Assessment of hindered phenol antioxidants on processing stability of peroxide‐cure LDPE by rheology and DSC analysis

Influence of commercial phenol antioxidants Irganox 300, 1010, 1035, and 1076 on peroxide‐cure reaction of low‐density polyethylene (LDPE) was evaluated through isothermal dynamic rheological and nonisothermal differential scanning calorimetry (DSC) testing. The results indicated that phenol antioxidants could reduce storage modulus of LDPE completely crosslinked at 175°C while they have a neglectable effect on gel fracture and activity energy of crosslinking reaction. On the other hand, time sweep dynamic rheological test revealed the antioxidants 1035 and 1076 with low molecular weight and low melting point could significantly depress scorch of crosslinkable LDPE at 135°C. The isothermal time sweep dynamic rheology test method was more sensitive than nonisothermal DSC test for characterizing the influence of phenol antioxidants on crosslinking kinetics of peroxide‐cure reaction of LDPE. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Performance and synergistic effect of phenolic and thio antioxidants in ABS graft copolymers

The synergistic effect of phenolic and thio antioxidants on the stabilization of acrylonitrile-butadiene-styrene (ABS) graft copolymers has been studied. Three commercial antioxidants Irganox245, Irganox1076 and dilauryl thiodipropionate (DLTP) were selected. Formulations based on hindered phenols and secondary antioxidant DLTP were prepared. Stabilization was monitored in terms of changes in the functional groups (oxidation products), tensile properties and yellowness index. Differential scanning calorimetry (DSC) and thermogravimetry (TG) were also used to assess the stability. The results indicated that the combination of Irganox245 and DLTP showed much better stabilization effect than the individual components due to the strong synergistic effect. Only weak synergism could be observed in the formulation that contained Irganox1076 and DLTP. Irganox1076 and Irgnox1076/DLTP exhibited similar behaviors between antioxidants with the highest and lowest efficiencies.     

抗氧剂增效剂SBDT在聚丙烯中的应用

用环氧大豆油和十二硫醇合成出抗氧剂增效剂SBDT，该增效剂耐挥发、耐抽提。考察了SBDT与酚类抗氧剂1010、1076复配对PP的加工稳定性及长期热氧稳定性的影响，并与DLTP、DSTP和168等辅助抗氧剂的性能进行了对比。实验结果表明：与酚类主抗氧剂复配并用，该增效剂SBDT抗热氧效能比DLTP、168好，有的配方的效能已接近DSTP。     

Improving the aging resistance of styrene‐butadiene‐styrene tri‐block copolymer and application in polymer‐modified asphalt

Thermal oxidation process of styrene‐butadiene‐styrene (SBS) copolymer was studied by using a variety of analytical and spectroscopic methods including thermal analysis, dynamic mechanical analysis and FTIR spectroscopy. The experimental results indicate that the thermal oxidation process of SBS is a free radical self‐catalyzed reaction containing four steps (initiation, growth, transfer, and termination of the chain) with both crosslinking and scission and the latter is confirmed to be the main process. The antioxidants 1010 as scavenger of free radicals and 168 acting decomposition of hydroperoxides were used to improve the oxidation aging resistance of SBS copolymer. It has been found that synergic effect of 1010 and 168 may be the best in practice and 0.2 wt % 1010 + 0.4 wt % 168 can effectively prevent SBS from the thermal oxidation at certain temperature. Furthermore, the aging resistance of the SBS‐modified asphalt was improved by addition of complex antioxidants. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structural effect of secondary antioxidants on mechanical properties and stabilization efficiency of polyamide 6/halloysite nanotube composites during heat ageing

Hindered phenol (Irganox 1010) was combined with two kinds of secondary antioxidants [i.e., tris(2,4‐di‐tert‐butylphenyl) phosphite (Irgafos168) and tris(nonylphenyl) phosphite (TNPP)] to form antioxidant mixtures, and their influences on mechanical properties and thermo‐oxidative degradation of polyamide 6 (PA6) and halloysite nanotube (HNT) filled composites were investigated. The results showed that the antioxidant combinations provided an improvement in the oxidative induction time, decomposition temperature (T_d), processability, and tensile properties of PA6. Irganox/TNPP (1:1) was found to exhibit the best thermal oxidative resistance. The study of heat ageing in the air oven at 130 °C showed that the stabilized composites with 5 wt % of HNT could retain 92% of strength without loss of modulus. The physical characteristics of antioxidants such as low volatility and possible interaction with filler in the composites played a crucial role in stabilizing efficiency during heat ageing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45360.     

新型抗氧剂HD在热塑性弹性体SBS加工中的应用*

采用吸氧量法和热烘箱老化法对新型抗氧剂ＨＤ在热塑性弹性体ＳＢＳ加工中的应用进行了研究。试验结果表明,在１００份ＳＢＳ中加入０８份抗氧剂ＨＤ６的抗氧化效果最好;抗氧剂ＨＤ３和ＨＤ４的抗氧化效果优于抗氧剂１０１０;抗氧剂ＨＤ／１０１０的并用效果优于辅助抗氧剂ＤＬＴＰ／抗氧剂１０１０的并用,抗氧剂ＨＤ３、ＨＤ４和辅助抗氧剂ＤＬＴＰ均与抗氧剂１０７６具有协同效应,抗氧剂ＨＤ３与辅助抗氧剂ＤＬＴＰ的抗氧化效果相近,而抗氧剂ＨＤ５则稍差     

Effects of phenolic antioxidants on ultrahigh molecular weight polyethylene/decalin solution

The degradation of ultrahigh molecular weight polyethylene (UHMW‐PE) during its dissolution into decalin is discussed. The stabilization of the solution by three phenolic antioxidants, octadecyl β‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate (1076), tetrakis[methylene‐β‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate]methane (1010), and 1,1,3‐tris(2‐methyl‐4‐hydroxy‐5‐tert‐butylphenyl)butane (CA), and an auxiliary antioxidant, dilaurylthiodipropionate (DLTP) is also discussed. Among the three phenolic antioxidants, 1076 had the greatest effect. The auxiliary antioxidant was effective in stabilizing the solution when combined with one of the three phenolic antioxidants. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2877–2881, 2000     

超高分子量聚乙烯溶液的降解与抗降解

讨论了超高分子量聚乙烯在十氢萘溶液中溶解过程的降解行为，以及抗氧剂和辅助抗氧剂对其降解行为的抑制作用，试验结果表明，酚类抗氧剂ＣＡ，１０１０和１０７６中１０７６的抗降解效果最好，而辅助抗氧剂ＤＬＴＰ对三种抗氧剂都有较好的协同作用。     

Process efficiency and long‐term performance of α‐tocopherol in film‐blown linear low‐density polyethylene

α‐Tocopherol was compared with a commercial phenolic antioxidant (Irganox 1076) as a long‐term and process antioxidant in film‐blown and compression‐molded linear low‐density polyethylene. The antioxidant function of α‐tocopherol was high in the film‐blown material, especially in the processing, according to oxygen induction time measurements with differential scanning calorimetry. The residual content of α‐tocopherol after processing, determined with chromatographic techniques, was less than that of the commercial phenolic antioxidant in both the film‐blown and compression‐molded materials. The process stabilizing efficiency was nevertheless higher for the material containing α‐tocopherol. During the long‐term stabilization, the efficiency of α‐tocopherol was less than that of the commercial phenolic stabilizer Irganox 1076 in the thin films, according to chemiluminescence and infrared measurements. The long‐term efficiency in the compression‐molded samples stabilized with α‐tocopherol or Irganox 1076 was equally good because of the low loss of both α‐tocopherol and Irganox 1076 from the thicker films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2427–2439, 2005     

环氧化苯乙烯-异戊二烯-苯乙烯嵌段共聚物的热氧老化研究

采用FI-IR研究了环氧化苯乙烯-异戊二烯-苯乙烯嵌段共聚物（ESIS）热氧老化前后的结构变化,并通过力学性能的测试考察了抗氧剂对ESIS抗热氧老化性能的影响。结果表明,ESIS在热氧老化过程中,环氧基和C=C双键减少,而由环氧基开环生成的羰基和羟基则显著增多。抗氧剂Irganox1010和Irgafos168的复合体系能够有效提高ESIS的抗热氧老化性能。     

Loss and transformation products of the aromatic antioxidants in MDPE film under long‐term exposure to biotic and abiotic conditions

The loss of a primary phenolic antioxidant Irganox 1010 and of a secondary phosphite antioxidant Irgafos 168 from a medium density polyethylene film (MDPE) was investigated after exposure of the film for 4 years to different environments such as aqueous media at pH5 and 7, open air, and compost, with an exposure of exposition of 25°C. An ultrasonic extraction technique using chloroform as extraction solvent was applied to recover the residual antioxidants from the polymeric matrix, and this was followed by High‐Performance Liquid Chromatography (HPLC) with acetonitrile as mobile phase and a quantitative analysis at a wavelength of 280 nm of the extracted antioxidants. The amount of antioxidant lost varied remarkably depending on the testing medium. The fastest loss of antioxidant was found on exposure to open air and sunlight while the slowest loss was observed in compost. Thermo‐analytical measurements were made to characterize the residual thermo‐oxidative stability of MDPE film in terms of oxidation temperature and oxidation induction time, to provide a greater insight into the underlying mechanisms of ageing in the different environments. Analysis by Gas chromatography–Mass Spectrometry (GC‐MS) revealed that degradation of the polymeric matrix resulted in the formation of hydrocarbons and oxygen‐containing compounds such as alcohols, carboxylic acids, aldehydes, and esters. The transformation products of the antioxidants formed as result of processing or exposure to the tested media were also identified. The transformation of the phenoxy radical of the Irganox 1010 produced the ester, acid, dealkylated cinnamate, and quinone products, whereas Irgafos 168 yielded oxidation products and the phenolic hydrolysis byproduct 2,4‐di‐tert‐butylphenol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 974–988, 2002     

复合型防老剂在低顺式聚丁二烯橡胶中的应用

以防老剂１０１０，防老剂１０７６，防老剂２６４，防老剂１６８和防老剂ＴＮＰ为基础，研究了二元，三元和四元复合型防老剂对低顺式聚丁二烯橡胶的防化作用，结果表明：复合型防老剂抗热，氧老化性能和抗热机械剪切性能均优于单一型防老剂，受阻酚类与亚磷酸酯类二元复合型防老综合性能最佳。     

Electron‐beam irradiation of low‐density polyethylene in the presence of phenolic stabilizer,carboxylic acid stabilizer,or both

The effects of Irganox 1010 and citric acid as antioxidants and modifiers of the network structure and mechanical and thermal properties of low‐density polyethylene (LDPE) during electron‐beam crosslinking with different irradiation doses (up to 120 kGy) were investigated. The results showed that the addition of these stabilizers had a retarding effect on the gel fraction of LDPE within the investigated range of electron‐beam‐irradiation doses. However, a noticeable effect on the gel fraction was found for the LDPE formulations compounded with citric acid alone or with its mixture with Irganox 1010 (in an equal ratio), as illustrated by a study of the gel‐fraction/dose relationships. Tensile testing measurements showed that the addition of both stabilizers caused a slight reduction in the stress at break and an increase in the strain at break. On the other hand, the thermal properties of the LDPE batches crosslinked with electron‐beam irradiation were greatly improved as a result of the compounding with these stabilizers, as shown by thermogravimetric analysis studies. In this respect, the temperatures at different weight losses, the temperatures of the maximum rate of thermal decomposition, and the activation energies indicated that compounding with citric acid was more effective for stabilization against thermal decomposition than compounding with Irganox alone or a mixture. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1275–1286, 2005     

Synthesis and performance of phenolic polybutadiene‐bound stabilizers

An antioxidant derivative, 6‐sulfanylhexyl 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propanoate, was synthesized and examined. With a radical initiator, the addition of this compound to pending vinyls of OH‐telechelic, low molecular weight liquid polybutadiene (LBH) was performed to various degrees of conversion to form polymeric antioxidants (PAOs) in which the phenolic moiety was separated from the main chain by a spacer [? CH₂CH₂? S? (CH₂)₆? O? CO? ]. Pure, unstabilized LBH was mixed in several ratios with PAOs, Irganox 1520, and Irganox 1076, and the oxidation stabilities of these mixtures, determined by thermogravimetric analysis and differential scanning calorimetry, were compared. Probably because of their good compatibility with LBH, PAOs exhibited equal or better effectiveness than commercial antioxidants of the Irganox type. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 885–889, 2003     

新型三元复配抗氧体系的设计及其在煤基均聚PP中的应用

设计了一系列由主抗氧剂、辅助抗氧剂、碳自由基捕捉剂组成的不同种类、不同配比抗氧剂体系,并将其用于煤基均聚聚丙烯（PP）的抗热氧老化性能改性中。其中以巴斯夫抗氧剂 Irganox®1010、Irgafos®168主辅抗氧剂质量比1∶1为对比基准,通过测试并对比添加新型三元复配抗氧体系改性 PP的氧化诱导时间（OIT）、黄色指数、熔体流动速率、力学性能等性能指标,从而开发煤基均聚PP的最佳耐热氧老化助剂配方。结果表明,当主抗氧剂为Irganox®1010、辅抗氧剂为 Irgafos®168质量比为 1∶1并与羟胺类抗氧剂 Revonox®420复合使用时,改性 PP的 OIT最长为 9. 8 min,黄色指数为 1. 3,熔体流动速率为 10. 7 g/10 min,综合性能最佳;当主抗氧剂为 Irganox®1010、辅抗氧剂为 Irgafos®168质量比为1∶2时,改性PP的抗黄变效果最好,由此设计并优化的抗氧剂体系及其配比对煤基均聚PP的耐长期热氧老化 改性配方设计具有重要的启示。     

Influence of the chemical structure of para-bridged group on the antioxidant behavior of hindered phenol antioxidants in HDPE resin

A hindered phenol antioxidant with rigid para-bridged group (antioxidant AP) was synthesized to study the effect of the chemical structure on the antioxidant properties of hindered phenol antioxidants in high density polyethylene (HDPE). Antioxidant behavior of series of hindered phenol antioxidants with different para-bridged groups in HDPE resin was also investigated by the thermal oxidation experiment, the mobility test, and the long-term accelerated thermal aging test. The results showed that the rigidity of para-bridged group and the molecule size have the important influences on the antioxidant performance of hindered phenol antioxidants in the HDPE resin, and the antioxidant abilities of antioxidant AP and Irganox 1,330 with the aryl para-bridged group was superior to Irganox 1,098 and 1.0G dendritic antioxidant with the alkyl para-bridged group at the same testing conditions. Compared with the hindered phenol antioxidants with alkyl para-bridged group, the hindered phenol antioxidants with aryl para-bridged group have better thermal oxygen stability and less mobility in the HDPE resin. Irganox 1,010 with ester groups is prone to hydrolysis to increase the mobility rate in hot water and the migration resistance of hindered phenol antioxidants in n-hexane. Moreover, the high content of phenolic OH group and the aryl para-bridged group are favorable for improving the antioxidant performance of hindered phenol antioxidants.     

高全同聚丁烯-1的防老化研究

研究了抗氧剂1010和辅助抗氧剂DLTP对高全同聚丁烯-1的防护效果。加工热稳定性测试试验表明:1010的最佳组分是0.3份;DLTP的加入能大幅度提高防护效果。长效热稳定性试验表明:防护效果随1010的加入量的增加而提高,当1010超过0.1份后防护效果趋于稳定;DLTP的加入能够提高热氧稳定性。     

Improving thermo‐oxidative degradation resistance of bamboo fiber reinforced polypropylene composite with antioxidants. Part I: Screening of antioxidants

In this study, the effect of antioxidant application (applied in different combinations, ratios and contents) on the thermo‐oxidative degradation resistance of bamboo fiber polypropylene composites (BFPCs) were investigated, with oxidative induction time (OIT), weight loss, surface color, and flexural mechanical properties as the main indicators for evaluation. The results showed the addition of antioxidants could greatly increase the OIT and reduce the weight loss and color change of the composites after 900 h of thermal weathering. Meanwhile, the flexural mechanical properties were little affected or even slightly improved. The combination of 1076 and DLTP antioxidants at a ratio of 2:1 and 0.2 wt % content was found to exhibit the best thermal oxidation resistance with respect to the OIT, mechanical properties and cost. Our study indicate that the OIT can serve as a simple and quick indicator for the evaluation of thermo‐oxidative resistance of BFPC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44198.     

新型功能复合型抗氧剂的合成及性能研究

以4-羟基苯乙酰胺和六氯环三磷腈为原料合成六（4-氨基苯氧基)环三膦腈;再通过β（3,5-二叔丁基4羟基苯基）丙酰氯与六（4-氨基苯氧基)环三膦腈的酰胺化缩合反应,最终合成了一种具有膦腈环结构和6个受阻酚单元的新型功能复合型枝化大分子抗氧剂六［β-（3,5-二叔丁基-4-羟基苯基）丙酰胺苯基］环三膦腈（HACP）。通过红外吸收光谱与核磁共振谱图对HACP的结构进行了表征。以HACP或抗氧剂1010为抗氧组分成功制备聚丙烯（PP）树脂共混物,并对共混物进行了热稳定性、耐老化性能的研究。结果表明,热失重过程中PP/HACP的失重5 %时的温度（T5 %）最高,为391.9 ℃(空气气氛)和410.0 ℃(N2气氛);同时,纯PP在老化7 d后失去力学性能,而PP/HACP或PP/抗氧剂1010,即使在老化14 d后依旧保持一定的力学性能,其中PP/HACP的拉伸强度由38.8 MPa下降到34.1 MPa,衰减率为11.6 %;PP/抗氧剂1010则以25.1 %的衰减率由38.7 MPa下降到29.0 MPa。     

抗氧剂在UHMWPE溶解过程中的作用

采用相对分子质量比较了抗氧剂1010和Ciba Irganox B 225混合抗氧剂在超高相对分子质量聚乙烯(UHMWPE)溶解过程中的抗降解作用。结果表明:在UHMWPE溶解过程中,随着温度的升高,加热时间的增长,UHMWPE的相对分子质量有明显的下降;而抗氧剂能有效抑制UHMWPE的降解,其用量增加,抑制 UHMWPE降解的作用也随之增大;当加热110 min,温度升至180℃时,加入质量分数为2％的混合抗氧剂, UHMWPE的相对分子质量下降33．9％,而未加混合抗氧剂时,UHMWPE的相对分子质量下降70．2％。相同用量时,混合抗氧剂效果比抗氧剂1010好。