紫外线吸收剂2,4-二(3′,5′-二甲苯基)-6-(2′-羟基-4′-辛氧基)苯基-1,3,5三嗪的合成

采用三聚氯氰与间二甲苯在三氯化铝存在下于50℃反应36h合成中间体Ⅰ,将其与间苯二酚于110℃反应4h,合成了中间体Ⅱ。将中间体Ⅱ与NaOH及溴辛烷在DMF中于70℃反应1h,经冷却、抽滤,用二氯甲烷重结晶,得到淡黄色的紫外线吸收剂2,4-二(3′,5′-二甲苯基)-6-(2′-羟基-4′-辛氧基)苯基-1,3,5三嗪各步骤的收率依次为93%,94%,88%。讨论了反应温度、时间及反应物配比对各步反应的影响。与苯并三唑类紫外线吸收剂Tinuvin326的应用对比结果表明,三嗪类紫外线吸收剂Cyasorb UV-1164具有较好的抗老化能力。     

紫外线吸收剂2,4-二(3'''',5''''-二甲苯基)-6-(2''''-羟基-4''''-辛氧基)苯基-1,3,5三嗪的合成

采用三聚氯氰与间二甲苯在三氯化铝存在下于50℃反应36h合成中间体Ⅰ，将其与间苯二酚于110℃反应4h，合成了中间体Ⅱ。将中间体Ⅱ与NaOH及溴辛烷在DMF中于70℃反应1h，经冷却、抽滤，用二氯甲烷重结晶，得到淡黄色的紫外线吸收剂2，4-二（3’，5’-二甲苯基）-6-（2’-羟基-4’-辛氧基）苯基-1，3，5三嗪各步骤的收率依次为93％，94％，88％。讨论了反应温度、时间及反应物配比对各步反应的影响。与苯并三唑类紫外线吸收剂Tinuvin326的应用对比结果表明，三嗪类紫外线吸收剂Cyasorb UV-1164具有较好的抗老化能力。     

一种三嗪类紫外线吸收剂的合成

采用三聚氯氰与间二甲苯在三氯化铝存在下于50℃反应36h合成中间体Ⅰ，将其与间苯二酚于110℃反应4h，合成了中间体Ⅱ。将中间体Ⅱ与NaOH及溴辛烷在DMF中于70℃反应1h，经冷却、抽滤，用二氯甲烷重结晶，得到淡黄色的紫外线吸收剂2，4-二（2’，4’-二甲基苯基）-6-（2’-羟基-4’-辛氧基苯基）-1，3，5三嗪，各步骤的收率依次为93％，91％，81％。讨论了反应温度、时间及反应物配比对各步反应的影响。与苯并三唑类紫外线吸收剂Tinuvin 326的应用对比结果表明，合成产品具有较好的抗老化能力。     

反应性紫外线吸收剂研究进展

对纺织品进行功能整理是提高其附加值的重要环节,反应性紫外线吸收剂可有效改善纺织品的紫外线防护能力。针对现有反应性紫外线吸收剂的国内外发展现状和趋势,详细介绍了二苯甲酮类、苯并三唑类、三嗪类、受阻胺类及其他类反应性紫外线吸收剂的制备过程和应用情况,并对它们的应用前景进行了展望。     

1,3,5-均三嗪类紫外线吸收剂的合成与应用

介绍了三嗪紫外线吸收剂的吸收机理和合成进展，并介绍了山西省化工研究所开发的三嗪－5和三嗪－425紫外线吸收剂的开发情况。     

新型三嗪类紫外线吸收剂的合成研究

以对溴甲苯、三聚氯氰、间苯二酚和溴代正丁烷为原料,通过格氏反应、傅克反应、醚化反应,合成了一种新型的三嗪类紫外线吸收剂;采用正交试验法讨论了各步反应温度、反应时间以及原料摩尔比等对合成产率的影响,并对合成产物进行了表征。结果表明:根据红外光谱,合成产物与目标产物相符,确定产物为2,4-二(2'-羟基-4'-丁氧基苯基)-6-(4″-甲基苯基)-1,3,5三嗪;该合成反应工艺简单,合成产率高,在较佳反应条件下,格氏反应、傅克反应、醚化反应的合成产率分别为80.60%,81.24%,73.58%;该紫外线吸收剂对UVA和UVB都有很强的吸收能力,最大吸收波长分别为345,275 nm。     

新紫外线吸收剂UV-S的合成工艺

以三聚氯氰为起始原料,通过四步取代反应,最终合成了新型三嗪类紫外线吸收剂UV-S。经测定化合物在产品总收率48%,含量在98%以上。测试了其紫外吸收性能。用MS、IR、HNMR确定了目标产物的结构。     

2,4,6-三(2-羟基-4-丁氧基苯基)-1,3,5-三嗪的新合成法

2,4,6-三(2-羟基-4-丁氧基苯基)-1,3,5-三嗪是一种新型高效紫外线吸收剂。是现有紫外线吸收剂中吸收能力较强和抗氧性能好的品种之一。主要用于农业聚氯乙烯薄膜、工程塑料、乳胶以及清漆涂料等方面。据国外专利记载,先用硝基苯作溶剂,通过付-克反应由三聚氯氰和间苯二酚反应,合成2,4,6-三(2,4-二羟基苯基)-1,3,5-三嗪,然后再与溴代烷反应。在七十年代,我国太原化工研究所、上海东方化工厂、东北师范大学     

化妆品防晒剂的研究进展及其安全性问题(待续)

从分子结构特点、光稳定性、应用性能以及安全性等方面综述了已被欧盟化妆品及非食品科学委员会、美国食品及药品管理局、日本厚生省以及中国卫生部批淮使用的化妆品用紫外线吸收剂。对全球近期在该领域的主要研究开发方向进行了综述和分析。三嗪类及苯三唑类衍生物因其优越的光稳定性和安全性仍然是两类研究活跃的化妆品用紫外线吸收剂。尽管高分子类紫外线吸收剂无疑是将来的主力，但要通过美国食品及药品管理局的批淮仍需时日。     

二苯甲酮类紫外线吸收剂发展趋势

本文介绍了二苯甲酮类紫外线吸收剂国内外发展及其光稳定化机理,着重介绍了紫外线吸收剂 UV—B 的合成工艺及其性能,证明该品种是一种工艺简单,成本低廉,性能优良的新型紫外线吸收剂,同时也指出了二苯甲酮类紫外线吸收剂应向多功能及反应型方向发展。     

Water‐soluble,antiyellowing polymeric fluorescence brighteners

In this study, a type of polymeric fluorescence brightener (PFB) with a triazine–stilbene structure was synthesized through a three‐step condensation reaction, and the performance of this PFB on antiyellowing was also investigated by the whiteness of paper coated with the as‐prepared PFB. Fourier transform infrared spectra revealed that the chlorine atom (·Cl) was substituted by a poly(vinyl alcohol) (PVA) group ([CH₂CHOH]_n). According to the UV aging experiment, the PFB not only enhanced the whiteness of the paper but also improved the anti‐UV aging properties [compared to those of VBL 4′‐double‐(6‐diethanolamine‐4‐sulfanilic acid‐1,3,5‐triazine‐2‐amino)‐stilbene‐2,2′‐disulfonic acid sodium, a type of commonly used fluorescent whitening agent as a light stabilizer and fluorescent brightening agent]. Moreover, the results of UV–visible spectra indicated that the substitution of PVA suppressed the isomerization of trans conformers to cis conformers under UV light irradiation; this was attributed to the big space steric hindrance of PVA in the as‐prepared samples being restricted the isomerization reaction. Meanwhile, the solubility of the as‐prepared sample was also improved because more hydroxyl groups were introduced into the PFB with the substitution of PVA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45536.     

地克珠利杂质三嗪酸乙酯的研究

对地克珠利中未知杂质2-[3,5-二氯-4-[(RS)-(4-氯苯)氰甲基]苯基]-3,5-二氧-2,3,4,5-四氢-1,2,4-三嗪-6-羧酸乙酯(简称三嗪酸乙酯)进行了定向合成,并用质谱、元素分析、红外、紫外及核磁共振对其进行结构确证。确认了该杂质是由中间体三嗪酸在酸催化下与残留的乙醇反应生成。对提高地克珠利的质量具有重要意义。     

Influence of different types of UV absorber/UV stabilizer combination on the photodegradation of PC/ABS blend

The polycarbonate/poly(acrylonitrile butadiene styrene) blends, (PC/ABS), are mainly degraded by sunlight known as photodegradation when exposed to outdoor conditions. It is the ultraviolet (UV) radiation that is responsible for the degradation of the blend. To stabilize against the harmful UV radiation and to scavenge the radical species which arise from UV or thermally induced degradation of the PC or the ABS, UV absorbers, and UV stabilizers are used. In this article three different UV absorbers namely, Tinuvin 1577—hydroxyphenyl triazine type, Cyasorb 5411—benzotriazole type, Uvinul 3030—cyanoacrylate type, and two different UV stabilizers, Tinuvin 765—monomeric hindered amine type, Tinuvin 622—oligomeric hindered amine were compounded in different combinations with PC/ABS blend at 240°C using a twin screw extruder. Accelerated aging of the compounded sample was done by Atlas Suntest apparatus. The photodegradation studies were done using UV–vis, attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy, and Yellowing index measurement. The molecular weight of the compounded sample before aging was determined by gel permeation chromatography (GPC). It was found that samples protected with hydroxyphenyl triazine type UV absorber and oligomeric hindered amine show the best result for decreasing the degradation products, oxidation rate, and yellowing of the PC/ABS blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

侧链含三嗪基团的改性聚苯醚的合成与性能表征

通过分子结构设计,对聚苯醚进行化学改性,合成了以聚苯醚为主体,侧链接枝三嗪基团的新型改性聚苯醚。最终的产物PPO-CzTA是由溴代聚苯醚与含有羟基的三嗪基团发生C-O偶联反应得到的,并对其进行了性能表征。结果显示,通过核磁和红外光谱的分析,确定了PPO-CzTA的结构,并且,接入三嗪单元的聚苯醚显示出了优异的热稳定性,并展现出了良好发光性能。     

Curing reaction of elastomers with triazine thiols and sulfen amides

Curing reaction of elastomers with triazine thiols and sulfen amides in the presence of ZnO and stearic acid was investigated for curing parameters and curing mechanism. The curing parameters such as curing rate, induction period, and curing efficiency were influenced by the pKa of thiol groups in triazine thiols and amines corresponding in sulfen amides, by the steric hinderance of 6-substituted groups in triazine thiols and on amino groups in sulfen amides, by the molar ratio of sulfen amides to triazine thiols, and by the reacting positions and the properties of elastomers. Triazine thiols acted as curing agents. Sulfen amides played two important roles in curing elastomers with triazine thiols. They gave poly(triazinyl disulfide) which is a curing precursor. Curing activators are formed in the reaction of the precursors, sulfen amides, and ZnO. The activators react with elastomers to give crosslinks, pendants and triazine dithiols or triazinyl disulfide oligomers. The pendants react with sulfen amides to give the crosslinks. The triazine thiols or triazinyl disulfide oligomers react with sulfen amides to reproduce the curing precursors. The structure of crosslinks is estimated to be      

Effect of hindered piperidine light stabilizer molecular structure and UV‐absorber addition on the oxidation of HDPE. Part 1: Long‐term thermal and photo‐oxidation studies

This series of papers explores the effect of structural characteristics of 2,2,6,6‐tetramethylpiperidine‐based hindered amine light stabilizers (HALS) on the long‐term (40 months) thermal (110°C in air) and photo‐stabilization (Microscal unit wavelength >300 nm) performance characteristics of high‐density polyethylene formulations. Possible synergism with a triazine functional UV absorber is also explored. Under thermal degradation (measured by carbonyl index) the polymeric HALS performed best, mainly because of reduced volatilization. Additionally, >N‐methyl HALS generally showed superior performance under thermal degradation. There was no synergism between an N‐CH₃ polymeric HALS and the UV1164 triazine additive. However, the equivalent N‐H polymeric HALS interacted in a complex manner with UV1164, giving synergism and antagonism, depending on HALS/UV1164 ratio. Strong synergism was evident with the monomeric HALS when the total stabilizer level was 0.2% w/w. Reduction in the overall stabilizer level to 0.05% w/w eliminated the synergism. The UV1164 alone led to rapid and intense yellowing; however, the rate and intensity of yellowing reduced dramatically upon combination with HALS, particularly when the UV1164 level was above 0.1% w/w. When the formulation was under UV attack, the molar mass and the type of N‐substitution had no influence on stabilization performance because of the relatively low temperature of testing (leading to reduced volatilization), and the similarly effective UV‐stabilization routes for N‐methyl HALS and N‐H HALS. Under UV attack, yellowing reached a maximum and then decreased to approximately the initial level, while HALS/UV1164 combinations generally showed weak antagonism. J. Vinyl Addit. Technol. 10:79–87, 2004. © 2004 Society of Plastics Engineers.     

苯氧基三嗪聚合物的合成及膨胀阻燃ABS的研究

合成了一种苯氧基三嗪聚合物,研究了合成反应的影响因素。利用FTIR、熔点测定仪、元素分析仪以及银定量法测定氯含量、磷钼酸喹啉重量法测定磷含量等方法对其结构进行了表征。将此苯氧基三嗪聚合物与聚磷酸铵和红磷复配为膨胀型阻燃剂,研究了此阻燃剂对丙烯腈-丁二烯-苯乙烯三元共聚物的阻燃性能及力学性能的影响。结果表明,该苯氧基三嗪聚合物的合成产率比较理想,用其复配的膨胀型阻燃剂对丙烯腈-丁二烯-苯乙烯三元共聚物表现出较好的阻燃性能及力学性能。     

氢氰酸法合成高品质原甲酸三甲酯

以氢氰酸、甲醇、无水氯化氢为原料,在溶剂R1存在下经成盐、醇解、精馏制备原甲酸三甲酯,总收率可达80%。成盐反应的最佳工艺为:投料配比n(HCN)∶n(CH3OH)∶n(HCl)=1∶1.05∶1.15,反应温度-15~5℃,反应时间10 h,体系w(H2O)<0.2%,在该工艺下,HCOCH3NH.HCl的收率达87.1%,残留氰根ρ(HCN)<0.1 g/L;醇解反应的最佳反应温度是30~35℃,反应时间8 h。两步合成有效地控制了产品的主要杂质三嗪,产品中w(三嗪)<0.1%,w(原甲酸三甲酯)≥99.80%。工业化中试在100 L搪瓷釜中进行,最好收率达81.1%,w(原甲酸三甲酯)=99.85%,w(三嗪)=0.07%。