聚合型受阻酚抗氧剂的研究进展

综述了以双环戊二烯、对甲苯酚和异丁烯为原料生成聚合型受阻酚抗氧剂CPL的反应机理、国内外文献报道的典型制备方法及应用情况。指出了聚合型受阻酚抗氧剂的发展趋势,强调了应加强此类抗氧剂的研究。     

聚合型受阻酚抗氧剂CPL的合成工艺优化

研究了以工业级双环戊二烯、对甲苯酚、甲基叔丁基醚为原料制备聚合型受阻酚抗氧剂CPL的合成工艺。考察了催化剂种类和用量、反应物的物质的量配比、反应温度、反应时间等因素对合成CPL收率、熔点的影响,并提出了新的产品纯化方法。     

非对称型受阻酚抗氧剂KY—586的合成

以邻甲酚、异丁烯、丙烯酸甲酯、二缩三乙二醇为原料,通过烷基化反应、加成反应、酯交换反应合成非对称型受阻酚抗氧剂KY－586,研究了合成的工艺条件及产品的表征。     

受阻酚抗氧剂Ky—586的合成及应用

介绍了受阻酚类抗氧剂Ｋｙ－５８６的合成路线及性能特点,了Ｋｙ－５８６、Ｉｒｇａｎｏｘ１０７６、Ｉｒｇａｎｏｘ２４５在通用聚苯乙烯、高冲聚苯乙烯和聚甲醛中的应用。     

聚合型受阻酚抗氧剂CPL在ABS树脂中的应用研究

聚合型受阻酚抗氧剂CPL[聚(双环戊二烯-CO-对-甲酚)]由对甲基苯酚与双环戊二烯合成,是一种新型通用型酚类抗氧剂.将CPL用于ABS树脂中,研究其抗氧化效果,结果发现,添加3‰CPL的ABS树脂的氧化放热温度比未添加的提高了14℃,添加5‰CPL的ABS树脂的氧化放热温度比未添加的提高了22℃,CPL的添加可以使ABS树脂的抗氧化效果得到有效提升.     

非对称型受阻酚抗氧剂ky-586结晶的研究

主要介绍非对称型受阻酚抗氧剂ky-586在结晶过程中的影响因素.     

高相对分子质量受阻酚抗氧剂KY-1330的合成与应用

介绍了高相对分子质量受阻酚抗氧剂KY-1330的特点、合成及应用。着重介绍了该抗氧剂在国内的研发、生产及应用情况。对现有的合成工艺路线进行了比较,认为2,6-二叔丁基苯酚加入多聚甲醛,再与均三甲苯缩合的二步法更适合于国内。     

浅谈受阻酚抗氧剂ky-586工业化生产的技术要点

本文从提高收率和产品质量出发,阐述了ky - 583工业化生产的技术要点。     

测氧法研究受阻酚抗氧剂的抗氧化活性及反应动力学

采用测氧法考察了4种市售受阻酚抗氧剂的抗氧化活性,同时对其清除ROO·反应进行了动力学分析。结果表明:4种受阻酚抗氧剂对ROO·均具有良好的清除作用,并且抗氧化活性随着酚羟基浓度增加而增大。在同等的酚羟基浓度下,抗氧剂的抑制速率常数kinh值从大到小的顺序为抗氧剂1098、抗氧剂BHT、抗氧剂1010、抗氧剂1076。抗氧剂的抗氧化活性与功能基团的个数和对位取代基的供电性密切相关,酚胺复合型抗氧剂体现出更高的抗氧化活性。     

Synthesis and antioxidant activities in polyolefin of dendritic antioxidants with hindered phenolic groups and tertiary amine

Two novel primary antioxidants with dendritic structure and hindered phenolic groups were synthesized using 3‐(3,5‐diter‐butyl‐4‐hydroxyphenyl) propionic acid as raw material and dendritic poly(amidoamine) (PAMAM) as linker in chloroform. The antioxidant activities of the dendritic antioxidants were evaluated in polyolefin by melt flow index (MFI), yellowness index (Y.I.), and oxidation induction time (OIT). The dendritic antioxidants had excellent processing property and oxidation resistance behavior in polyolefin. At the same weighed amount of antioxidant, the MFI and Y.I. values of mulitiple‐extruded polyethylene (PE) stabilized with the dendritic antioxidants were smaller than those of the commercial antioxidants, as well as the OIT values of polyethylene (PE) stabilized with the dendritic antioxidants were larger. Applying to polypropylene, the antioxidant ability of the second‐generation dendritic antioxidant (G2.0 dendritic antioxidant) with larger molecular weight was superior to the commercial antioxidants and that of the first‐generation dendritic antioxidant (G1.0 dendritic antioxidant) was equal to the commercial antioxidants. The dendritic antioxidants can prevent polyolefin from breaking of macromolecular chain in processing and had stabilizing effect in polyolefin in service life by donating H‐atoms and electron to free radicals. The dendritic antioxidants combined with Irgafos 168 had improvement of antioxidant activities of the dendritic antioxidants in polyolefin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

受阻酚类抗氧剂结构与其抗氧化性能的影响关系

选取了3种酚羟基个数不同的受阻酚类抗氧剂为研究对象,通过性能测试、氧化诱导温度测试以及羰基指数测试等对添加抗氧剂后合成的聚乙烯进行对比分析,考察抗氧剂结构对聚乙烯性能的影响。结果表明,虽然受阻酚类抗氧剂中酚羟基的个数增多可以提高抗氧剂的抗氧化效果,但耐老化性能变弱,因此优选适宜的酚羟基个数对于提升受阻酚类抗氧剂的抗氧化性能十分必要。     

受阻酚抗氧剂对NBR/WCB共混胶耐热老化性能的影响

研究了抗氧剂2-叔丁基-6-(3-特丁基-2-羟基-5-甲基苯基)-4-甲基苯酚丙烯酸酯(简称GM)、抗氧剂264和抗氧剂2246对NBR/WCB共混胶的硫化特性、力学性能和耐热老化性能的影响,并通过TG分析表征NBR/WCB共混胶的耐热稳定性。结果表明,与抗氧剂264和抗氧剂2246相比,抗氧剂GM对NBR/WCB共混胶具有防止焦烧、加快硫化速度和软化胶料的作用。添加抗氧剂GM的共混胶比加入抗氧剂264和2246的共混胶具有更优异的耐热老化性能。TG分析表明,在3种抗氧剂中,加入抗氧剂GM的NBR/WCB共混胶的耐热稳定性最高。     

Polyolefin elastomer grafted unsaturated hindered phenol esters: synthesis and antioxidant behavior

Monomeric antioxidants are synthesized from esterification of 3,5-di-tert-butyl-4-hydroxybenzoic acid and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with unsaturated fatty alcohols. The antioxidant activity is evaluated both in blending and radical grafting processes. The effect of chain length and phenolic group is investigated on efficiency of antioxidants. It is demonstrated that the esters of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid exhibit significantly longer induction time. The results of radical grafting reaction shows synthesized antioxidants can be successfully grafted onto polymer chains and the phenolic moiety is functional after extraction process, while pure and commercially stabilized samples are degraded instantaneously. Also, different initiator systems are utilized to enhance the extent of grafting. Among MEK, DCP, and DHBP peroxides, DHBP can be more effective in increasing the antioxidant grafted onto polymer. In addition, possibility of rising in graft content is investigated in presence of redox initiator. Using this approach, polymer-bound antioxidant with prolonged thermal stability can be achieved.     

多乙烯多胺桥联受阻酚类抗氧剂的合成及其清除DPPH·性能

以二乙烯三胺和三乙烯四胺为桥联基,β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为抗氧化功能基团,通过酰胺化缩合反应合成了两类具有不同对位桥联基团的受阻酚类抗氧剂。采用傅里叶红外光谱和核磁共振氢谱证实了合成的多乙烯多胺桥联受阻酚类抗氧剂的化学结构。DPPH法研究了多乙烯多胺桥联受阻酚类抗氧剂清除自由基的性能,并探索了酚羟基个数和对位桥联基结构对受阻酚类抗氧剂清除自由基性能的影响。结果表明,多乙烯多胺桥联受阻酚类抗氧剂具有良好的清除DPPH·能力,且随着抗氧剂分子中酚羟基个数的增加,清除DPPH·的活性增加,分子中含有4个酚羟基的三乙烯四胺受阻酚类抗氧剂的抗氧化效率（AE）达到2.65×10^-2 L/(mol·s)。对位桥联基结构对受阻酚类抗氧剂清除DPPH·能力有较大影响,季戊四醇为桥联基的受阻酚类抗氧剂1010清除DPPH·能力最强,其抗氧化效率（AE）为3.08×10^-2L/(mol·s);乙二胺为核的1.0代树枝状受阻酚类抗氧剂清除DPPH·能力最弱,其抗氧化效率（AE）为2.60×10^-2 L/(mol·s)。     

Extraction resistance and mechanism of a macromolecular hindered phenol antioxidant in natural rubber

Due to low thermal stability, poor migration, and extraction resistances, the antioxidant with low molecular weight is easy to physically lose during processing and long‐term service, and its applications are severely restricted. To increase the molecular weight of antioxidant is one of the promising methods to overcome such drawbacks. In this study, the extraction resistance of a macromolecular antioxidant, namely polyhydroxylated polybutadiene containing thioether binding 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) (PHPBT‐b‐TPH), was investigated by extraction resistance test and equilibrium swelling experiment. The results exhibited that the PHPBT‐b‐TPH offered much better extraction resistance in natural rubber (NR) than the low molecular weight antioxidant TPH. In addition, the extraction resistance of hydroxyl‐terminated polybutadiene (HTPB), polyethylene glycol (PEG), and polypropylene glycol (PPG) in NR were also compared to study the extraction mechanism of the PHPBT‐b‐TPH. It was found that the higher molecular weight of PHPBT‐b‐TPH and the co‐vulcanization between PHPBT‐b‐TPH and NR were the main reasons for the excellent extraction resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44905.     

Melt free‐radical grafting of hindered phenol antioxidant onto polyethylene

A monomeric antioxidant (3) was prepared by reacting 3,5‐di‐tert‐butyl‐4‐hydroxybenzyl alcohol (1) with N‐[4‐(chlorocarbonyl) phenyl] maleimide (2). This reactive antioxidant was grafted onto polyethylene (PE) by melt processing with free‐radical initiators in a mini‐max molder. The IR spectra of the grafted PE showed that the monomeric antioxidant was introduced onto the PE. IR spectroscopic methods and titration were used for the quantitative determination of the extent of grafting of the monomeric antioxidant. Also, the extent of crosslinking was indicated by the gel content. Grafting occurred in the following order: dicumyl peroxide (DCP) > benzoyl peroxide > 2,2′‐azobisisobutyronitrile. The influences of the DCP concentration and monomeric antioxidant on the extent of grafting were studied. The effects of the reaction time and temperature were also determined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2968–2973, 2000     

液体酚抗氧剂的合成及在燃料油中的应用研究

在有机锡催化下,以3–(3,5–二叔丁基–4–羟基苯基)丙酸甲酯和异辛醇为原料合成了液体酚抗氧剂,在优选的反应条件下,抗氧剂的收率95%,质量分数99%。经分析和应用验证,所合成的抗氧剂可明显抑制或延缓燃料油的氧化老化。     

国产抗氧剂在聚乙烯农膜中的应用

目前我国农业塑料薄膜的生产量,地膜和棚膜的覆盖面积已居世界首位,并持续高速发展。农用塑料薄膜以其生产使用的树脂原料不同一般可分为聚氯乙烯农膜和聚乙烯农膜两类。农业的发展以及人们环保意识和观念的提高,对聚乙烯农膜提出了更高的要求,同时促进了聚乙烯农膜所用助剂,特别是国产抗氧剂的科研、生产和应用研究。本文着重探讨和论述了国产抗氧剂在聚乙烯农膜中的应用。