Preparation and Characterization of Partially Degraded High-Density Polyethylene in an Internal Mixer

The partial degradation of high-density polyethylene was done in an internal mixer for different residence time. The oxidative thermomechanical degradation resulted in the formation of carbonyl groups in the polymer. The carbonyl index values estimated from the FTIR studies indicate the increase of carbonyl groups without any induction time. The common phenomenon during oxidative degradation of polyethylene is the increase in trans-vinylene groups and decrease in vinyl groups and these phenomena are observed in the current investigation. Owing to the chain scission occurring during the mixing at processing temperature, the change in morphology was studied by the amount of crystallinity estimated through DSC. The variation in the molar mass of the material was followed by SEC method.     

添加剂对橡胶籽油生物柴油氧化稳定性的改进

测定了橡胶籽油的物化性能及组成. 加入6种抗氧化剂,采用Rancimat法研究了其添加量及复配、温度、0#柴油添加量、金属铜、铁等对橡胶籽油生物柴油氧化稳定性能的影响. 结果表明,橡胶籽油所制生物柴油不饱和脂肪酸含量达82.1%,诱导期为0.81 h,达不到国家标准(6 h). 6种抗氧化剂在添加量为4000′10-6(w)时对橡胶籽油生物柴油的氧化稳定性能均有提升,其中TBHQ效果最好,使其氧化稳定性诱导期达13.09 h,6种抗氧化剂的抗氧化效果为TBHQ>BHT>D-TBHQ>OG>PG>BHA. PG与其他抗氧化剂复配后效果较好,而TBHQ与其他抗氧化剂复配后效果降低. 温度和0#轻柴油添加量对橡胶籽油生物柴油的氧化稳定性能影响很大,随温度升高,诱导期明显缩短,而随0#柴油添加量增大,诱导期增加,添加量较大时诱导期增幅很大. 铁、铜对其氧化稳定性能也有一定影响.     

Efficiency of antioxidants in thick-walled natural rubber samples evaluated by differential scanning calorimetry and compression stress–relaxation

The effect ot two antioxidants, IPPD and DENA, on the aging properties of TMTD-vulcanized natural rubber was studied by DSC. In the case of IPPD, the results were compared with mechanical measurements. The DSC measurements were carried out on specimens taken at different depths from cylindrical samples. The decrease in oxidative induction time was less pronounced for IPPD than for DENA at the edge of the samples. In the interior, the opposite behaviour was observed.     

Coupled analysis on heterogeneous oxidative aging and viscoelastic performance of rubber based on multi-scale simulation

An oxidative aging-viscoelastic constitutive model was established to study the coupled heterogeneous oxidation and viscoelastic performance of rubber during aging process. The basic elasticity and viscoelasticity of rubber materials were comparatively considered as the function of ongoing aging. The dynamic compression process of natural rubber at different aging times was analyzed by the finite element method. And then the effects of oxygen uptake, diffusion, and oxidative reactions on the dynamic viscoelasticity of rubber were analyzed. The permeability of the oxygen in natural rubber was determined by means of molecular dynamics simulation. The results reveal that the heterogeneous degradation caused by diffusion-limited oxidation can lead to a complex stress distribution in the natural rubber specimen under dynamic loading condition; the relaxation time and the energy dissipation of the rubber specimen also increased after aging. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47452     

Organotellurium compounds as stabilizers for polymeric materials

The thermal stability of a series of organotellurium compounds was determined by thermogravimetric analysis and the stabilizing capacity of the most heat-resistant compounds assessed in natural rubber, polyethylene, and polypropylene by measurement of the oxidative induction time (OIT). The most active compounds, bis[4-(dimethylamino)phenyl]telluride ( 5 ) and bis[2,6-dimethyl-4-(dimethylamino)phenyl]telluride ( 10 ) stabilized natural rubber considerably at the 1% level and even more so at the 2% level. A similar stabilizing effect of compound 5 was found in polyethylene and polypropylene at the 0.1% level. © 1996 John Wiley & Sons, Inc.     

Einfluß von Licht und Tocopherolgehalt auf die Oxidationsstabilität von Fettsäuremethylestern

Influence of light and contents of tocopherols on the oxidative stability of fatty acid methyl esters The oxidative stability of different plant oil based fatty acid methyl esters can be estimated by determining the induction period with the active oxygen method. Measuring the volatile and oil soluble acids for a long period preceding the induction period shows that the values are approaching a certain limit. Even if the esters do not differ dramatically in the composition of fatty acids it is a fact that the different production processes influence the amount of tocopherols significantly. The exclusion of light is more crucial than the exclusion of air when storing plant oil based fatty acid esters.     

氧化降解天然胶乳制备液体天然橡胶的研究

使用正交试验和单因素试验研究了氧化降解法制备液体天然橡胶时的工艺条件。结果表明,影响降解胶乳相对分子质量的因子主次顺序为反应时间、温度、丙醛用量和引发剂用量。最佳降解条件为引发剂,2份;丙醛,30份;反应条件80℃×24h,得到Mn为1.2×104。随引发剂用量的增加,降解胶乳相对分子质量先下降后上升;随丙醛用量的增加或温度的升高或反应时间的延长,降解胶乳相对分子质量都下降。     

硅烷偶联剂在粘土胶中的抗热氧老化作用

本文主要讨论了硅烷偶联剂的抗热氧老化作用通过采用天然橡胶塑性保护率的测定方法、橡胶热空气老化试验方法、扫描电子显微镜分析等，对硅烷偶联剂对粘土胶性能的影响进行了探讨，研究结果表明硅烷偶联剂不仅可以大大提高材料的强度，而且有明显的抗热氧老化效果。     

Effect of non‐rubber substances on vulcanization kinetics of natural rubber

Effect of non‐rubber components on vulcanization kinetics of natural rubber was studied with the use of a Rheometer MDR‐2000. The results show that the rate constants of induction period and curing period of natural rubber (NR) are greater than that of natural rubber extracted with acetone (NR_E), and the activation energies of induction period and curing period of NR are lower than that of NR_E. The activation energy of induction period of NR is reduced by16.9% and the activation energy of curing period of NR is reduced by 3.2% compared to the activation energies of NR_E. The time t_dis of NR is shorter than that of NR_E at the same temperature. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermo-oxidative degradation of polyolefins observed by isothermal long-term DTA

Isothermal differential thermal analysis (DTA) is well known for measuring thermal stability of polyolefins by determining the oxidative induction time at elevated temperatures. Oxidative induction time, measured up to 7,000 hours and over a temperature range from 240°C to 120°C, has been used to study the stability of polybutene-1 and crosslinked polyethylene in the melt state. The Arrhenius plots of DTA results show that straight line extrapolation from high to low temperatures is not possible. Thermoanalytically measured oxidation induction times and mechanical failure in oven aging experiments agree for polybutene and crosslinked polyethylene, Measurements of molecular weight and of mechanical properties of polybutene-1 during the induction period of oven aging experiments at low temperatures revealed that molecular weight and tensile properties are not sensitive indicators for the beginning of aging. The state of deterioration can be estimated easier by measurement of residual lifetime in the isothermal DTA experiment. Diffusion processes of stabilizers in polyolefins, as well as the consumption of stabilizer at elevated temperatures, especially during the induction period also was observed by DTA. Finally the extraction of stabilizer by hot water was measured by isothermal DTA.     

Estimation of the shear deformation exerted by a roll-mill upon a rubber compound

The shear deformation which a rubber compound undergoes when passing through a mill nip was calculated. For this purpose the pressure distribution was measured using a strain gauge mounted in the table of a RAPRA micro-mill. The method has been applied to black-loaded master batches of natural rubber and styrene-butadiene rubber, where the shear deformation was estimated as a function of the mill nip opening. Furthermore, the physical properties of a latex-mixed powder vulcanizate was measured as a function of the estimated shear deformation.     

Effects of different drying methods on the microstructure and thermal oxidative aging resistance of natural rubber

In this work, the wet natural rubber granules were dried by hot air and by microwave at 115°C, respectively; the morphological structures of dried natural rubber granules were studied by using a scanning electronic microscope, whereas the thermal oxidative properties of dried natural rubber granules were investigated by comparison of variation in properties before and after aging, and the changes in the thermal oxidative decompose temperatures. The results showed that it needed 13.47 min for microwave drying and 210.00 min for hot air drying to reduce the moisture content of wet natural rubber to the required value. The granules of natural rubber dried by microwave were of rough surfaces and the cutting traces produced during the processing of wet natural rubber remained on the natural rubber surface; whereas, the natural rubber granules dried by hot air were of smooth surfaces, and the cutting traces produced during the processing of wet granules disappeared. The thermal oxidative resistance of vulcanized natural rubber dried by microwave improved significantly. The initial plasticity (P₀), plasticity retention index, and thermo‐oxidative decomposition temperature of natural rubber dried by microwave were higher than those of natural rubber dried by hot air. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

有氧再生废轮胎橡胶粉的制备与表征

在管式炉中对废轮胎橡胶粉进行了有氧再生,并考察了气氛、再生温度和再生时间对废轮胎橡胶粉有氧再生过程的影响。结果表明,有氧条件下橡胶粉的质量损失和溶胶质量分数均随温度升高而增大,溶胶中合成胶分子链之间易发生二次重组再交联反应,天然橡胶分子链则主要发生断裂。240 ℃下橡胶粉在有氧条件下再生10 min时,溶胶质量分数达55.9%。橡胶主链和交联键断裂主要发生了氧化反应,生成含羰基和亚砜基的化合物,同时伴有水和二氧化碳等生成,说明橡胶粉中的橡胶分子链有效断链。     

不同喷雾干燥方式对粉末橡胶结构与性能的影响

采用热空气喷雾干燥和过热蒸汽喷雾干燥制备粉末橡胶,并研究其干燥胶粉的形态结构及性能。FT-IR表明,热空气喷雾干燥比过热蒸汽喷雾干燥更容易引入含氧基团,造成粉末橡胶氧化分解。SEM表明过热蒸汽喷雾干燥使物料干燥程度更高,有利于水分蒸发。GPC表明热空气喷雾干燥容易破坏橡胶分子链,降低橡胶分子量,过热蒸汽喷雾干燥更能保持橡胶原有分子链。     

酸凝固天然橡胶和微生物凝固天然橡胶硫化特性研究

采用硫化仪分析2种天然橡胶的硫化过程,探讨了炭黑和硫化温度对硫化诱导期、正硫化时间和最大转矩的影响。研究结果发现：微生物凝固胶和酸凝固胶的硫化诱导期和正硫化时间随硫化温度的上升显著下降,且都能很好符合阿仑尼乌斯方程;胶样的最大转矩与硫化温度呈很好的线性关系,且随着硫化温度的升高,逐渐降低;当采用纯胶配方时,微生物凝固胶的MH0显著高于酸凝固胶,而加入炭黑后．2种胶样的MH0均显著提高。但微生物凝固胶的MH0稍低于酸凝固胶。     

Effect of oven aging on polypropylene

Injection-molded tensile bars of unstabilized polypropylene were oven aged at 90°C. After an induction period, tensile elongation decreased catastrophically. During the induction period no evidence of oxidation was observed by infrared reflectance; however, a definite surface etching was noted by electron microscopy. Differential scanning calorimetry measurements indicated that, for samples aged beyond the induction time, oxidative degradation caused a decrease in the melting temperature of polypropylene. Toluene immersion was used to remove selectively material from the surface of tensile bars aged for various times. Using this technique, changes in melting behavior were observed for partially aged polypropylene even prior to the catastrophic decrease in tensile elongation. Similarly, oxidation products and a reduction in molecular weight were detected for the dissolved surface layer during the apparent induction time. Results indicate that molecular weight measurement is the most sensitive indicator of oxidative degradation during the induction period.     

天然橡胶的热氧老化研究

为了改善天然橡胶的热氧老化性能，试验了防老剂D提纯品和工业品对天然橡胶热氧老化性能的影响，调试了其热氧化诱导期、热失重、热老化的性能变化。结果表明：含杂少纯度高的防老剂D使天然橡胶的抗热氧老化得到改善。     

天然橡胶光/热氧老化及抗老化性能研究进展

对天然橡胶的老化失效行为，特别是光/热氧老化机理进行了总结，同时综述了自然老化和人工加速老化等常见老化方法及天然橡胶的防老化技术，并展望了天然橡胶防老化技术未来的发展趋势。     

Studies on thermal–oxidative degradation behaviours of raw natural rubber: PRI and thermogravimetry analysis

Abstract

Thermal–oxidative degradation behaviours of raw natural rubber (NR) have been investigated by using thermogravimetry analysis in inert and oxidative atmospheres and the plasticity retention index (PRI). The activation energy E_a, was calculated using Horowitz–Metzger and Coats–Redfern methods and compared with PRI. The E_a values obtained by each method were in good agreement with each other. The June samples are the least stable rubbers among the studied ones, whereas February samples exhibited the highest values of activation energy, therefore in agreement with the PRI behaviour, which indicates that the thermo-oxidative stability of the June samples are the poorest during the thermo-oxidative degradation reaction. Natural rubber is a product of biological origin, and thus these variations in the values of thermal behaviour and PRI might be related to the genetic differences and alterations of climatic conditions that act directly on the synthesis of non-rubber constituents, which are generally reflected in latex and rubber properties.     

De-link处理时间对废胶粉制备热固性塑料结构与性能的影响

利用废胶粉制备出一种高强度、高模量热固性塑料。ESEM观察发现，热固性塑料基体中残存有少量胶粉颗粒，且胶粉颗粒与基体界面处存在硫黄的梯度分布。材料力学性能与硬质橡胶近似并具有较好的缺口冲击强度。还考察了De—link处理时间对材料微观结构和力学性能的影响。研究表明，随着De—link处理时间的延长，初始废胶粉的交联密度下降，基体中残存的胶粉颗粒明显减少，材料拉伸强度和模量呈上升趋势，而缺口冲击强度降低并趋于稳定。