DSD酸-三嗪型荧光增白剂研发新进展及发展趋势

在简要介绍荧光增白剂发展状况的基础上,着重介绍了近几年DSD酸-三嗪型荧光增白剂的研究进展,包括改变取代基、开发复配产品、两性荧光增白剂的研究、研制稳定易储存液态型产品、改进基础原料与中间体、应用膜技术纯化荧光增白剂以及不对称型荧光增白剂的研究等,并叙述了此类荧光增白剂的发展趋势,指出具有良好应用性能的产品国产化和产业化,高档专用、复配、两性、不对称型产品的开发,剂型及后处理工艺的研究等可能成为新的研究重点.     

荧光增白剂中间体合成与发展

一、概述 荧光增白剂是“染料索引”中染料的一个类别,可以认为是一种“白色染料”,作为染料工业的一个重要分支,广泛应用于纺织印染、合成纤维、塑料、造纸、合成洗涤剂等多个领域。20世纪70年代以来随着全球科学进步和社会发展,荧光增白剂得到快速发展,而且近五年来世界新增商品染料1300余个,其中荧光增白剂就占230余种,占新增染料总数的近18％,显示强劲的发展势头和良好的发展前景。20世纪90年代以来我国染料工业快速     

DSD酸-三嗪类荧光增白剂的复配与增效

本文简介了复配型荧光增白剂的概念、复配的种类和方法、复配型荧光增白剂能产生加和增效的原理。介绍了国内DSD酸-三嗪类复配型荧光增白剂的研究和生产概况并列举了几项研究成果在实际应用中的效果。     

催化加氢法合成DSD酸

研究了４，４＇－二硝基二苯乙烯－２，２＇－双磺酸（ＤＮＳ酸）液相催化加氢合成４，４＇－二氨基二苯乙烯－２，２＇－双磺酸（ＤＳＤ酸）的工艺，在优化条件下达到了较好的纯度和收率。     

DSD酸制备新方法的研究

ＤＳＤ酸制备新方法即铵盐法较铁酸法产品收率高，产品质量好，缓解了设备腐蚀。     

荧光增白剂CXT生产工艺研究

在工业生产中,将DSD酸用Na2CO3打浆,在-5℃-5℃,pH=6.5-7用三聚氯氰缩合,再在30℃-35℃时与苯胺缩合,然后在95℃-100℃,pH=7-8与吗啉缩合,经晶型转变,得标题化合物。对于DSD酸的溶解,NaOH优于Na2CO3;作为综合反应的缚酸剂,NaOH和CaCO3较好。     

DSD酸在荧光增白剂中的应用与展望

本文全面系统的介绍了DSD酸用于合成荧光增白剂，按化学结构类型可分属：双三嗪氨基二苯乙烯类型、双三唑基二苯乙烯类型、双酰胺基二苯乙烯类型、4-酰胺基-4’-三嗪氨基二苯乙烯类型。还介绍了在合成DSD酸过程中的过渡产物对硝基甲苯邻磺酸可用于合成单三唑二苯乙烯类型荧光增白剂。详细列出了这几类荧光增白剂目前还在使用的主要品种的化学结构式。预测在相关消费一产业链的持续拉动下，今后十年内DSD酸在荧光增白剂中的消费量仍将逐年递增，年均递增速率约为5．27％。指出DSD酸要进一步提高质量以满足生产高品质荧光增白剂及多种商品剂型的要求。     

催化氢化法合成DSD酸进展

回顾了DSD酸催化合成的进展,重点介绍了国内外采用Ni和Pt/Pd催化剂氢化的研究成果,并对国内生产厂家提出建议。     

催化氢化法合成DSD酸进展

回顾了DSD酸催化合成的进展，重点介绍了国内外采用Ni和Pt/Pd催化剂氢化的研究成果，并对国内生产厂家提出建议。     

季铵盐类荧光增白剂的合成及性能

三聚氯氰与4,4′-二氨基二苯乙烯-2,2′-二磺酸和两种氨基化合物经过三步缩合反应得到三嗪基氨基二苯乙烯型荧光增白剂,用三乙醇胺和三乙胺分别替代二乙醇胺和二乙胺,合成新型两性季铵盐类荧光增白剂,研究其与对比的非季铵盐类荧光增白剂的应用性能和在水溶液中的紫外吸收性能、光致异构化现象、荧光发射性能及其应用性能.结果表明：该季铵盐类增白剂耐酸碱性能明显提高,使用范围扩大,但其紫外吸收和荧光发射性能下降,且同样存在较为明显的光致异构化现象,耐光性也较差.     

新型不对称结构荧光增白剂的合成及其性能

用4-硝基-4′-氨基二苯乙烯-2,2′-二磺酸替代4,4′-二氨基二苯乙烯-2,2′-二磺酸,与三聚氯氰和氨基化合物经过四步缩合得到2个新型不对称结构和用作参比的3个传统对称结构荧光分子。对比研究这两类增白剂在水溶液中的紫外吸收、荧光发射、光致异构化现象及其应用性能。结果显示不对称结构增白剂紫外吸收和染色性能提高,但其荧光发射性能下降,且同样存在较为明显的光致异构化现象,耐光性也较差。     

The synthesis and properties of triazine-stilbene fluorescent brighteners containing a monophenolic antioxidant

Various triazine-stilbene fluorescent brighteners that were substituted with four different amine derivatives including a phenolic antioxidant on 4,4′-bistriazine moieties were synthesized. The obtained compounds (6a–m) were characterized by the analysis of proton NMR spectrum and confirmed by UV spectrum. The physical properties of the new compounds (6a–m) were determined by fastness test and whiteness measurement and compared with those of CI86.     

Synthesis and properties of vinylic copolymers with fluorescent moieties as optical brighteners for liquid crystals

The synthesis and characterization of new side‐group copolymers of styrene or methylmethacrylate with fluorescent 1,8‐naphthalimide derivatives are described. Basic photophysical characteristics of produced low molar and polymeric fluorescent brighteners are reported. The utility of the brighteners in liquid crystalline displays of the guest‐host type is discussed on the basis of their spectral properties and their effect on the behavior of nematic liquid crystal ZLI 1840 (Merck, Darmstadt, Germany) at phase transition. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 151–157, 1999     

三嗪基氨基二苯乙烯型荧光增白剂研究新进展

介绍了三嗪基氨基二苯乙烯型荧光增白剂的结构、性质、增白机理及影响其增白效果的因素,重点讨论了其合成与共聚改性、晶型改变与复配。按照亲核性由弱到强次序,原料依次与三聚氯氰反应,其中,含烯丙醇基或丙烯酰胺基的荧光增白剂与苯乙烯或丙烯腈共聚,可使其荧光反式活性分子固定在大分子链上,显著提高其增白性能、光化学稳定性和荧光量子产率,同时降低其光致异构现象;对得到的无定型增白剂进行转晶,可防止黄变,提高其商业价值;复配则对增白剂光吸收和荧光发射起到加和增效作用。指出今后应重点开发高效环保液态型及耐强酸强碱的荧光增白剂,并认为膜分离技术、中间体质量的提高以及复配增效将是研究热点。     

Synthesis and optical properties of organic-inorganic hybrid gels containing fluorescent molecules

Organic-inorganic hybrid gels containing fluorescent molecules, pyrene, anthracene, pelyrene, 9,10-diphenylanthracene, were synthesized from multi-functional cyclic siloxane, 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS), or cubic silsesquioxane, 1,3,5,7,9,11,13,15-octakis(dimethylsilyloxy)pentacyclo-[9,5,1,1,1,1]octasilsesquioxane (POSS), as crosslinking reagents with α,ω-nonconjugated dienes, 1,5-hexadiene (HD) or 1,9-decadiene (DD), as spacer monomers, using a photo hydrosilylation reaction with a bis(acetylacetonato)platinum catalyst in toluene. The gels containing pyrene showed higher emission intensity than the toluene solution of pyrene. The emission intensity of pyrene increased as proceeding of the network formation in the gel. The gels composed of long spacer monomer of DD or cubic cross-linking reagent of POSS showed higher intensity of the emission than the gels synthesized by HD or TMCTS. Only a slight increase of the emission intensity was observed in the gels containing anthracene, pelyrene, 9,10-diphenylanthracene.     

含可聚合基团的1，8-萘酰亚胺荧光单体的合成与光学性质

以4-溴-1,8-萘酐和乙醇胺为原料,经过酰胺化、胺化、季铵化3步反应,得到一种水溶性荧光单体4-(N'-甲基-1-哌嗪基)-N-羟乙基-1,8-萘二甲酰烯丙基氯化铵.采用红外光谱、质谱、核磁共振氢谱、元素分析等测试技术对产物进行了结构表征,并对其紫外光谱、荧光光谱等光学性质进行了初步的研究.     

含三嗪环非离子表面活性剂制备及其性能研究

以三聚氯氰、脂肪胺、聚乙二醇单甲醚(mPEG)为原料合成了6种均三嗪非离子表面活性剂。采用FTIR1、HNMR对中间体和目标产物进行了结构表征。考察了25℃时6种产品的表面张力、临界胶束浓度及其乳化力。结果表明,该类非离子表面活性剂具有较好的表面活性,其中DMAT-600的临界胶束浓度(cmc)和cmc下的表面张力(γcmc)分别可达0.162g/L和31.94mN/m;产品具有较强的乳化力,乳化力介于8.2~20.5min。     

Synthesis and fluorescent properties of europium-polymer complexes containing naphthoate and 1.10-phenanthroline ligands

Highly fluorescent Eu-polymer complexes were synthesized through copolymerization of EuPhen(Nap)₂AA with methyl methacrylate or styrene and their luminescent properties were investigated. The Eu-polymer luminophores showed intense red emission under UV excitation, and the emission intensities were much stronger than that of the EuPhen(Nap)₂AA complex. Typical relationships between emission intensity and Eu content in copolymers exhibited some extent of concentration quenching in our studies. However, ⁵D₀ lifetime results suggested that the concentration quenching phenomena cannot be accounted for by deactivation of the ⁵D₀ state through exchange and multipolar interactions. Ligand energy migration along or crosspolymer chains can interpret the emission concentration quenching phenomena reasonably. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1405–1410, 1997