Structural characterization of vulcanized natural rubber by latex state 13C NMR spectroscopy

Structural characterization of vulcanized natural rubber was performed by high‐resolution latex‐state ¹³C NMR spectroscopy. The vulcanized natural rubber latex was prepared by vulcanization of high ammonia natural rubber latex with sulfur and sodium di‐n‐butyldithiocarbamate as vulcanizing agents. High resolution was attained for latex‐state ¹³C NMR spectroscopy even after vulcanization of the rubber latex, as is evident from no background in spectrum and narrow half width of signals, which were independent of vulcanization time. Small signals at 44 and 58 ppm in the carbon region were assigned by measurements of both distortionless enhancement by polarization transfer (DEPT) and attached proton test (APT) to secondary, tertiary, and quaternary carbons of crosslinking points. The assignment was proved by high‐resolution solution‐state NMR spectroscopy of vulcanized liquid cis‐1,4‐polyisoprene as a model, in which DEPT, APT, 2‐dimensional ¹H‐¹³C correlation (HETCOR), and 2‐dimensional heteronuclear multiple bond correlation (HMBC) measurements were applied. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1003–1009, 2007     

Degradation of polychloroprene/natural rubber (PCP/NR) blends by photo-Fenton process

The effect of light and FeCl₃·6H₂O on polychloroprene (PCP)/natural rubber (NR) blends in toluene solution were investigated to demonstrate the influence of each polymer on the degradation process. The contributions of total polymer concentration (C_p), temperature (T) and polychromatic light exposure (L) on the degradation process were investigated through a 2³ factorial design approach. Degradation kinetics was examined by solution viscosity time data. FTIR spectroscopy and TGA were used to characterize the degradation. The exposure of the PCP/NR blend solution containing FeCl₃·6H₂O to light induces degradation in the polymers. A decrease of up to 70% in solution efflux time at constant temperature and without aggregation or phase separation was observed. PCP degradation by-products amplify the degradation of NR, as evidenced by the decrease in the PCP/NR 1:99 (w/w) solution efflux time, which was larger than that of the pure NR solution. The film cast from the solution exposed to light was thermally less stable than the one which was cast without FeCl₃·6H₂O.     

Comparative study of natural rubber and acrylonitrile rubber reinforced with aligned short aramid fiber

The aims of this paper are three-fold. The first is to determine the reinforcement of high performance short aramid fiber in two representative rubber matrices, namely natural rubber and acrylonitrile rubber. The second is to ascertain the effect of rubber polarity on the reinforcement. The third is to establish a pattern of reinforcement for use with less studied fibers. The rubbers were reinforced either with only aramid fiber or with a hybrid of aramid fiber and carbon black. The fiber contents were varied at 0, 2, 5 and 10 parts (by weight) per hundred rubber (phr) while those of carbon black were 0, 10, 20 and 30 phr. Conventional sulfur vulcanization was used. It was found that aramid fiber can reinforce both rubbers in the low strain region effectively, although to a significantly different degree. The hybrid carbon black provides additional reinforcement at low to medium strains and allows high strain stress upturn to occur in both rubber matrices. The findings enable the preparation of rubber composites having a wide, controllable range of mechanical behavior for specific high-performance engineering applications. Significantly, they also serve as a benchmark for developing reinforced systems from alternative fibers, particularly those from natural sources.     

Studies of thermooxidative degradation process of chlorinated natural rubber from latex

The thermooxidative degradation of chlorinated natural rubber (CNR) from latex were studied by thermogravimetry (TG) coupled with Fourier Transform Infrared Spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy and difference FTIR. The CNR degraded in air atmosphere with two distinct steps of weight loss. The first step ranging from 160 to 390 °C, mainly is a dehydrochlorination reaction with a little oxidative scission of molecular backbones to release carbon dioxide and the conjugated polyene sequences (---[C=C]---)_n=3,4 are formed on the molecules of CNR. The second step ranging from 390 to 585 °C, is an oxidative degradation reaction of the molecular backbones of CNR and the evolved gas is only carbon dioxide.     

Crack initiation and evolution in vulcanized natural rubber under high temperature fatigue

The nanoscaled crack initiation and evolution of natural rubber under high temperature (85 °C) and small strain amplitude (strain maximum α = 1) fatigue condition were investigated. It was shown by scanning electron microscopy (SEM) images that cracks and cavities with dimensions in nanoscale in the NR matrix appear during the high temperature fatigue. FTIR study indicated that thermal oxidation effect leads to the crosslinking structure destruction. According to the combined analysis of SEM, energy-dispersive X-ray (EDX) spectrometer and small angle X-ray scattering investigations, it was deduced that the destruction of crosslinking structure mainly locates in the vicinity of the ZnS particles with a diameter of 20.2 nm. The ZnS particles are generated as a byproduct in the vulcanization process. Further, the real-time SAXS analysis revealed that the cracks are primarily initiated at relative higher strains (0.7<α < 1) in the region of ZnS aggregations and larger cavities are derived from the enlargement of the cracks.     

Preparation and properties of natural rubber/rectorite nanocomposites

Natural rubber (NR)/rectorite nanocomposite was prepared by co-coagulating NR latex and rectorite aqueous suspension. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) were employed to characterize the microstructure of the nanocomposite. The results showed that the nanocomposite exhibited a higher glass transition temperature, lower tan δ peak value and slightly broader glass transition region compared with pure NR. The gas barrier properties of the NR/rectorite nanocomposites were remarkably improved by the introduction of nanoscale rectorite because of the increased tortuosity of the diffusive path for a penetrant molecule. The nanocomposites have a unique stress-strain behavior due to the reinforcement and the hindrance of rectorite layers to the tensile crystallization of NR.     

Stabilization effect of lignin in natural rubber

A series of carbon black filled natural rubbers containing lignin was tested from the view point of their thermo-oxidative aging. Lignin is biopolymer that belongs to the main components of wood. Mechanical properties and crosslink density of lignin stabilized vulcanisates were measured before and after thermo-oxidative aging for 24, 72, 168, 240 and 408 h at 80 °C. The results were compared with those from NR vulcanisates stabilized with the commercial rubber antioxidant N-phenyl-N-isopropyl-p-phenylene diamine (IPPD). The results obtained show that lignin exerts a stabilizing effect in carbon black filled natural rubber. Its effect is comparable with that of conventional synthetic antioxidant. Moreover, the addition of lignin increased the stabilizing effect of IPPD.     

Morphology of peroxide-prevulcanised natural rubber latex: effect of reaction time and deproteinisation

A non-uniform mesh structure, i.e. a dense network near the surface of peroxide-prevulcanised natural rubber latex particles, was observed under transmission electron microscopy. In the initial period of prevulcanisation, the swelling ratio of the latex sheet decreased with longer reaction time while an increase in crosslink density of rubber particles containing polystyrene, prepared using the phase transfer/bulk polymerisation process, was noticed. The modulus of the rubber sheet increased up to maximum crosslinking and thereafter decreased. After removal of proteins from the latex membrane layer, derived from protein-lipid originally existing at the rubber particle surface, could not be detected. The absence of proteins, which act as free radical scavengers, resulted in a rapid diffusion of alkoxy radicals into the rubber phase of deproteinised latex and, therefore, a uniform crosslink distribution inside each particle was obtained.     

Effects of epoxidized natural rubber as a compatibilizer in melt compounded natural rubber-organoclay nanocomposites

Nanocomposites containing natural rubber (NR) as matrix, epoxidized natural rubber (ENR) as compatibilizer and organophilic layered clay (organoclay) as filler were produced in an internal mixer and cured using a conventional sulphuric system. The effects of ENR with 25 (ENR 25) and 50 mol% epoxidation (ENR 50), respectively, were compared at 5 and 10 parts per hundred rubber (phr) concentrations. The organoclay content was fixed at 2 phr. Cure characteristics, clay dispersion, (thermo)mechanical properties of the nanocomposites were determined and discussed. Incorporation of ENR and organoclay strongly affected the parameters which could be derived from Monsanto MDR measurements. Faster cure and increased crosslink density were attributed to changes in the activation/crosslinking pathway which was, however, not studied in detail. The organoclay was mostly intercalated according to X-ray diffraction (XRD) and transmission electron microscopic (TEM) results. The best clay dispersion was achieved by adding ENR 50. This was reflected in the stiffness of the nanocomposites derived from both dynamic mechanical thermal analysis (DMTA) and tensile tests. The tensile and tear strengths of the ENR 50 containing nanocomposites were also superior to the ENR 25 compatibilized and uncompatibilized stocks.     

Cuttlebone as reinforcing filler for natural rubber

Cuttlebone was proved to be a biomass for new reinforcing filler for natural rubber (NR). The cuttlebone particles were obtained by crushing cuttlebone and followed by sieving. Density and crystal structure of the cuttlebone were 2.70 g/cm³ and an aragonite form of CaCO₃, respectively. The surface area and average diameter of the cuttlebone particles were measured and the reinforcement effect as filler for NR was investigated. The cuttlebone particles did not prevent a peroxide cross-linking reaction of NR, and mechanical properties of peroxide cross-linked NR filled with cuttlebone particles were found to be comparable with those of peroxide cross-linked NR filled with commercial CaCO₃ filler. Presence of chitin on the surface of the cuttlebone particles was speculated to result in a good interaction between cuttlebone particles and NR, which may be ascribed to the mechanical properties of cuttlebone filled NR samples.     

Natural rubber/clay nanocomposites: Influence of poly(ethylene glycol) on the silicate dispersion and local chain order of rubber network

A novel preparation of natural rubber (NR)/Na⁺-montmorillonite (MMT) nanocomposites in only one step by using poly(ethylene glycol) (PEG) has been investigated. PEG behaves as dispersing agent favouring the intercalation of rubber chains into the silicate galleries and providing substantially improved clay dispersion. Intercalated/exfoliated miscible hybrids were observed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The influence of PEG on the network structure has also been evaluated by static proton double-quantum nuclear magnetic resonance spectroscopy (¹H DQ NMR) at low-field. Silicate nanoparticles with a high aspect ratio (clay tactoids) and a more crosslinked rubber network have been obtained for an optimum PEG/MMT ratio. Both effects were responsible of the enhancement on mechanical properties.     

Improving the mechanical properties of short pineapple leaf fiber reinforced natural rubber by blending with acrylonitrile butadiene rubber

This work proposes a simple method for improving the rubber to filler stress transfer in short pineapple leaf fiber-reinforced natural rubber (NR). This was achieved by replacing some of the non-polar NR by polar acrylonitrile butadiene rubber (NBR). The amount replaced was varied from 0% to 20% by weight. The mixing sequence was designed so that the fiber would be coated with polar NBR before being dispersed in the NR matrix. A comparison system in which the mixing was carried out in a single step was also examined. Despite the fact that the two rubbers are immiscible, it was found that significant improvement of the stress transfer in the low strain region can be obtained. The mixing sequence affected the mechanical properties of the resulting composites. It is concluded that frictional stress transfer between the immiscible rubbers contributes more to the total stress transfer than does the frictional stress transfer between non-polar NR and polar cellulose fiber.     

Gel permeation chromatographic characterization of sodium hyaluronate and its fractions prepared by ultrasonic degradation

Summary High-molecular-weight sodium hyaluronate isolated from rooster combs was degraded by ultrasonication. The molecular weight of hyaluronate and its polydispersity was determined by gel-permeation chromatography. During 75-min treatment the molecular weight value decreased from 1.39×10⁶ Da to 2.25×10⁵ Da while the polydispersity of the molecular weight increased from 1.29 to 2.36. The reciprocal value of the square of the hyaluronate's molecular weight was linearly proportional to the time of ultrasonication.     

Influence of alkaline treatment and acetone extraction of natural rubber matrix on properties of carbon black filled natural rubber vulcanizates

In this study, air dried sheet (ADS) showed higher molecular weight, proteins, lipids and more gel content than the low protein natural rubber (LPNR) from alkaline treatment or acetone-extracted natural rubber (AENR). After removal of proteins and lipids, LPNR and AENR had shorter scorch and cure times among the rubber compounds observed. This is due to higher content of free fatty acids, glycerides and sodium salts of fatty acid that might act as cure activators with sulfur curing. Furthermore, a finer dispersion of CB was found in ADS, due to chemical interactions of CB with proteins and lipids at terminal ends of NR molecules. Also, high molecular weight and gel in ADS could induce a higher reinforcing index (α) resulting to superior mechanical, dynamic, thermo-mechanical, hardness and crosslink density. In contrast, CB agglomerates occurred in LPNR and AENR with low molecular weight and reduced proteins and lipids, causing inferior mechanical, dynamic, thermo-mechanical, along with loss of stiffness and crosslink density.     

Preparation and characterization of acidified chitosan immobilized in epoxidized natural rubber

Biocomposites comprising chitosan (CTS) trapped in an epoxidized natural rubber (ENR) was prepared by homogenizing CTS in ENR50 (ENR with about 50% epoxy content) latex in the presence of curing agents and acetic acid. Micrographs of CTS-t-ENR reveal no phased-out entity. Infrared spectra of CTS-t-ENR show only vibrational bands belonging to CTS and ENR, affirming that the former was not bonded but immobilized in the matrix of the latter. CTS loading up to 5 phr resulted in the increase in the tensile strength and elongation at break, modulus of the CTS-t-ENR. Thermal stability of CTS-t-ENR is higher than that of CTS but lower than that of ENR. Increase in CTS loading from 2.5 to 20 phr resulted in the decrease in toluene absorbency but increase in water uptake of CTS-t-ENR.     

Effect of montmorillonite intercalant structure on the cure parameters of natural rubber

Two quaternary phosphonium salts (aromatic and aliphatic) have been used as intercalants for Na-montmorillonite and the effect of intercalant structure on clay morphology and natural rubber vulcanization kinetics was investigated. Due to its lower rigid structure the aliphatic salt was easier to intercalate into the clay galleries giving rise to a higher interlayer distance and facilitating the rubber intercalation obtaining an exfoliated structure in the nanocomposite. The vulcanization process was sensibly accelerated by this organoclay and a higher crosslinking degree was observed in the nanocomposite which gave rise to materials with improved processing and physical characteristics.     

Synthesis of natural rubber-based telechelic cis-1,4-polyisoprenes and their use to prepare block copolymers via RAFT polymerization

A new trithiocarbonate functionalized cis-1,4-polyisoprene was obtained from oxidative degradation of natural rubber followed by reductive amination and amidation. The structure of the resulting functionalized cis-1,4-polyisoprene was confirmed by a combination of ¹H NMR spectroscopy, ¹³C NMR spectroscopy, MALDI-TOF mass spectrometry and FTIR spectroscopy. ¹H NMR spectroscopy showed that the trithiocarbonate functionality was equal to one. The well-defined trithiocarbonyl-end functionalized cis-1,4-polyisoprene was used as a macromolecular chain transfer agent (macroCTA) to mediate the RAFT polymerization of t-BA using AIBN as the initiator ([t-BA]₀/[macroCTA]₀/[AIBN]₀ = 250/1/0.2) in toluene at 60 °C. The resulting PI-b-P(t-BA) diblock copolymer presents an unimodal SEC trace shifted toward higher molecular weight in comparison with the SEC trace of the macroCTA, indicating that the polymerization of the second block is effective. The characteristics of the copolymer were determined by SEC = 26,000 g mol⁻¹, PDI = 1.76) and ¹H NMR spectroscopy ( (PI) = 62 and (P(t-BA)) = 87).     

Influence of gel content on the physical properties of unfilled and carbon black filled natural rubber vulcanizates

Recently, gel content has been considered as a standard property for evaluating commercial grade natural rubber (NR). In this study, NR containing various amounts of gel was prepared by accelerated storage hardening as a model to clarify the influence of gel content on the physical properties of both unfilled and carbon black filled vulcanizates. Furthermore, the NR samples were investigated to determine the effect of gel fraction on Mooney viscosity and the structure of the gel after mastication. The results revealed that Mooney viscosity was related to the percentage of gel fraction that has been proven to be the result of interactions between proteins and phospholipids at chain ends. After mastication, although the gel fraction of NR can be decomposed to ∼0% w/w, the interactions of proteins and phospholipids at the chain ends still existed, corresponding to the gel content of the raw rubber. In the case of unfilled vulcanizates, the gel content showed no effect on cure characteristics, crosslink density and ultimate tensile strength, whereas the upturn of stress occurred at a smaller strain when the gel content increased. However, in the case of carbon black filled vulcanizates, the gel content played a dominant role in the carbon black dispersion, which was poorer when gel content increased, contributing to a decrease of crosslink density and ultimate tensile strength.     

Insight into vulcanization mechanism of novel binary accelerators for natural rubber

A novel TU derivative, N-phenyl-N′-(у-triethoxysilane)-propyl thiourea(STU), is prepared and its binary accelerator system is investigated in detail. Compared to the control references, the optimum curing time of NR compounds with STU is the shortest, indicating a more nucleophilic reaction occurs. The Py-GC/MS results present that the phenyl isothiocyanate fragment still remains in the NR/STU compounds with or without extracting treatment, but no silane segment can be found in the vulcanizate with extracting treatment. Vibrations of C=S, NH and aromatic ring in FTIR experiments and a new methyne carbon peak, as well as the peaks of phenyl group of STU, in the solid state 13C-NMR experiments are found in the NR/STU vulcanizate with extracting treatment. Moreover, the crosslinking density of vulcanizates with STU evolves to lower level, indicating the sulfur atom of STU does not contribute to the sulfur crosslinking. Therefore, a new vulcanization kinetic mechanism of STU is propounded that the thiourea groups can graft to the rubber main chains as pendant groups by chemical bonds during the vulcanization process, which is in accordance with the experimental observations quite well.