3–(3,5–二叔丁基–4–羟基苯基)丙酸甲酯及新型抗氧剂的合成

简述了3–(3,5–二叔丁基–4–羟基苯基)丙酸甲酯的合成方法及以其为原料合成新型抗氧剂的方法,介绍了部分新型抗氧剂品种及性能。     

降低酚酯型抗氧剂合成中的残留锡含量

以β–(3, 5–二叔丁基–4–羟基苯基)丙酸甲酯为原料、二丁基氧化锡为催化剂,通过酯交换反应,分别合成了抗氧剂1135(3, 5–二叔丁基–4–羟基苯基丙酸异辛酯)和1035[2, 2′–硫代双(3, 5–二叔丁基–4–羟基苯基)丙酸乙酯]。采用原子吸收光谱研究了柠檬酸对产物中残留锡的脱除效果。结果显示,柠檬酸与催化剂摩尔比为2:1时,在温度110℃、绝对真空度0.003 MPa下处理反应物1 h,抗氧剂中残留锡较少,质量分数20×10–6。     

长玻纤增强聚丙烯中抗氧剂的液相色谱分析与应用

通过液相色谱分析5种抗氧剂及其复配抗氧剂,发现不同抗氧剂的保留时间、信号响应值与其种类和用量之间存在明确的对应关系。在此基础上,以正己烷为溶剂分别抽提3种长玻纤增强聚丙烯(LGFPP)样品A,B和C中的抗氧剂并进行液相色谱分析,结果表明,样品A的抗氧剂体系为抗氧剂AO–K1和AO–K5的二元复配,样品B和C的抗氧剂体系相同,是抗氧剂AO–K1,AO–K2和AO–K4的三元复配;3种样品在A3.05的响应值分别为70,66和34 mAU,抗氧剂AO–K1的含量以样品A中最高、样品B中次之、样品C中最低,样品A中含有长效耐热抗氧剂AO–K5;液相色谱分析结果表明,样品A的长期耐热老化性能最佳、样品B次之、样品C最差,与长期热老化测试结果相一致。该方法在原材料筛选和质量监控方面应用价值良好。     

2,2’-亚甲基双(4-甲基-6-α-甲基苄基苯酚)的合成与性能评价

以单苯乙烯化对甲酚(单酚)为底物,与35%~37%的甲醛水溶液在酸催化的条件下进行反应,合成了一种酚羟基邻位取代具有活泼α-H原子的双酚类抗氧剂2,2’-亚甲基双(4-甲基-6-α-甲基苄基苯酚)。最佳工艺条件:n(单酚)∶n(甲醛)=1∶3,80℃回流反应5 h,产率85%。测定加抗氧剂的润滑油油样的过氧化值(POV)表明,合成双酚抗氧剂具有比抗氧剂2246更好的抗氧性。     

抗氧剂736的制备及其在聚丙烯树脂中的应用

叙述了新型硫代酚类抗氧剂736的制备方法,合成的抗氧剂736收率达到82%以上,产物结构经红外光谱和元素分析确证.采用DSC法测定抗氧剂736及抗氧剂1010在聚丙烯中的抗热氧性能,以氧化诱导期(OIT)为指标评价抗氧剂功效.试验表明:抗氧剂736优于抗氧剂1010.     

新型受阻酚类抗氧剂的合成与性能研究

以2,6-二叔丁基苯酚原料,合成了1种新型受阻酚抗氧剂2,6-二叔丁基-4-氨基苯酚,研究了该新型抗氧剂对聚烯烃材料的抗氧化作用。结果表明,以锌粉为还原剂,8.5 %氯化钙水溶液用量为90 mL,溶剂乙醇用量为100 mL, 在80 ℃下反应8 h,新型受阻酚抗氧剂的产率达80 %以上,熔程为112.2~113.3 ℃。该抗氧剂在2种聚烯烃材料中均具有良好的加工稳定性和抗氧化性能,氧化诱导期与市售抗氧剂1076相当,优于抗氧剂BHT;经5次挤出后,添加新型抗氧剂的聚烯烃材料的熔体流动速率变化很小,但拉伸强度和断裂伸长率大幅度提高。     

家电专用ABS耐候白色母的研制

研究了ABS色母中钛白粉、抗氧剂、光稳定剂、调白颜料对ABS耐候性能的影响。结果表明,金红石钛白粉、抗氧剂和光稳定剂能够提高ABS的耐候性能。通过优化配方,研制出一种UV–B老化168 h,色差6.0的家电专用ABS耐候白色母,其中钛白粉、光稳定剂、抗氧剂、调白颜料的质量分数分别为30%,30%,5%,0.01%。     

抗氧剂425的合成与结构表征

研究了以对乙基苯酚、叔丁醇为原料,在酸性条件下,进行烷基化反应,合成2 叔丁基 4 乙基苯酚,再进一步缩合成抗氧剂425的工艺条件。并对产品进行了熔点,相对分子质量,高效液相色谱(HPLC)及核磁共振谱(NMR)的测定。结果表明,两步反应的收率分别为85%～90%和50%～60%。产品熔程为121～123℃,相对分子质量为368 3,均与文献相符。HPLC分析在5 272min出峰,NMR谱图证明所得到产品为抗氧剂425。     

抗氧剂1520的合成工艺研究

以邻甲基苯酚为主要原料,合成了抗氧剂1520,并对抗氧剂1520的合成工艺条件进行了优化研究,产品的颜色和收率达到了国外同类产品水平。在反应过程中采用氮气保护下,以DMF作为溶剂,n(邻甲苯酚):n(多聚甲醛):n(正辛硫醇):n(哌啶)=1:4:1:1.4,反应温度为120℃,反应时间在5 h,产品收率达到96.96%,纯度为98.30%,颜色近似水色。     

高含量单取代异辛基二苯胺的制备与性能

以自制的选择性固体酸为催化剂,采用二苯胺和2,4,4-三甲基-1-戊烯制备了高含量单取代异辛基二苯胺(M-IDPA)抗氧剂,并研究了其合成工艺。采用热稳定分析仪、旋转氧弹测试仪、加压差示扫描量热仪测试了产物的热稳定性及抗氧化性能。结果表明:通过选择不同的固体酸催化剂,在最优工艺条件下,M-IDPA的质量分数高达78.01%;高含量M-IDPA抗氧剂在基础油150N中的质量分数分别为0.5%和1.0%时,氧化诱导时间为1 044,2 713 min,说明所制抗氧剂具有优良的抗氧化性能;热稳定性分析结果表明该抗氧剂具有很好的热稳定性能。     

喹喔啉化合物的脂质过氧化活性

研究了一系列先前合成的喹喔啉化合物的抑制脂质过氧化活性,实验得到了这些化合物的体内和体外脂质过氧化抗氧化活性数据,发现这类喹喔啉化合物具有优异的抗氧化活性,其中,脂质过氧化清除率最高的化合物是2-(3-(3-甲氧基-4-羟基苯基)-2氧喹喔啉-1(2H)-烷基)乙酸,它在浓度为100μmol/L时,对应的清除率达到了57.7%。构效关系研究认为对羟基苯乙烯这一结构单元对于喹喔啉化合物在提高抗氧化活性有重要意义。     

脲基含量和抗氧剂对HMDI型WPU耐黄变性的影响

以4,4'-二环己基甲烷二异氰酸酯(HMDI)、聚四氢呋喃二醇(PTMEG)或聚己二酸新戊二醇-1,4-丁二醇酯二醇(CMA654)为主要原料合成了水性聚氨酯(WPU)乳液,并制膜进行耐黄变性测试。探讨了聚氨酯分子链中脲基含量、抗氧剂的种类及添加量对WPU胶膜耐黄变性的影响。结果表明,提高脲基含量可以提高胶膜的耐黄变性;添加质量分数0.9%的2,6-二叔丁基对甲苯酚(BHT)或0.3%的抗氧剂1010可有效提高胶膜的耐黄变性;受阻酚与亚磷酸酯复配型抗氧剂相对于传统抗氧剂1010对胶膜的耐黄变性提高更为明显,且添加量少于单独使用抗氧剂1010。     

新型双酚类抗氧剂2,2′-亚甲基双（6-壬基对甲酚）的合成

抗氧剂2,2′-亚甲基双（6-壬基对甲酚）是新型大分子量液体双酚类抗氧剂,我们以对甲酚为原料,通过酯化反应、Fries重排反应、傅克酰化反应、羰基Clemmensen还原反应和酸介导的甲醛亲和取代反应合成了2,2′-亚甲基双（6-壬基对甲酚）,中间体和最终产物都通过NMR、MS表征确证,以大于90%的总收率实现产品的合成。     

Novel N-Substituted Amino Acid Hydrazone-Isatin Derivatives: Synthesis,Antioxidant Activity,and Anticancer Activity in 2D and 3D Models In Vitro

A series of novel mono and bishydrazones each bearing a 2-oxindole moiety along with substituted phenylaminopropanamide, pyrrolidin-2-one, benzimidazole, diphenylmethane, or diphenylamine fragments were synthesized, and their anticancer activities were tested by MTT assay against human melanoma A375 and colon adenocarcinoma HT-29 cell lines. In general, the synthesized compounds were more cytotoxic against HT-29 than A375. 3-((4-Methoxyphenyl)(3-oxo-3-(2-(2-oxoindolin-3-ylidene)hydrazinyl)propyl)amino)-N′-(2-oxoindolin-3-ylidene)propanehydrazide and (N′,N‴)-1,1′-(methylenebis(4,1-phenylene))bis(5-oxo-N′-(2-oxoindolin-3-ylidene)pyrrolidine-3-carbohydrazide) were identified as the most active compounds against HT-29 in 2D and 3D cell cultures. The same compounds showed the highest antioxidant activity among the synthesized compounds screened by ferric reducing antioxidant power assay (FRAP). Their antioxidant activity is on par with that of a well-known antioxidant ascorbic acid.     

复合型受阻酚抗氧剂的制备及清除DPPH·活性研究

以二苯基氯化磷和2,2′亚甲基双(4甲基6叔丁基苯酚)为原料,合成具有亚磷酸酯及受阻酚结构的复合型抗氧剂2(2羟基3叔丁基5甲基苄基)4甲基6叔丁基苯基二苯基亚磷酸酯,产率为65.12 %,产物经FT-IR表征,符合理论设计构型。将产物与商用抗氧剂2,6二叔丁基4甲基苯酚(BHT)进行热稳定性及DPPH自由基清除能力的对比测试,结果表明,产物较抗氧剂BHT分子量更高,热稳定性更好;同时其对DPPH自由基具有良好的清除效果,其抗氧化能力强于抗氧剂BHT。     

Synthesis and antioxidant properties of fullero-steroidal covalent conjugates

Four new fullero-steroids were synthesized starting from γ-aminobutyric acid (GABA)-incorporated fulleropyrrolidine and corresponding sterols. The synthesis, characterization, preliminary study on in vitro antioxidant activity as well as the steady state photophysical properties are presented. All synthesized compounds showed antioxidant activity 2-3-fold higher than the parent fullerene. The most active compound appeared to be as potent as standard antioxidant BHT (2,6-di-tert-butyl-4-methylphenol). Also, all of them fluoresce 6-8-fold stronger than C₆₀, thus representing potential irradiation assisted pro-oxidants. With significantly increased lipophilicity, it could be expected that attached steroidal subunit enables better penetration of C₆₀ to living cell membranes, thus facilitating its antioxidant activity. Based on all obtained results, newly synthesized covalent fullero-steroidal conjugates represent good candidates for potential antioxidants as well as pro-oxidants.     

藤茶黄酮绿色制备纳米氧化锌及其抗氧化和抗菌性能

以藤茶黄酮为原料,采用溶液燃烧法绿色制备纳米氧化锌(Nano ZnO)粉末,并利用FTIR、XRD、SEM和EDS对所得样品进行结构分析和形貌观察;使用布兰德-威廉姆斯法、透明抑菌圈法和最小抑菌浓度法考察了绿色合成Nano ZnO的抗氧化性能和抑菌性能。结果表明,以藤茶黄酮为生物模板制备的Nano ZnO粒子为六方晶系纤锌矿结构,结晶度良好,晶粒平均尺寸约为32.7nm;该纳米材料具有良好的抗氧化活性,2.5g/L的Nano ZnO溶液对1,1-二苯基-2-三硝基苯肼自由基(DPPH·)的清除率为98.24%;藤茶黄酮绿色合成Nano ZnO对金色葡萄球菌的抑菌活性高于传统化学合成的Nano ZnO。绿色合成Nano ZnO的最小抑菌浓度为1.00 g/L,而化学合成Nano ZnO的最小抑菌浓度为1.50 g/L。     

Degradation and stabilization of cosmetic polyetherurethane in alcoholic solution

A polyetherurethane (PEU) was synthesized for potential cosmetic applications by coupling poly(tetramethylene oxide) (PTMO, M_n = 2000 g mol^?1) and poly(ethylene oxide) (PEO, M_n = 2000 g mol^?1) with 4,4′‐diphenylmethane diisocyanate (MDI), without using a chain extender. The PEU polymer, synthesized with PEO and PTMO in the ratio of 1:3 by weight, was soluble in ethanol–water mixed solvents. The solution formed a thin film in situ on the skin by coating, which was flexible and elastomeric with appropriate skin adhesiveness. However, PEU was susceptible to degradation when it was exposed to an ethanol–water (80/20 v/v %) mixed solvent and stored in an air‐filled and sealed bottle at 60°C for 4 weeks. These conditions resulted in deterioration of PEU molecular weight (M_n), viscosity, and mechanical properties. Peak analysis of the Fourier transform infrared spectrum of the aged PEU revealed that >97% of the urethane carbonyl bonds remained, whereas ether bonds were significantly reduced (～82% of initial value). The degraded PEU contained ester bonds, which were confirmed by proton and carbon‐13 nuclear magnetic resonance spectroscopy. This observation suggests that oxidative chain cleavage rather than hydrolysis was the dominant reaction in the degradation process. Two approaches were adopted to minimize oxidative degradation of PEU dissolved in an ethanol–water (80/20 v/v %) mixed solvent; they were, applying a nitrogen environment and adding an antioxidant (1.8 wt % dry PEU). The results indicate that reduction of oxidative degradation produced a synergistic effect. Vitamin E was a more effective antioxidant than butylated hydroxytoluene (BHT), which is a typical antioxidant for commercial polyurethanes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2270–2276, 2003     

聚烯烃中抗氧剂330的快速分析方法研究

研究了红外光谱法定性定量分析聚乙烯、聚丙烯中的抗氧#1330。分析了抗氧剂330和PE、PP粉料的FT-IR图,确定了抗氧剂330在聚乙烯、聚丙烯中的特征吸收峰分别为1152cm^-1,3650cm^-1。详细分析了抗氧剂330分别与定量的PE、PP及硬脂酸钙所制样品对所测谱图和所制曲线的影响。抗氧剂330的标准曲线表明,抗氧剂330的含量与其特征峰的吸收强度呈良好的线性关系,相关系数达0．97以上,相对百分偏差最大为11．765％。