气氛对低氮天然橡胶热降解的影响

采用热重分析(TG),研究了恒定升温速率下,低蛋白橡胶在氮气和空气气氛中的热降解行为,考察了反应气氛对降解速率、降解率和动力学参数的影响,分析了两者降解机理的可能差别。发现降解温度和降解率,氮气中均高于空气中;表观反应级数氮气中为2.0级,空气中为1.9级。     

氯化天然橡胶的热降解研究

用傅立叶变换红外光谱法和热失重分析法研究了氯化天然橡胶(CNR)的热氧降解和热降解过程。结果表明,CNR的热降解为一步反应,在160～390 ℃时CNR 发生脱氯化氢反应,在390 ℃时CNR 仍有质量分数为0.35的残留物存在,而且较稳定。CNR的热氧降解为两步反应,在160～390 ℃时,产生氯化氢和二氧化碳;在390～575 ℃时分解产物为二氧化碳,且分解彻底。     

低蛋白天然橡胶的性能研究

分析了LPNR(低蛋白天然橡胶)和NR(天然橡胶)中的C、H、N和S元素的含量。结果表明，两者N元素的含量差异显著。而其它元素的含量差异不大；研究了LPNR和NR的弹性模量(G′)随频率变化和应变变化的响应曲线。结果表明，LPNR和NR的弹性模量随频率的增大而增大，随应变的增大而减小，在整个变化过程中LPNR的弹性模量比NR的弹性模量大；研究了LPNR和NR在N2中的热降解性能，发现LPNR的耐热性较NR的差。     

溴化天然橡胶的热降解研究

用傅立叶变换红外光谱法和热失重分析法研究了溴质量分数分别为31%、51%和69%的溴化天然橡胶（BNR）的热降解和热氧降解过程。结果表明,BNR热降解为两步反应,第1步BNR发生脱溴化氢反应,失重率近似等于其溴含量;第2步BNR31、BNR51和BNR69在475℃降解时仍有9.7%、15.6%和12.7%的残留物存在,且较稳定。BNR热氧降解分3步进行,第1步反应的温度及降解率与热降解相近,产物主要是溴化氢,此外还有少量二氧化碳;第2步和第3步产物为二氧化碳,且分解彻底。     

环氧化天然橡胶硫化胶在不同气氛下的热降解行为？

利用热重-微商热重（ TG-DTG-DSC）研究了在氮气、空气氛围中ENR硫化胶的热降解动力学,根据不同升温速率下得到的热重数据,通过Ozawa-Flynn-Wall模型求取热降解过程的活化能E、指前因子A等参数,得到ENR硫化胶在不同气氛下降解反应过程中动力学参数方面的差异。 ENR在氮气气氛中降解时为一步反应,在空气中为复杂多步反应。另外,空气气氛中的活化能E和指前因子A均大于氮气中。     

淀粉加速凝固天然橡胶的热降解研究

采用热重分析法(TGA)和差热分析法(DTA)研究了自然微生物凝固天然橡胶(N-NR)和淀粉微生物凝固天然橡胶(S-NR)在空气气氛中的热降解行为,为探索新的天然胶乳加工工艺提供科学依据。研究结果表明:(1)实验条件下,两种凝固方式的橡胶在空气气氛中的降解均为多步反应。(2)S-NR的抗氧化性能较N-NR好。     

天然橡胶和胶清橡胶的热氧降解特性研究

采用热重分析法(TGA)研究了胶清胶(NR-s)和天然橡胶(NR)在空气气氛中的热氧降解行为。结果表明:(1)NR-s和NR的TG图中均出现多个平台,对应的DTG图中均出现多个峰,因此其热氧降解均属于多步反应。(2)NR-s的T0.05(质量损失率为5%时的温度)为283℃,NR的T0.05为316℃,说明NR-s的热稳定性较NR有一定的下降。     

胶乳法溴化天然橡胶的热降解研究

采用胶乳法分别制备了溴质量分数为0.28和0.41的溴化天然橡胶(BNR),并采用傅里叶变换红外光谱法和热重分析法研究其热降解和热氧降解过程.结果表明:胶乳法BNR热降解为2步反应,第1步发生脱溴化氢反应,试样的质量损失率近似等于其溴质量分数;第2步BNR在475℃降解时仍有6.9%～8.8%的残留物存在,且较稳定.胶乳法BNR热氧降解分3步进行,第1步反应的温度及质量损失率与热降解相近,产物主要是溴化氢,此外还有少量二氧化碳;第2步和第3步产物为二氧化碳,且分解彻底.     

热氧老化对氮气气氛下聚碳酸酯热稳定性的影响

采用热空气加速聚碳酸酯(PC)老化的方式进行不同时间下的老化实验,然后在氮气气氛下进行热失重分析,并用Coats-Redfern法和Freeman-Carroll法进行热分解动力学分析。结果表明:老化初期,PC起始分解温度、半失重温度和最大失重温度以及热降解活化能均呈下降趋势;PC的热稳定性下降,主要发生断链和端基脱落;老化后期,PC的起始分解温度、半失重温度和最大失重温度以及热降解活化能又均增大,因PC的交联可使其热稳定性有所提高。     

霉化对天然橡胶组分及其热降解过程的影响

采用红外光谱仪分析了微波干燥未霉化天然橡胶(NR)和霉化天然橡胶(NR—m)的组分。图谱显示,NR在1541.20cm-1处有酰胺Ⅱ吸收峰,而NR—m没有。采用热重分析法分别在氮气和空气气氛中测试了微波干燥的NR和NR—m热降解和热氧降解。TG和DTG曲线显示,NR和NR—m的热降解均为1步反应,热氧降解均为2步反应。在等速升温条件下,NR的热降解温度和热氧降解温度均高于NR—m,NR降解时的活化能明显低于NR—m;2试样的反应级数为:在热降解中n2,在热氧降解中n2;在热降解中NR的相关系数r均大于NR—m;随升温速率的增大,2试样的A值和A1值均增大。     

Thermal degradation of cellulose in air and nitrogen at low temperatures

Thermal analysis and kinetic studies have shown that oxidative reactions are responsible for acceleration in the rates of weight loss and depolymerization of cellulose on pyrolysis in air at temperatures below 300°C. The oxidative reactions include production of hydroperoxide, carbonyl, and carboxyl groups, which have been investigated at lower temperatures along with the rates of depolymerization and production of carbon monoxide and carbon dioxide. The experimental results are consistent with an autoxidation mechanism involving initiation, propagation, and decomposition reactions. At temperatures above 300°, the rate of pyrolysis is essentially the same in both air and nitrogen, indicating that thermal degradation is independent of the oxidative reactions.     

CNR热氧降解历程的研究

采用电导率法测定氯化橡胶（CNR）热氧降解产生氯化氢的量,研究CNR的热氧降解历程。结果表明,CNR的热氧降解过程分为诱导期和高速降解期,随着降解温度的升高,CNR热氧降解诱导期缩短,生成氯化氢的量增大。在高速降解期,CNR脱氯化氢的速率恒定,热氧降解反应级数为零,表观活化能为50.68kJ·mol^-1。     

Thermal degradation of cellulose and its phosphorylated products in air and nitrogen

The thermal degradation of cellulose and its phosphorylated products (phosphates, diethylphosphate, and diphenylphosphate) were studied in air and nitrogen by differential thermal analysis and dynamic thermogravimetry from ambient temperature to 750°C. From the resulting data various thermodynamic parameters were obtained following the methods of Broido and Freeman and Carroll. The values of E_a for decomposition for phosphorylated cellulose were found to be in the range 55–138 kJ mol^?1 in air and 85–152 kJ mol^?1 in nitrogen and depended upon the percent of phosphorus contents in the samples. The mass spectrum of cellobiose phosphate indicated the absence of the molecular ion, indicating that the compound was thermally unstable. The IR spectra of the pyrolysis residues of cellulose phosphate gave indication of formation of a compound having C?O and P?O groups. A fire retardancy mechanism for the thermal degradation of cellulose phosphate has been proposed.     

低蛋白天然胶乳的制备及性能研究

分别采用蛋白酶法、取代吸附法、多次离心法和普通离心法制备低蛋白天然胶乳(LPNRL)和普通天然胶乳(NRL),并对胶乳和硫化胶膜性能进行研究.结果表明,与NRL相比,LPNRL的氮含量、塑性初值和塑性保持率均较小;与NRL硫化胶膜相比,LPNRL硫化胶膜的物理性能、老化性能和玻璃化温度(Tg)较低,温度低于Tg时的储能模量较高.     

Thermal aging properties and chemical resistance of blends of natural rubber and epoxidized low molecular weight natural rubber

Studies into solvent resistance and aging properties of blends of natural rubber and epoxidized low molecular weight natural rubber were carried out. Vulcanization of the blends using the semi‐efficient vulcanization (semi‐EV) system was found to have curing advantages over conventional vulcanization (CV) and efficient vulcanization (EV) systems. The rheological properties (cure time, t₉₀, and scorch time, t₂), solvent resistances, and aging properties of the vulcanizates were found to improve as the level of epoxidized low molecular weight natural rubber in the blends increases. The mechanical properties of the blends were also found to be within the accepted level for NR vulcanizates. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1733–1739, 2005     

Metathesis degradation of natural rubber

Summary Metathesis reaction of natural rubber was carried out using tungusten hexachloride and tetramethyl tin in chlorobenzene. The rubber had to be purified by several times precipitations before the reaction. Molecular weight decreased very much with the progress of reaction and with the increase of temperature. However, NMR studies indicated considerable decreases of carbon-carbon double bonds, which can not be explained by simple metathesis reaction. Some other reactions which consumed unsaturation have to be taken into account to elucidate the exact structure of resultant oligomers.     

Thermal behavior of natural rubber and chlorinated rubber blends

A solid-state chemical reaction occurs when a solvent cast film of a blend of masticated natural rubber and chlorinated natural rubber is heated in the presence of air at 150°C. The thermal behavior of solvent cast films of chlorinated natural rubber, masticated natural rubber, and a 1 : 1 w/w blend (2% w/v in xylene) of these two polymers has been studied using differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy, and nuclear magnetic spectroscopy. The results suggest that carbonyl groups are incorporated into the blend on heating and that the vinyl functionality of the isoprene units is modified during this apparent oxidation. Heating for 2 h at 150°C results in a material that no longer contains the rubber-like cis-1,4-polyisoprene units. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1379–1384, 1997     

Study on hot air aging and thermooxidative degradation of peroxide prevulcanized natural rubber latex film

The air‐aging process at 120°C and the thermooxidative degradation of peroxide prevulcanized natural rubber latex (PPVL) film were studied with FTIR and thermal gravity (TG) and differential thermal gravity (DTG) analysis, respectively. The result of FTIR shows that the ? OH and ? COOH absorption of the rubber molecules at IR spectrum 3600–3200 cm^?1, the ? C?O absorption at 1708 cm^?1, and the ? C? OH absorption of alcohol at 1105 and 1060 cm^?1 increased continuously with extension of the aging time, but the ? CH₃ absorption of saturated hydrocarbon at 2966 and 2868 cm^?1, the ? CH₃ absorption at 1447 and 1378 cm^?1, and the C?C absorption at 835 cm^?1 decreased gradually. The result of TG‐DTG shows that the thermal degradation reaction of PPVL film in air atmosphere is a two‐stage reaction. The reaction order (n) of the first stage of thermooxidation reaction is 1.5; the activation energy of reaction (E) increases linearly with the increment of the heating rate, and the apparent activation energy (E₀) is 191.6 kJ mol^?1. The temperature at 5% weight loss (T_0.05), the temperature at maximum rate of weight loss (T_p), and the temperature at final weight loss (T_f) in the first stage of degradation reaction move toward the high temperature side as the heating rate quickened. The weight loss rate increases significantly with increment of heating rate; the correlation between the weight loss rate (α_p) of DTG peak and the heating rate is not obvious. The weight loss rate in the first stage (α_f1) rises as the heating rate increases. The final weight loss rate in second stage (α_f2) has no reference to heating rate; the weight loss rate of the rubber film is 99.9% at that time. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3196–3200, 2004     

Thermal degradation of polytetrafluoroethylene in flowing helium atmosphere

The thermal degradation of polytetrafluoroethylene in flowing helium atmosphere was studied in the temperature range 510–600C. The products of thermal degradation were analyzed by an on-line gas chromatography and the rates of degradation were obtained. At relatively lower temperatures (less than 530°C) the rate curves as a function of time showed two peaks. This phenomenon was explained in terms of diffusion limitation of the gaseous products. Further research was carried out by scanning electron microscopy (SEM) in order to observe the diffusion limitation and these facts were confirmed by observing the matrix of partially degraded polymer. The rate curves which have two peaks indicated that the diffusion limitation was disappeared above ca. 50% conversion. The activation energy in diffusion limitation free region was 78.1 kcal/mole and it was very similar to the result obtained by Madorsky (80.5 kcal/mole). The activation energy was also consistent with that obtained by thermogravimetry.