The service life of a polyolefin product depends to large extent on the type and amount of the antioxidants added. During the manufacturing,storage and use of the product the antioxidants are depleted by physical proc...The service life of a polyolefin product depends to large extent on the type and amount of the antioxidants added. During the manufacturing,storage and use of the product the antioxidants are depleted by physical processes and chemical degradation,and this impairs its long-term performance.The initial and in-use oxidation stability is often characterized and monitored by the measurement of the oxidative induction time(OIT),and service life predictions are based on the rate of decrease of the OIT value.To study the correlation between the OIT value and the actual antioxidant concentration,eight random arrays of high-impact polypropylene(PP)strands stabilized using six different antioxidant packages(composed of Irgafos 168,Irganox 1010 and 1330,Chimassorb 944)were immersed in hot water(80℃and 90℃)and oven aged in air (80℃)for more than two years,and the change of OIT values and antioxidant concentrations was measured.For phosphitic and phenolic stabilizers water immersion is generally a more critical aging condition than oven aging in air,while for the hindered amine stabilizers(HAS)the opposite was observed.As expected,a linear correlation between OIT values and concentrations was found for the'classical'package of phosphitic and phenolic stabilizers.In the case of Irganox 1330,the change of the OIT values during aging was considerably slower than the change of concentration.Even when zero concentration was reached according to the vanishing peak height in the chromatogram,a considerable OIT value was still measurable.This may be due to unidentified degradation products of Irganox 1330 which still act as antioxidants in the long run.Addition of HAS(Chimassorb 944)seems to enhance the initial OIT of stabilized phenolic samples and the long-term effectiveness of the phenolic stabilization under air oven aging conditions.However,the marked long-term effectiveness of the HAS itself and the slow change with time of the concentration were not detectable by OIT measurements above the PP melting point of about 170℃.展开更多
为了考察油酸甲酯的氧化衰变特性,采用自制氧化模拟装置将样品加速氧化,定时取样检测样品过氧化值、酸值和运动黏度(40℃),考察不同温度和氧气流量对氧化速率的影响;利用傅立叶红外光谱定性表征油酸甲酯氧化前后的结构变化;通过Rancima...为了考察油酸甲酯的氧化衰变特性,采用自制氧化模拟装置将样品加速氧化,定时取样检测样品过氧化值、酸值和运动黏度(40℃),考察不同温度和氧气流量对氧化速率的影响;利用傅立叶红外光谱定性表征油酸甲酯氧化前后的结构变化;通过Rancimat法加速氧化试验,测定油酸甲酯的氧化诱导期,同时从氧化反应活化能角度进一步研究油酸甲酯的氧化反应机制。结果表明,氧气流量对油酸甲酯热氧化稳定性影响较小,但随着反应温度的升高,氧化诱导期缩短,氧化安定性显著下降;傅立叶红外光谱定性表征结果表明,油酸甲酯在氧化过程中可能发生不饱和双键的异构化;通过计算得到油酸甲酯的氧化反应表观活化能为34.058 k J/mol。展开更多
文摘The service life of a polyolefin product depends to large extent on the type and amount of the antioxidants added. During the manufacturing,storage and use of the product the antioxidants are depleted by physical processes and chemical degradation,and this impairs its long-term performance.The initial and in-use oxidation stability is often characterized and monitored by the measurement of the oxidative induction time(OIT),and service life predictions are based on the rate of decrease of the OIT value.To study the correlation between the OIT value and the actual antioxidant concentration,eight random arrays of high-impact polypropylene(PP)strands stabilized using six different antioxidant packages(composed of Irgafos 168,Irganox 1010 and 1330,Chimassorb 944)were immersed in hot water(80℃and 90℃)and oven aged in air (80℃)for more than two years,and the change of OIT values and antioxidant concentrations was measured.For phosphitic and phenolic stabilizers water immersion is generally a more critical aging condition than oven aging in air,while for the hindered amine stabilizers(HAS)the opposite was observed.As expected,a linear correlation between OIT values and concentrations was found for the'classical'package of phosphitic and phenolic stabilizers.In the case of Irganox 1330,the change of the OIT values during aging was considerably slower than the change of concentration.Even when zero concentration was reached according to the vanishing peak height in the chromatogram,a considerable OIT value was still measurable.This may be due to unidentified degradation products of Irganox 1330 which still act as antioxidants in the long run.Addition of HAS(Chimassorb 944)seems to enhance the initial OIT of stabilized phenolic samples and the long-term effectiveness of the phenolic stabilization under air oven aging conditions.However,the marked long-term effectiveness of the HAS itself and the slow change with time of the concentration were not detectable by OIT measurements above the PP melting point of about 170℃.
文摘为了考察油酸甲酯的氧化衰变特性,采用自制氧化模拟装置将样品加速氧化,定时取样检测样品过氧化值、酸值和运动黏度(40℃),考察不同温度和氧气流量对氧化速率的影响;利用傅立叶红外光谱定性表征油酸甲酯氧化前后的结构变化;通过Rancimat法加速氧化试验,测定油酸甲酯的氧化诱导期,同时从氧化反应活化能角度进一步研究油酸甲酯的氧化反应机制。结果表明,氧气流量对油酸甲酯热氧化稳定性影响较小,但随着反应温度的升高,氧化诱导期缩短,氧化安定性显著下降;傅立叶红外光谱定性表征结果表明,油酸甲酯在氧化过程中可能发生不饱和双键的异构化;通过计算得到油酸甲酯的氧化反应表观活化能为34.058 k J/mol。
