三种组成不同多支链酚类抗氧剂的合成和评价

合成了抗氧剂改性第二代、第三代和第四代Boltron。3-（3，5-二叔丁基-4-羟基苯基）丙酸是连接到三种不同多支链聚酯的活性基团。合成成功地实现了高度取代。抗氧剂使用示差扫描量热法（DSC）测定在角鲨烷中和在聚丙烯（PP）软片中的氧化诱导时间（OIT）来评价。它们和按0．1％（重量）加入的工业用抗氧剂Irganox 1010相比较，所有合成的抗氧剂在角鲨烷中均比Irganox 1010好，不过对PP稳定性所起的作用则不太大。由于低流动性和低溶解性所导致的多支链抗氧剂在PP中的低抗氧性能可以得出上述结论。     

红外光谱在抗氧剂1010晶型判定中的应用

分别采用熔点法、粉末X射线衍射法和红外光谱法对α,β和δ三种晶型的抗氧剂1010进行了晶型判定。结果表明,3种晶型抗氧剂1010的红外光谱分别在1500～500cm^-1指纹区内有与之对应的特征吸收峰,可用于抗氧剂1010的晶型判定。用红外光谱法进行抗氧剂1010的晶型判定快捷、准确。     

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。     

星形受阻酚抗氧剂的抗氧化性能研究

利用星型聚合物的端基可以进行功能基转化这一特殊性能,将具有抗氧化性能的化合物β-（3,5-二叔丁基-4-羟基苯基）丙酰氯引入到以氨为核的低代聚酰胺-胺（PAMAM）星型高分子上,合成了一种星型受阻酚抗氧剂,研究了该星型抗氧剂对线形低密度聚乙烯（PE-LLD）和聚丙烯（PP）的抗氧化作用。结果表明,该抗氧剂在2种聚烯烃材料中均具有良好的加工性能和抗氧化性能,在PE-LLD 中的氧化诱导期为市售抗氧剂1010的1.3倍、抗氧剂3114的1.4倍,在PP中的抗氧化性能与这2种抗氧剂相当;添加该星型抗氧剂可使PE-LLD的拉伸强度和断裂伸长率分别从12.6 MPa和652 %升高到17.9 MPa和696 %,使PP的拉伸强度和断裂伸长率分别从36.9 MPa和182 %升高到40.0 MPa和248 %;经25 min塑炼后,添加该星型抗氧剂的PE-LLD和PP的熔体流动速率变化很小。     

抗氧剂1010在低碳醇中溶解度与活度系数模型

抗氧剂1010是一种高分子量的受阻酚类抗氧剂,广泛用于塑料、橡胶、合成纤维和弹性体中.抗氧剂1010的粒度、堆密度及晶型等特性与结晶溶剂和工艺密切相关.采用静态平衡法测定了抗氧剂1010分别在甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇和仲丁醇溶剂中的溶解度数据,为结晶工艺研究和工业生产提供必要的基础数据.考虑到抗氧剂1010分子较大的特点,引入了自由体积活度系数项,并将看作一个参数KFV,得到了适合所研究物系的UNIFAC-KFV方程.采用UNIFAC和UNIFAC-KFV方程对研究物系进行计算,UNIFAC-KFV计算结果与实验数据符合较好,结果表明,文中提出的模型是成功的.     

抗氧剂对PMMA树脂的热稳定作用

采用连续本体法合成了纯聚甲基丙烯酸甲酯（PMMA）树脂,将不同种类的抗氧剂与PMMA树脂进行熔融共混,在空气气氛中采用热失重法测试了PMMA树脂的热稳定性。考察了抗氧剂种类、用量及复配比例等因素对PMMA树脂热稳定性的影响。实验结果表明,分别加入抗氧剂1076、抗氧剂2246、抗氧剂245和抗氧剂1010等主抗氧剂可以显著提高PMMA树脂的热稳定性,辅助抗氧剂（抗氧剂168）可以提高PMMA树脂的起始热分解温度,改变抗氧剂1010与抗氧剂168的复配比例时,抗氧剂1010用量越多,PMMA树脂的热稳定性越好。抗氧剂总量为2.5 ‰（质量分数,下同）,抗氧剂1010与抗氧剂168的比例为3：1时,PMMA树脂的热稳定性显著提高。     

高效多功能抗氧剂300

抗氧剂300又称防老剂300,化学名称4,4’-硫代双（3-甲基-6-叔丁基苯酚）,是一种高效多功能受阻酚类抗氧剂,具有终止游离基和分解氢过氧化物的双重作用,即具有主辅抗氧剂的双重功效。因此,可以单独使用,而其他抗氧剂,如1010、1076、264等仅有游离基终止作用,不能分解氢过氧化物,单独使用时效果不佳,需要配合辅助抗氧剂,如DLTP、DSTP、DNP、168等。抗氧剂300为白色或淡黄色粉末,密度（p25）1．06～1．12．熔点155～162℃。溶于乙醇、丙酮、甲苯等,微溶于溶剂汽油,不溶于水。     

抗氧剂对聚乙烯光降解膜结构及性能的影响

采用紫外光加速老化的方法研究了抗氧剂1010对聚乙烯(PE)光降解膜的影响,并通过红外光谱、紫外光谱分析和拉伸性能测试对老化前后的薄膜的结构和性能进行了研究。结果表明,抗氧剂1010能抑制PE的光氧化降解,且导致薄膜光降解过程中羰基化合物的生成量和类型减少;添加抗氧剂1010的光降解薄膜降解的诱导期延长,PE光降解膜紫外照射3 d后其断裂伸长保留率小于80 %,而添加0.3 %（质量分数,下同）抗氧剂1010的PE光降解膜照射4~5 d后其断裂伸长保留率小于80 %。     

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。     

高效液相色谱法测定复配添加剂中抗氧剂1010、1076和168的含量

采用Eclipse XDB-C_(18)色谱柱建立了复配添加剂中抗氧剂1010、1076和168含量的测定方法。抗氧剂的含量与其峰面积均呈现了良好的线性关系,相关系数r均大于0.9999。样品中抗氧剂1010、1076和168的平均回收率(n=9)分别为100.98%(RSD=0.85%)、99.34%(RSD=1.16%)、98.55%(RSD=1.24%)。该方法具有快速、准确、灵敏度高及方法稳定的特点,适用于复配添加剂中抗氧剂1010、1076、168含量的测定。     

A rapid microwave‐assisted solvent extraction method for assessment of stabilizer concentration in crosslinked polydimethylsiloxane

Crosslinked polydimethylsiloxanes were prepared containing 0.05 to 0.2 wt % of either a phenolic antioxidant (Irganox® 1010) or a hindered amine stabilizer (Tinuvin® 144). The stabilizer concentration was assessed by HPLC and UV‐Vis spectroscopy of Soxhlet and microwave‐assisted solvent extracts. Almost complete recovery of stabilizer was achieved with Soxhlet extraction. High stabilizer recovery was achieved when acetone was used as the solvent in the microwave‐assisted extraction. HPLC was shown to be an efficient method for determining the concentration of Irganox 1010. For Tinuvin 144 the selectivity of both UV‐Vis spectroscopy and HPLC was poor, leading to imprecise evaluation of the antioxidant concentration. The loss of stabilizer by migration from polymer to hot water (75 and 95°C) was monitored for the systems stabilized with Irganox 1010 and the diffusion coefficient of the antioxidant in the polymer was determined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2185–2192, 2004     

Investigating effect of ferric stearate on stabilization efficiency of a phenolic antioxidant during thermal oxidation of polyethylene

This study aimed to achieve a formulation for an additive to produce oxo-biodegradable films that accelerates oxidative degradation of the films after preservation of properties over a span of desired service life. Thermal oxidation behavior of high-density polyethylene (HDPE) films (approximately 250 μm thick) containing various weight ratios of a commercially used phenolic antioxidant (Irganox 1010) to ferric stearate as pro-oxidant has been studied in both melt and solid states. Thermo-oxidative stability in melt state was studied using differential scanning calorimetry. The rate of thermal oxidation in solid state was investigated via oven aging experiments at 90 °C followed by measuring changes in tensile properties, gel content, carbonyl index and density. Comparing thermo-oxidative stability of the HDPE samples containing a combination of Irganox 1010 and ferric stearate with the samples containing Irganox 1010 alone confirmed that ferric stearate reduces the stabilization efficiency of the phenolic antioxidant in the polymer either in melt or in solid state. It was also shown that the efficiency of the phenolic antioxidant in thermo-oxidative stabilization of the polymer in both melt and solid states could be changed by altering weight ratio of Irganox 1010/ferric stearate. On the basis of the obtained results, it was concluded that weight ratio of 0.1/0.1 wt% of the antioxidant to the pro-oxidant is suitable for attaining desired stability during melt processing as well as retaining properties during a reasonable service life when is used as a film and a favorable rate of thermal oxidation after the service life.     

Water extraction and degradation of a sterically hindered phenolic antioxidant in polypropylene films

Water extraction of the sterically hindered phenolic antioxidant Irganox 1010 from three polypropylene based polymeric films has been studied in isothermal conditions at 40, 50 and 70 °C. The films made of isotactic polypropylene and two different heterophasic polypropylene/ethylene–propylene monomers copolymers (PP/EPM copolymers) were immersed in closed water baths under nitrogen atmosphere in order to minimise the oxidative process. The amounts of antioxidant that have left the films and are dissolved in the water bath have been monitored over time by HPLC analysis and faster extraction kinetics were observed from the polymers than from the homopolymer. No appreciable amounts of Irganox 1010 were found in the extraction water at any time, whereas its degradation by-products were found by LC/MS analysis in the extraction water.

The experimental extraction kinetics from the three polymers were compared with the theoretical curves based on the Fick's diffusion equations solved both for a semi-infinite (degradation reaction faster than extraction) and a finite system (no degradation reaction) and Irganox 1010 was demonstrated to be extracted by water from polypropylene based material faster than predictable only on the basis of the values of its coefficient of diffusion in the polymers and of partition between water and polymer.     

Influence of binary combined systems of antioxidants on the stabilization of peroxide‐cured low‐density polyethylene

The secondary antioxidants Irganox 168 and 242 and dilaurylthiodipropionate (didodecyl‐3,3′‐thiodipropionate) (DLTP) were chosen to be combined with the primary phenol antioxidants Irganox 300, 1010, 1035, and 1076, and the effects of the binary combined systems of antioxidants on the peroxide curing reaction and the long‐term stability of crosslinked low‐density polyethylene (XLPE) were studied through isothermal dynamic rheological and mechanical testing. The results show that the primary phenol antioxidants with lower melting points had better resistance to scorching and exhibited good synergistic effects with the secondary antioxidants. Irganox 168 had little resistance to scorching, whereas Irganox DLTP had moderate resistance, and Irganox 242 had the greatest resistance. Irganox 168 and DLTP guaranteed the mechanical properties well, whereas Irganox 242 reduced the tensile strength obviously. Irganox 300 and 1035 combined with secondary antioxidants performed poorly in long‐term thermal aging test, whereas Irganox 1076 in combination with secondary antioxidants displayed a moderate effect of aging resistance, and Irganox 1010 showed the best effect. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

复配型受阻酚类抗氧剂对聚甲醛的稳定作用

将受阻酚类抗氧剂Irganox245和Irganox1010进行复配并加入聚甲醛中，通过将物料在设定温度下多次挤出，测定挤出物料的黄色指数、拉伸强度、冲击强度、熔体质量流动速率、热失重率等方法对单剂和复配抗氧剂在聚甲醛中的稳定作用进行了研究。结果表明：将抗氧剂Irganox245和Irganox1010复配后，提高了聚甲醛的分解温度，较好地保持了聚甲醛的各项性能，没有发生劣化现象，作用效果介于两种抗氧剂单独作用效果之间；在聚甲醛的热氧稳定性能方面起到一定的协同作用。     

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。     

Thermo-Oxidation of Polyethylene Stabilized with Irganox 1010 and Tinuvin 622

Abstract

Thermal oxidation of polyethylene stabilized with the mixture of Irganox 1010 and sterically hindered amine Tinuvin 622 confirmed that the occurrence of synergism or antagonism in the effect of sterically hindered amines towards antioxidants is concentration dependent. Provided that the concentration of phenolic antioxidant Irganox 1010 in polytheylene exceeds that of Tinuvin 622, synergism is observed at 185 and 190°C. Chemiluminescence, oxygen absorption method, nonisothermal differential scanning calorimetry (DSC) and differential thermal analysis (DTA) were used for testing of stabilizing efficiency of mixtures of stabilizers and the mutual correspondence of the results have been pointed out.     

Natural compounds from Punica granatum peel as multiple stabilizers for polyethylene

Punica granatum peel extractive (PPE), a novel stabilizer of polyethylene, is investigated in this study. Oxidation onset temperature (OOT), carbonyl index (CI), melt flow rate (MFR), tensile strength, and elongation at break are used to characterize the effects of PPE, which are also compared with commercial antioxidant (Irganox 1010) with the presence of tetrakis (2,4-di-tert-butylphenol)[1,1-biphenyl]-4,4′-diylbisphosphite (PEPQ). Long-term and short-term aging results show that samples modified by PPE or Irganox 1010 (PE-PPE_0.12%-P and PE-1010_0.12%-P samples) have comparable CI value and stability of OOT. However, compared with PE-PPE_0.12%-P sample, much higher CI and larger change of MFR is detected for PE-1010_0.12%-P after UV irradiation and five extrusions. It suggests that PPE is better protector for PE against UV light and mechanical shear force. All results indicate that the effect of PPE in protecting PE is comparable or much better than Irganox 1010 and it can be used as multiple stabilizers for PE. Moreover, the stabilities of PE modified with PPE alone (PE-PPE_2%) is also investigated. Results show that PE-PPE_2% sample has good thermo-oxidative, UV and processing stabilities. All results reveal that PPE is a good candidate of PE stabilizer and it could avoid the usage of PEPQ in protecting PE.     

耐候性聚氨酯用稳定剂

介绍了聚氨酯的稳定化机理，综述了用于聚氨酯的紫外线吸收剂、抗氧剂、光稳定剂的一些品种。讨论了紫外线吸收剂(UV-571、UV-328)、抗氧剂(Irganox 1010、Irganox 1135、Irganox3125)，受阻胺(HALS)(UV-770、UV-765)等稳定剂对聚氨酯光氧老化的影响，结果表明，同时使用上述3类稳定剂可得到较好的效果。     

The effect of carbon black on the oxidative induction time of medium-density polyethylene

An extensive series of: (i) oxidative induction time (OIT) measurements derived from differential scanning calorimetry experiments, and (ii) stabilizer analyses by high performance liquid chromatography were conducted on medium-density polyethylene (MDPE) stabilized with various levels of Irganox 1010 (penta-erythrityl-tetrakis-(3,5-di-tert-butyl-4-hydroxyphenyl propionate), Irgafos 168 (tris-(2,4-di-tert-butyl-phenyl)-phosphite), and carbon black (CB). The OIT data were analyzed using a novel interpretation method, which is described and applied. It was found that: (i) addition of CB to base-stabilized MDPE increases stability and reduces OIT variability; (ii) the optimum effective concentrations of Irganox 1010, Irgafos 168 and CB are 1690 ppm, 1580 ppm and 2.5% w/w, respectively; and (iii) interactions between CB and the base co-stabilizers may occur at high loadings of the latter but CB does not affect the extraction of the base co-stabilizers which are extracted with efficiencies of ca. 80% and 100% for Irganox 1010 and Irgafos 168, respectively.