Influence of gel and molecular weight on the properties of natural rubber

The influence of gel and molecular weight on the properties of natural rubber has been described. Crystallization, stress relaxation and orientation properties of different samples have been studied. Samples having different gel contents but similar molecular weights and samples having the same gel content with varying molecular weights have been prepared by extracting whole natural rubber. The gel content was varied from 1.5 to 29% and molecular weight from 1 × 10⁵ to 9.9 × 10⁵ g mol⁻¹. The gels reduce the overall crystallinity measured by differential scanning calorimetric experiments after freezing the samples for different time periods at −15°C. They also have a stiffening effect on the tensile relaxation modulus and decrease the rate of relaxation significantly. Birefringence, which measures the orientation and stress-induced crystallization, increases with time at high elongation for samples containing gels. At lower elongation, however, the birefringence of unvulcanized samples decreases with time. This decrease is less for gel samples. Natural rubbers of high molecular weight behave similarly in the above properties when compared to low molecular weight samples. The effect of gel is more predominant than that of molecular weight.     

用门尼粘度仪测试天然橡胶的相对分子质量

研究了门尼粘度仪测试的门尼粘度和凝胶渗透色谱仪测试的相对分子质量的关系。结果表明,Mark-Houwink方程η=kMa可以描述复数粘度与相对分子质量间的关系,并有较好的相关性。用门尼粘度值计算的数均相对分子质量和重均相对分子质量与凝胶渗透色谱仪测试的相对分子质量的相对误差分别为11.3%和2.4%。     

Unusual stress-strain properties of natural rubber vulcanizates with high primary molecular weight

Summary Natural rubber vulcanizates with high primary molecular weight were prepared by mixing raw rubber and dicumyl peroxide in benzene followed by freeze-drying. The stress-strain properties of these vulcanizates were quite different from those prepared by conventional mastication method. The important characteristics of these vulcanizates is high tensile modulus, high tensile strength, large hysteresis loss, and higher degree of strain-induced crystallization. The difference in the stress-strain behavior between these rubbers and conventional vulcanizates are discussed from the standpoint of the network structure.     

Synthesis of sulphonic lanthanum complex based on C-methylcalix[4]resorcinarene and its thermo-oxidative aging resistance for natural rubber

Sulphonic lanthanum complex based on C-methylcalix[4]resorcinarene (CMCR-La) was synthesised for the thermal-oxidative aging resistance of natural rubber. The structure of CMCR-La was confirmed by FT-IR, ¹³C NMR and element analysis. TG analysis revealed CMCR-La possessed better thermal stability than commercial antioxidant BHT. Accelerated thermal aging tests and oxidation induction time indicated that CMCR-La could obviously improve the thermal-oxidative aging resistance of NR vulcanisates, which was due to multi-phenolic groups, higher molecular weight, the binding and scavenging effect of La ions on free radicals as well as the extra steric hindrance for phenolic groups.     

Study on preparation of chlorinated natural rubber from latex and its thermal stability

The effects of pH value of reaction system, reaction time, and reaction temperature on the chlorination reaction in the preparation of chlorinated natural rubber (CNR) from natural rubber latex were discussed. It has been found from the thermal analysis that the thermal degradation of CNR in nitrogen is a one-step reaction, and 30% carbonide with a stable structure remained at 360 to 700°C; whereas the thermo-oxidative degradation of CNR in air is a multistep reaction, and the thermal degradation ratio reaches to 100% at 560°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2863–2867, 1999     

Photochemical reduction of molecular weight and number of double bonds in natural rubber film

Natural rubber (NR) can be degraded depending on various factors such as heat, mechanical force, chemical reaction, and light. Light is a very interesting factor because it can cause the NR to degrade under low temperature and pressure. The photo-degradation of NR films was carried out to investigate the effects of the light and the temperature on the reduction of the weight-average molecular weight (Mw) and the double bonds in the NR films. The NR films, with and without catalysts, titanium dioxide (TiO₂), and potassium persulfate (K₂S₂O₈), were exposed to light from a mercury light bulb at 7,000 and 36,000 lux, and at the temperature of 25 °C and 80 °C for 192 hrs. After exposure, the Mw of the NR films was analyzed by gel permeation chromatography (GPC). Changes in the Mw were used to construct a kinetic model for the process, (1/Mw)=(1/Mw₀)+(kt/2M₀) where k is the rate constant, and M₀ is the Mw of the monomer unit. The linear relationship between 1/Mw and time suggested pseudo first-order processes with random scission. The Mw distribution information from the GPC was used to calculate the number of double bonds in the NR films. The trend of the double bonds reduction curves was quite similar to the result obtained from the calculation from the FTIR spectra. This indicated that this calculation method might possibly be another alternative way to obtain the number of double bonds in the NR.     

The influence of anilino-substituted salicylanilide on the physicomechanical properties of ultraviolet-aged natural rubber

The effect of nine derivatives of salicylanilides on the elastic properties of ultraviolet-aged natural rubber have been investigated. The results are compared with similar blends without additives and also with reference samples containing phenyl salicylate. The compounds showed variable effects, but both o-Cl and p-OCH₃ derivatives showed remarkable effects. They both help in the thermal crosslinking. Also, natural rubber samples containing these derivatives showed remarkable stability in tensile stress, elongation, and swelling.     

天然橡胶胶乳热稳定性测定方法

论述了几种天然橡胶胶乳热稳定性测定方法的特点及其在应用上存在的问题,指出了进一步研究胶乳热稳定性测定方法的必要性     

The influence of molecular weight on the melt rheology of polypropylene

Melt viscosity and melt elasticity data were obtained over a broad range of temperatures and shear rates on a series of four polypropylenes of different molecular weight but approximately the same molecular weight distribution. The superposition technique was used with both temperature and molecular weight to shift flow curves for all four materials at three temperatures each along the shear rate axis to generate a master flow curve at a given temperature and molecular weight. For polypropylenes of this type, and molecular weight distribution shift, factors which can be used to extend the useful range of experimentally obtained flow data were determined. The dependency of apparent viscosity on weight average molecular weight at shear stresses as high as 10⁶ dynes/cm² is shown. The dependency of melt elasticity on molecular weight and temperature is discussed.     

The effect of an epoxidized plasticizer on the thermo-oxidative ageing of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers

The effects of an epoxidized plasticizer on the mechanical properties and thermo-oxidative ageing behaviour of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers (TPEs) were investigated. Aged and unaged blends were characterized by FTIR, tensile properties, tear strength, hardness and dynamic mechanical analysis (DMA). The properties of the epoxidized soya oil (ESO) plasticized TPEs were compared with those of the di-2-ethylhexylphthalate (DOP) plasticized counterparts. The presence of epoxide groups in ESO has been shown to produce two conflicting effects. On the one hand, the presence of excessive epoxide groups has resulted in poor ageing behaviour. On the other hand, it has resulted in a good interaction and compatibility with PVC/ENR. It was found that the tensile strength of the ESO plasticized blends were comparable with the DOP plasticized ones, but the elongation at break (EB) of the ESO blends fell short of that of the DOP blends. Also the retention of both tensile properties for the ESO blends was poorer than for DOP blends. Hardening and embrittlement also occurred in the ESO blends. Despite these weaknesses, ESO could be an ideal plasticizer for the PVC/ENR system as indicated by plasticizer permanence and the greater efficiency of plasticization. © 1998 SCI.     

Molecular weight characterization of polybutadiene rubber with high molecular weight and broad molecular weight distribution

Following the molecular weight characterization of two polybutadiene samples, it was found that M _w from gel permeation chromatography with universal calibration and light scattering were in agreement, but M _n by gel permeation chromatography was less than M _n from membrane osmometry. A more detailed analysis revealed that the high molecular weight and broad molecular weight distribution of the two samples forced two corrections to the membrane osmometry results for (a) diffusional layer effects caused by high solution viscosities, and (b) solute permeability of the membrane. In the latter effect, the high viscosities of the solutions prevented actual diffusion through the membrane, but “reflection” of these species as defined by the Staverman coefficient prevented an accurate M _n determination. After making these corrections, it was found that M _n from membrane osmometry using a very tight membrane was in very good agreement with M _n from gel permeation chromatography. A method is demonstrated for obtaining M _n from a combination of membrane osmometry and gel permeation chromatography, where membrane osmometry data from membranes of different porosities (after corrections for diffusional layers and membrane reflection) are used to verify the accuracy of the gel permeation chromatography data as representing the true molecular weight distribution, allowing the gel permeation chromatography data to be used to calculate M _n.     

磷脂对浓缩天然胶乳机械稳定性的影响

在天然胶乳中添加磷脂,研究磷脂对天然胶乳机械稳定性的影响,结果表明,随着磷脂用量和氨含量的增加,天然胶乳的机械稳定度逐渐升高。气相色谱-质谱联用仪(GC-MS)分析表明,磷脂在碱性条件下水解产生亚油酸、棕榈酸、油酸、反油酸、硬脂酸、α-亚麻酸等长链脂肪酸,进一步与氨水反应形成脂肪酸铵,并吸附在橡胶烃粒子表面,提高了天然胶乳的机械稳定性。随着碱度的升高和水解时间的延长,磷脂水解产物的化学组成和含量存在一定差异。     

碳酸钙晶须表面处理及其对天然橡胶复合材料性能的影响

碳酸钙晶须用表面改性剂Si-69、硬脂酸钠、钛酸酯偶联剂NDZ101进行表面处理,并用于天然橡胶（NR）的补强。结果表明,表面处理后碳酸钙晶须的表面性能提高,与NR的界面作用增强,对NR起到明显的补强作用。表面处理后碳酸钙晶须的加入使改性碳酸钙晶须／NR复合材料的损耗因子tan艿降低,热稳定性提高。其中以Si-69改性碳酸钙晶须补强效果最优,Si-69改性碳酸钙晶须／NR复合材料300％定伸应力、拉伸强度、撕裂强度比未改性的分别提高36．9％、34．2％、24．7％。     

相对分子质量及其分布对稀土顺丁橡胶性能的影响

研究了5种不同相对分子质量及其分布的稀土顺丁橡胶(NdBR)的性能。结果表明,NdBR生胶和混炼胶的门尼黏度随相对分子质量的增加而升高;窄相对分子质量分布(多分散指数小于3.00)NdBR的生胶门尼黏度略高于与其相对分子质量相近而分布较宽的NdBR。相对分子质量对NdBR的正硫化时间影响不大,但最小转矩和最大转矩有随相对分子质量的增加而增大之趋势。生胶相对分子质量较低的NdBR,其硫化胶的300%定伸应力和拉伸强度较低,生热值较高,耐磨性能下降,滚动阻力升高。生胶门尼黏度为39~49的NdBR,其硫化胶的综合性能良好。填充适量操作油可以提高硫化胶的物理机械性能。窄相对分子质量分布NdBR硫化胶的300%定伸应力、拉伸强度、扯断伸长率、回弹性、永久变形、耐磨性以及滚动阻力等都优于相对分子质量相近而分布较宽的NdBR。     

Application of computed X-ray tomography scanning in the study of thermo-oxidative degradation of thick-walled filled natural rubber vulcanizates

The aging of five thick-walled natural rubber compounds has been studied by computed X-ray tomography scanning and crosslink density measurements. The compounds were compouded as ordinary carbon-black-filled rubbers with sulfur and peroxide as curing agents. The rubber samples were aged in air at 70, 100, and 150°C for 1000h. The relatively new technique of computed X-ray tomography scanning proved to be a good method for studying the aging procedure, and especially for following the crack propagation in the surface. Antioxidants (TMQ and 6PPD) had a low effect on the resistance toward oxidative degradation and crosslinking under these conditions. Surprisingly, the efficient sulfur-vul-canized material had a poor resistance toward thermal degradation. When the crosslink density and the computed X-ray tomography scanning results were compared, it was assumed that the computed X-ray tomograph detected oxygen in the surface, both as elementary oxygen and as oxygen in degradation products, i.e., in carbonyls. The results agree well with the theory that oxidative aging is limited by the ability of the oxygen to diffuse into the material.     

Controlling the characteristics of butadiene rubber on the basis of molecular weight distribution

Mathematical modeling of the synthesis of diene rubber on a neodymium-based catalytic system is performed for a cascade of continuous reactors. The influence of operating parameters on molecular weight distribution and, as a consequence, on molecular weight characteristics and physicomechanical properties of the synthesized polymer is studied. The averaging of molecular weight characteristics obtained by mixing the polymers from the cascades of reactors with various process modes is simulated.     

增稠剂对天然胶乳热稳定性的影响

介绍了增稠剂在天然胶乳工艺中的应用，试验表明在胶乳中加入0．5－2．0份阿拉伯树胶粉，不仅对胶乳的粘度有影响，而且对胶乳的热稳定性也有明显的作用。