Effect of maturation on the bulk viscosity and molecular chain length of cuplump natural rubber

The effects of the maturation and storage of naturally coagulated latex, generally termed cuplumps, on some bulk rheological properties and on parameters characterizing the macromolecular chain length were investigated for natural rubbers of different clonal typologies. The sensitivity of the clonal material to the degradative effects of cuplump maturation increased with the level of tree energetic metabolism, with the most metabolically active plant materials (e.g., PB 235) being most sensitive, whereas the less active clone PB 217 was less sensitive. A definite relationship evolves between Hevea tree metabolism and the stability of the structure of the biosynthesized rubber. The results presented here highlight at a macromolecular level the effects of maturation previously demonstrated on bulk processing parameters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 703–708, 2002     

Role of short polyisoprene chains in storage hardening of natural rubber

Drying of natural rubber (NR) crumb (grade TSR10) requires high temperatures (100–120 °C). In order to determine the changes in bulk viscosity during the drying process, ageing kinetics at 120 °C were studied on model NR samples. During the process, changes in Mooney viscosity and weight‐average molar mass (M_W) were monitored. Rubber from clones GT 1 and PR 107, with a bimodal inherent molar mass distribution (MMD₀), was degraded in a two‐phase process. During the first phase, Mooney viscosity and M_W increased, undoubtedly owing to a predominance of storage hardening over chain scissions [0 < t (min) <120]. During the second phase, chain scissions predominated (t > 120 min) and Mooney viscosity and M_W decreased. For rubber samples from clone PB 217, with a unimodal MMD₀, no or reduced storage hardening was observed throughout the ageing process. These results showed that the key parameter involved in storage hardening seems to be the quantity of short polyisoprene chains and probably the nature of the chain ends. Copyright © 2003 Society of Chemical Industry     

New crosslinked polyurethane elastomers with various physical properties from natural rubber derivatives

New hydroxytelechelic cis‐1,4‐oligoisoprenes exhibiting variable values and distributions of the hydroxyl functionality were successfully prepared. The synthesis reactions involved chemical modifications of carbonyl telechelic cis‐1,4‐polyisoprene, which was obtained by controlled degradation of synthetic or natural rubber. These new oligomers were reacted with toluene diisocyanate to elaborate crosslinked polyurethane elastomers. The thermomechanical properties of the prepared polyurethanes were investigated. The results show a strong relationship between the chemical structures and properties. This work mainly shows the potentiality of making new crosslinking polyurethane materials with controlled and various properties from natural rubber, a renewable resource. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Determination of the molecular characteristics of commercial polyethylenes with different architectures and the relation with the melt flow index

The molecular weight distribution curves of several commercial polyethylene samples were evaluated by high‐temperature gel permeation chromatography with two detectors (a refractive‐index detector and a viscometer) to determine the molecular sizes and architectures (branching). The polymer samples included high‐ and low‐density polyethylenes with different molecular weight distributions (wide, medium, unimodal, and bimodal) from nine producers. The results were tested against the melt flow index and zero‐shear melt viscosity to find correlations. The data for high‐density polyethylene correlated well with the molecular weight, whereas the data for low‐density polyethylene did not correlate. However, when the weight‐average molecular weight was corrected by the branching parameter and a factor form, all the polyethylene samples fit a single equation. These results indicate that the melt flow index is dependent not only on the molecular weight but also on the molecular shape, including branching. The relation accounted for samples of different resin producers, molecular weights (65,000–638,000), and polydispersities (2.9–20). The use of the branching parameter for the correction of the molecular weight allowed the correlation of these parameters despite differences in the technologies, molecular weights, and molecular architectures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1572–1578, 2007     

Relations between Wallace plasticity and Mw for natural rubber

Wallace plasticity and the weight‐average molar mass (M_w) were measured on natural rubber samples of different origins. A sigmoidal model describes the relations between Wallace plasticity and M_w (0.872 > r² > 0.992) for given families of samples. The families of samples analyzed differed through their clonal origin, collection method (cup lumps or latex), and type of processing (CV or non‐CV). This study showed that two samples of natural rubber can be identical in terms of plasticity, but very different in terms of the average polyisoprene chain length or M_w. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3078–3087, 1999     

Correlating Polymer Parameters to the Entire Molecular Weight Distribution: Application to the Melt Index

Summary: A method that takes into account the entire molecular weight distribution (MWD) for the prediction of polymer point properties and/or indexes is presented. The method is based on the convolution of the polymer mass molecular weight distribution and an empirical kernel function. Thus, the problem of relating the polymers properties to the MWD is reduced to the estimation of this empirical function. The proposed methodology is able to successfully predict melt indexes (MI) of a set of poly(propylene) samples.

     

Molecular dynamics simulation of diffusion behavior of cyclohexane in natural rubber during reclamation

Reclaiming oil is a common additive involved in many physical rubber reclamation processes. In this work, molecular dynamics simulation is used to investigate the diffusion of oil in natural rubber (NR) under different temperatures and pressures. The structures of polyisoprene and cyclohexane molecules are constructed. The diffusion coefficients (Ds) of cyclohexane molecules in polyisoprene under different temperatures and pressures are calculated. The free volumes are also obtained to better understand the change in microstructure. The diffusion experiments of oil in NR samples under different temperatures and pressures are also conducted. The simulation results show that D increases as the temperature rises, especially at temperatures above 400 K, while the pressure does not affect D significantly. The fractional free volume calculated from the free volume and occupied volume exhibits a similar trend to that of D. Furthermore, the calculated Ds agree well with the experimental results. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40347.     

Preparation and characterization of high‐molecular‐weight sericin by γ irradiation

We conducted this study to examine the changes in the molecular structure and physiological activities of silk sericin after γ irradiation. Sericin from Bombyx mori was extracted with an Na₂CO₃ solution. The molecular weight distribution of sericin increased in the gel permeation chromatography and sodium dodecyl sulfate/polyacrylamide gel electrophoresis results as the irradiation dose increased. Circular dichroism data also revealed that the α‐helix contents decreased with the irradiation dose. Ultraviolet absorption was shown a different pattern between the irradiated and unirradiated sericin. However, the Fourier transform infrared spectrum was not changed in all of the groups. Furthermore, the irradiated sericin was significantly increased in 2,2‐diphenyl‐1‐picryl‐hydrazil radical scavenging, and the tyrosinase inhibitory activities increased with irradiation dose. Therefore, γ irradiation was an effective method for producing high‐molecular‐weight sericin and for developing functional foods and cosmetics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of the processing conditions and the addition of trans-polyoctenylene rubber on the properties of natural rubber/styrene–butadiene rubber blends

In this study, the influence of the processing conditions and the addition of trans-polyoctenylene rubber (TOR) on Mooney viscosity, tensile properties, hardness, tearing resistance, and resilience of natural rubber/styrene–butadiene rubber blends was investigated. The results obtained are explained in light of dynamic mechanical and morphological analyses. Increasing processing time produced a finer blend morphology, which resulted in an improvement in the mechanical properties. The addition of TOR involved an increase in hardness, a decrease in tear resistance, and no effect on the resilience. It resulted in a large decrease in the Mooney viscosity and a slight decrease in the tensile properties if the components of the compounds were not properly mixed. The results indicate that TOR acted more as a plasticizer than a compatibilizer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melting Properties of Syndiotactic Polystyrenes and Effect of Hydrogen on Molecular Weight Distribution

Summary: The melting properties of syndiotactic polystyrenes are significantly affected by the structural molecular properties of the polymers. The most important influences on the melting behavior are stereoregularity, molecular weight and molecular weight distribution of the polymers. The melting temperature is increased by an enhanced syndiotacticity at sufficiently high molecular weights and at narrow molecular weight distributions. The degree of syndiotacticity obtained primarily depends on the kind and structure of the cyclopentadienyl ligand of the transition metal catalyst, whereas the effect of the other ancillary ligands on stereoregularity is negligible at the same cyclopentadienyl ligand. At narrow molecular weight distributions with below 2.8 and at constant stereoregularities, the molecular weight has a remarkable effect on the melting behavior at weight‐average molecular weights lower than about 80 000 g · mol^?1, resulting in a significant decrease of the melting temperature until below 230 °C. The presence of hydrogen during polymerization leads to a significant shift to lower molecular weights at comparably small amounts of hydrogen, but results in the occurrence of an additional peak in the molecular weight distribution at larger hydrogen concentrations giving evidence for the formation of a second active polymerization site producing lower molecular weight polymers. At constant stereoregularity, the broadening of the molecular weight distribution leads to decreased melting temperatures and to improved flow properties of the syndiotactic polystyrenes with increasing shear rates at moderate molecular weight distributions.

Detailed molecular weight distributions of syndiotactic polystyrenes in dependence on the hydrogen concentration.     

Seasonal and clonal variations in technological and thermal properties of raw Hevea natural rubber

This study was undertaken over a 10‐month period under environmental conditions within the state of Mato Grosso, Brazil, to evaluate the causes of variation in the technological and thermal properties of raw natural rubber (NR) from different clones of Hevea brasiliensis (GT 1, PR 255, FX 3864, and RRIM 600). These clones were chosen to represent good clones available in Brazil. The technological properties of raw NR were evaluated in terms of their dry rubber content (DRC), Wallace plasticity, plasticity retention index (PRI), and Mooney viscosity. The thermal performance was evaluated with the thermogravimetry (TG)/differential thermogravimetry (DTG) technique. There were significant variations (p < 0.01 and p < 0.05) between clones and tappings for all technological properties, except for the percentage DRC among the clones. Of the clones studied, clone PR 255 presented the highest sensitivity to thermooxidation, as measured by its PRI value. The clone type and period of the year did not significantly influence the thermal behavior (TG/DTG under a nitrogen atmosphere) among the four clones evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of the molecular structure of masticated natural rubber using rheological techniques

Mastication can improve the plasticity and reduce the molar mass of natural rubber (NR). The end product properties greatly depend on the efficiency of mastication. For NR before and after mastication, the changes in molecular properties are mainly attributed to the effects of mechanical and thermo-oxidative degradation. We investigated the variations in molecular weight, molecular weight distribution, degree of branching, and thermal stability of NR after mastication at 35, 75, and 110 rpm for 20 min. The results show that NR has a smaller molecular weight, broader molecular weight distribution, and a lower degree of structural branching at higher rotor speeds. Additionally, the rheological measurements were compared with gel permeation chromatography results, and the comparative outcomes reflect a strong correlation between these data. Rheological analysis reveals considerable complex relationships, and this measurement is more efficient, simple, and convenient than the other technique.     

Effect of the epoxy molecular weight on the properties of a cyanate ester/epoxy resin system

Bisphenol A dicyanate (BADCy) was modified by diglycidyl ether of bisphenol A epoxy resins with different molecular weights [E20 (weight‐average molecular weight = 1000) and E51 (weight‐average molecular weight = 400)] to investigate the effects of the epoxy molecular weight on the properties of the modified systems. The reactions were monitored with differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy, and the results showed that more pentacyclic oxazolidinone rings were formed in BADCy/E51 than in BADCy/E20 with the same epoxy resin weight content. DSC showed that BADCy/E20 had a lower curing temperature than BADCy/E51 because of the higher concentration of hydroxyl groups (? OH) in E20. Thermal, moisture absorption, and mechanical testing showed that E51‐modified BADCy performed better because of its lower molecular weight. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1744–1750, 2006     

Cure characteristics and physical properties of ground‐rubber‐filled natural rubber vulcanizates: Effects of the curing systems of the ground rubber and rubber matrix

Recycling discarded rubber is important for both environmental and economic reasons. One of the most attractive methods of recycling rubber waste is to use ground rubber (GR) as a compounding ingredient or as a replacement for raw polymers. In this study, ground natural rubber was prepared with different curing systems and compounded into the parent compounds. The cure behaviors and physical properties of the GR‐filled vulcanizates were investigated, and they were largely affected by the curing systems of the rubber matrix and GR. GR‐filled vulcanizates with GR and the rubber matrix, having a conventional curing system, showed the largest changes in the cure characteristics. The greatest decrease in the physical properties was observed for peroxide‐cured‐GR‐filled vulcanizates. The addition of GR decreased the crosslink density of the GR‐filled vulcanizates. This was thought to be the main reason for the reduction of the mechanical properties of the GR‐filled vulcanizates. However, the adhesion between the GR and rubber matrix may also have caused the differences in the physical properties of the GR‐filled vulcanizates with respect to the curing systems of the rubber matrix and GR. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of natural coagula maturation on the processability,cure, and mechanical properties of unfilled vulcanizates of Hevea natural rubber

Fresh latex from different Hevea brasiliensis clones was naturally coagulated, subjected to different durations of maturation, processed into solid rubber, and compounded into pure gum stocks and vulcanized. Coagula maturation had clone‐specific effects on the processability of the raw rubber: reduced for some clones, while others was less sensitive. The cure and mechanical behaviors of the compounded stocks and vulcanizates, respectively, were not sensitive to the clonal origin of coagula and their duration of maturation. Although coagula maturation could be associated with leaching, deactivation of inherent antioxidants in Hevea latex, as well as crosslinking and/or oxidation of polyisoprene chains, these results show that compounding with a standard pure gum recipe compensates for the Hevea latex constituents affected by maturation. Hence, extended maturation of Hevea coagula, for economic or other reasons, would influence much more the bulk behavior of raw rubber and have insignificant effects on the compounded stocks and vulcanizates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2359–2363, 2007     

Modeling of molecular weight distribution of gas‐phase polymerization of butadiene

A mathematical model of the molecular weight distribution (MWD) based on a multilayer model and an improved intrinsic kinetics model was proposed to simulate the MWD of the gas‐phase polymerization of butadiene with a heterogeneous catalyst. Intrinsic kinetics and heat and mass‐transfer resistances based on the multilayer model of a polymeric particle were considered in the modeling of the MWD. The effects of the reaction conditions, catalyst particle size, mass‐transfer resistance, deactivation of active sites, and transfer of the polymer chain on the molecular weight and MWD were simulated. The results show that the effects of the deactivation of active sites and transfer of the polymer chain on the average molecular weight are significant and that the effect of the catalyst particle size on the MWD is not significant. The simulation results of the molecular weight and MWD are compared with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 88–103, 2003     

Effect of foaming temperature and rubber grades on properties of natural rubber foams

Foaming temperature and grade of dry natural rubber were varied to evaluate their effects on the morphology and mechanical properties of natural rubber (NR) foams. Three different grades of NR were used; namely ENR‐25, SMR‐L, and SMR‐10. NR foams from these grades were produced at three different foaming temperatures, i.e. 140, 150, and 160°C. The study was carried out using formulated compositions containing sodium bicarbonate as the chemical blowing agent and were expanded using conventional compression molding technique via a heat transfer foaming process. The NR foams were characterized with respect to their relative foam density, density of crosslinking, cell size, compression stress, and compression set. Increase in foaming temperature resulted in lower relative density and larger cell size. It was also discovered that the crosslink density slightly decrease with increasing foaming temperature. For mechanical properties, the highest foam density resulted in the highest compression stress. Compression stress at 50% strain increased with increasing foaming temperature and ENR‐25 foam has the highest compression stress among the produced foams. The results showed that the morphology, physical, and mechanical properties of the rubber foams can be controlled closely by the foaming temperature and rubber grades. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermomechanical study of butyl rubber mastication during compounding

A thermomechanical method was used to study the topological and molecular structure of model rubber compounds. This structure changes because of mastication during compounding. It was found that raw butyl rubber has a diblock structure. The molecular weight distribution of the chains between the junctions of the polymer network, the coefficient of polydispersity, a share of low-temperature and high-temperature blocks, and changes in their glass transition temperatures as a result of the mixing of butyl rubber depend on both the presence of sulfur and the kind of sulfur (polymeric or mineral). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2159–2167, 1998     

液体聚硫橡胶对聚硫密封剂性能的影响

以G系列液体聚硫橡胶为生胶、MnO2为密封剂的硫化剂,制备相应的聚硫密封剂。考察了生胶的不同相对分子质量(Mr)和交联度对相应密封剂性能的影响。结果表明:不同Mr或交联度的生胶均赋予相应密封剂良好的力学性能,特别是由低Mr的G44制成的密封剂具有相对更好的力学性能;密封剂的耐高温性能与生胶的Mr关系不大,主要受交联度影响较大;生胶的Mr越大或交联度越高,密封剂的耐水性越好,但Mr或交联度对密封剂的耐油性能(增重率<3%)和粘接性能影响较小。     

Modeling of semibatch styrene suspension polymerization processes

We developed a mathematical model to describe the behavior of semibatch styrene suspension polymerization processes, where the constituents of a typical emulsion polymerization process are added into the reaction vessel during the course of a typical suspension reaction. This technique was recently described for the production of core–shell polymer particles. The model assumes that the nucleated emulsion particles can agglomerate with the sticky and much bigger suspension particles and that the agglomeration rate constant is a function of the internal states of the suspended droplets. The proposed model presented good agreement with experimental conversion, average molecular weight, and molecular weight distribution data. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1950–1967, 2005