系列目标产物的紫外和荧光性能、耐光性能、荧光量子产率,斯托克斯位移等光物理化学性质进行研究,探讨溶液的pH值、光照时间、浓度、有机溶剂极性等因素对其荧光性能的影响。通过IR、元素分析,核磁共振、HPLC等对其结构、纯度进行表征与测试。更多还原

【Abstract】 Triazinyl aminostilbene fluorescent brighteners (FBs for short) is an important type of dyes,which reduce yellowness and increase fabric brightness and whiteness by a process of absorption light in the near ultraviolet region of the spectrum and re-emit the light as violet-blue fluorescence in the visible region of the spectrum. They are the most widely used type of fluorescent brighteners in the market recently in many industry fields, such as paper manufacture,textile,leather,paint and detergents and so on because of their excellent properties and moderate price. In solution these FBs have low photo resistance,which will lead to decrease the degree of whiteness. In addition, they cannot be used in strong acid/alkali conditions and its environmental impact, thus their application is restricted.The basic structure of chromogen in polymeric fluorescent brighteners (PFBs for short) remains the same, so PFBs have increasing whiteness properties, too. Covalent bonds between chromogen and macromolecule chains enhances their photochemical stability and photo resistance, increases their whitening performance and fluorescence quantum yield. Resistance to wet process and organic solvent is greatly improved, and the less environmental impact be referred to as an new environmental efficient products. PFBs expands the using range of traditional fluorescent brighteners in paper manufacture and printing because of being more suitable for dyeing in strong acid/ alkali conditions. PFBs have higher dyeing whiteness and uptake, no move, easy to metabolism even erosion into organisms, so they are high safety.Polymeric fluorescent brighteners have also been active field in the polymeric material for years, but how to design and synthesis new structure PFBs or functional polymeric fluorescent brighteners with outstanding performance such as using in strong acid and alkali conditions and asymmetrical ploymeric fluorescent brighteners as well as potential applications have still attracted the world attention recently. Domestic research reports rarely. Foreign research mainly focus on triazine-stilbene fluorescent brighteners copolymers by fluorescence monomer with unsaturated polymerizable allyloxy group or acrylamide group in the triazine ring polymerization with styrene or acrylonitrile. Covalent bonds between chromogen and macromolecule chains enhance their photochemical stability, increase their fluorescence quantum yield and whitening performance being coated in substrate. But synthetic PFBs have poor water-soluble and single synthetic products, the application is limited.Main research is divided into two parts:synthetic experiment and performance testing experiment.(1) Synthesis of symmetrical triazinyl aminostilbene polymeric fluorescent brighteners.①Series of polymeric-4,4’-bis(4-N’-methyl-l-piperazi- nyl-R-1,3,5-triazin-2-ylamino)-stilbene-2,2’-disulfonic acid-imine allylic chlorine-acrylamide FBs are synthesized by polymerization of acrylamide and N’-methyl-l-piperazinyl-imine allylic chlorine quaternary ammonium salt from quaterisation reaction with allylic chlorin. Comparing with4,4’-bis(4-N’-methyl-l-piperazinyl-R-1,3,5-triazin-2-ylamino)-stilbene-2,2’-disulfonic acid, photo resistance and heat resistant of polymeric 4-N’-methyl-l-piperazinyl-imine allylic chlorine-acryla-mide is enhanced, and water soluble is improved. Whitening performance and adsorptivity for paper fiber, resistant to hard water and washing fastness ability as well as tensile strength is enhanced notably.The synthetic products have bigger concenteation of fluorescence quenched and wide pH use range.②The series of polymeric-4,4’-bis(4-N-ylmaleimide-R-1,3,5-triazin-2-ylamin-o)- stilbene-2,2-disulfonic acid -styrene fluorescent brightenes are synthesized by using styrene, maleic anhydride (MAH) as monomers modified by tradition triazinyl aminostilbene fluorescent brightener with N,N’- dimethyl formamide (DMF) as solvent, acetic anhydride as dehydrating agent. Comparing with non polymeric fluorescent brighteners, covalent bonds of N-triazene-maleimide polymeric fluorescent brighteners between chromogen and macromolecule chains can enhance chromogen photochemical stability, increase their whitening performance and fluorescence quantum yield. Meanwhile, with the solvent polarity reduce, fluorescence quantity greatly increases, the maxima absorbed wavelength and emission wavelength happen redshift.The type of substituents in the triazine ring can affect directly the concentration of trans and cis isomers, but not affect significantly absorption-fluorescence assignments. In equilibrium of aqueous solution, the concentration of trans-isomers prevails for N-triazene-maleimide polymeric fluorescent brighteners containing aliphatic residues as substituents whereas the aromatic residues increase the cis-isomers.③The synthesis of hanging type macromolecule fluorescent brighteners by of polyhydroxyl or ployamino macromolecule. Replacing one of amino compounds with polyvinyl alcohol (PVA) and chitosan(CS), hanging type triazinyl aminostilbene macromolecule fluorescent brighteners (CS-FBs, PVA-FBs) are synthesized through condensation reaction of fluorescent small molecules like as gourd are hanged one by one according to certain spacing to carbon chain of 4,4’-diaminostilbene-2,2’-disulfonic acid with cyanuric chloride (CC) and two kinds of amino compounds, one of them is CS and PVA. The polyhydroxyl fluorescent brighteners can enhance adsorptivity for paper fiber, the tensile strength and burst index as well as light resistance of coated paper notably.(2) Synthesis of asymmetrical ploymeric fluorescent brighteners.Using 4-nitro-4-aminostilbene-2,2’-disulfonic acid (ANSD) as raw materials, containing 4-nitro group fluorescent brighteners got hold through variant amine compounds replacing the chlorine of triazine rings with condensation reaction and nitro-group being deoxidated to amino group by using sodium bisulfide.The asymmetrical ploymeric fluorescent brighteners are synthesized through condensation reaction with another dibasic triazine compound grafted polyadipoyl diethylene triamine.Comparing with asymmetrical and symmetrical FBs, the active fluorescent component being bonded in the macromolecule chains of the asymmetrical polymeric fluorescent brighteners can enhance chromogen photochemical stability, in addition to the more substituents in triazine ring, their respective photophysical and photochemistry can play an additive synergistic effect and promote each other,the ultraviolet absorption and dyeing properties increases greatly, photo and heating stability as well as water-soluble is improved. The quenche concenteation of polyadipoyl diethylene triamine FBs is 5×10-4 g/mL.(3) Synthesis of amphoteric quaternary ammonium salt fluorescent brighteners.The amphoteric quaternary ammonium salt fluorescent brighteners are synthesized by ring-opening reaction of glycidyl trimethyl ammonium chloride (GTMAC) with triazinyl aminostilbene fluorescent brighteners (FBs) under substituting sulfhydryl, amino and hydroxyl group for one of amino compounds. The absorption spectra and fluorescence spectra of quaternary ammonium salt FBs is a good mirror symmetry relations. Comparing with the traditional FBs, such as CXT and VBL,the light stability is greater, the acid/alkali resistance and ultraviolet absorption performance are improved. The adsorptivity for paper fiber, washing fastness and rubbing fastness ability is enhanced notably. Whitening performance and physical tensile strength of quaternary ammonium salts fluorescent brighteners are higher Use scope is expanded, but fluorescence emission performance is lower slightly.(4) Performance testing experiment.The photophysics and photochemical properties of the synthesis target products is studied, such as ultraviolet absorption and fluorescenc emmission performance, light resistance performance, fluorescence quantum yield, stockes shift and so on. Meanwhile the influence factors on fluorescence performance are discussed, such as pH value in solution, light irradiation time, concentration, organic solvent, etc. The structures and purity are characterized and determined by IR, elemental analysis, nuclear magnetic resonance, HPLC and so on.更多还原