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%。     

Study of molecular weight and chain branching architectures of natural rubber

The origin of the unique bimodal molecular weight distribution (MWD) of natural rubber (NR) has been controversial up to now. Studying the connection between particle size and molecular weight (MW) might be a key approach to revealing the mystery of NR architectures. In this study, through constructing NR models as objectives and employing gel‐permeation chromatography coupled to a viscosity detector as well as a multiangle laser light scattering detector (GPC‐DP‐MALLS), we have acquired branching parameters for NR from solid experiments and data fitting. It is found that small rubber particles (SRPs) and large rubber particles (LRPs) jointly construct the unique bimodal MWD of NR. SRPs with low branching numbers (Bn) and branching frequency (λ) are believed to be composed of almost linear rubber molecules having no chain‐end groups to be branched. In contrast, LRPs transform their MWD curve into a clear bimodal peak after transesterification and possess high Bn. Meanwhile, the formation of branch points in LRP by hydrogen bonding and ionic linkages has been clearly confirmed. Thus, a clear and exact structure of NR has been revealed for the first time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2016.     

Effect of molecular weight of epoxidized natural rubber on shear strength of adhesives

The dependence of shear strength of epoxidized natural rubber (ENR)‐based adhesives on molecular weight of the rubber is studied using coumarone–indene resin, gum rosin, and petro resin as tackifiers. The adhesive was coated on polyethylene terephthalate (PET) film substrate using a SHEEN hand coater at various coating thickness. The shear strength of adhesives was determined by a Texture Analyzer. Results show a maximum at 6.63 × 10⁴ and 4.14 × 10⁴ for ENR 25 and ENR 50, respectively, after which the shear strength decreases with further increases in molecular weight for all the coating thickness. This observation is attributed to varying degree of cohesiveness which culminates at the respective optimum molecular weight of ENR. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

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 effect of di-2-ethylhexyl phthalate on the thermo-oxidative ageing of poly(vinyl chloride)/epoxidized natural rubber blends

The effect of di-2-ethylhexyl phthalate (DOP) plasticizer on the degradation behaviour of 50/50 poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend was studied by long-term exposure to ambient conditions (27–30°C) in the laboratory. While the unplasticized blend showed obvious changes in physical properties such as hardening, loss of elasticity and embrittlement, the plasticized blend retained its properties. Thermo-oxidative ageing studies were carried out by evaluating the mechanical properties before and after ageing in an air oven at 80°C for 168 h. The relatively rapid degradation of PVC/ENR blend has been attributed to the high concentration of epoxy groups and the occurrence of ring-opening reactions to form ether crosslinks. It was found that the plasticizer confers adequate stabilization upon the addition of a certain threshold amount. The optimum amount of plasticizer required to adequately stabilize the blend is 20 phr. Above this there is a tendency for plasticizer migration to occur. The use of an antioxidant in conjunction with the plasticizer further stabilizes the blend. The general trend is of decrease in mechanical and physical properties with increase in DOP concentration. In addition, ease of processing also increases as indicated by the torque maxima and minima obtained from the Brabender plastograms.     

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.     

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.     

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.     

壳聚糖相对分子质量的测定方法

讨论了利用HPLC、特性黏度、动态黏度3种方法的关联来推导测定壳聚糖相对分子质量的简便方法。对6种壳聚糖样品,采用HPLC凝胶系统测定相对分子质量,利用乌氏黏度计一点法测定特性黏度,得出MHS方程为[η] = 3.72 × 10^－5M_w^1.37。同时还建立了10 mg/mL壳聚糖溶液降解过程中相对分子质量和动态黏度之间的关系。     

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     

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.     

不同金属离子催化剂制备氢化天然橡胶的热氧老化性能对比

采用不同金属离子催化剂,通过乳液氢化方法制备了氢化天然橡胶（HNR）,研究了生胶的等温氧化诱导时间（OIT）和硫化胶热氧老化前后的拉伸性能变化,考察了金属离子催化剂对HNR热氧老化性能的影响。结果表明,过氧化氢/水合肼/铜离子催化体系中的铜离子对材料的热氧老化性能影响较大,采用铜离子制备的HNR热氧老化后拉伸性能变化率高于天然胶乳,OIT缩短至2.5 min。将铜离子替换为锌离子后制备的HNR,100 ℃热氧老化72 h后拉伸强度变化率减小至23.91%,扯断伸长率变化率为32.12%,150 ℃ OIT延长至32.4 min,具有更好的热氧老化性能。     

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％。