Comparative study of natural rubber/clay nanocomposites prepared from fresh or concentrated latex

Rubbers are usually compounded with different chemicals and fillers in order to modify their properties to suit the end applications. Natural rubber (NR) contains different natural occurring materials and this brings about subtle complexities in controlling compound and vulcanizate properties. Thus, the aim of this paper is to illustrate that the properties of compounds and vulcanizates of NR/clay prepared from fresh field latex and from concentrated latex are different. Different amounts of pristine clay were added to the two latices and their viscosity determined. The latex mixtures were next coagulated to form solid filled rubbers and their properties examined. Vulcanizates of these solid rubbers were then prepared and their properties, also, were determined. The cause of an observed variation is attributed to soluble proteins in the fresh field latex. Structural models to explain this are proposed.     

Preparation of phenyl‐modified natural rubber in latex stage

Phenyl‐modified natural rubber was prepared in latex stage by bromination of deproteinized natural rubber followed by Suzuki‐Miyaura cross‐coupling reaction. First, the bromination of natural rubber was carried out using N‐bromosuccinimide in latex stage. The bromine atom content increased as amount of N‐bromosuccinimide increased. Second, the allylic bromine atom was replaced with a phenyl group using phenyl boronic acid in the presence of a palladium catalyst, according to the Suzuki‐Miyaura cross‐coupling reaction in latex stage. The resulting products were characterized by nuclear magnetic resonance (NMR) spectroscopy. Signal at 7.13 ppm was assigned to the phenyl group of the product, while signals at 3.98, 4.14, and 4.44 ppm were assigned to the remaining allylic brominated cis‐1,4‐isoprene units. The estimated phenyl group content and the conversion of the Suzuki‐Miyaura cross‐coupling reaction were 1.32 and 23.7 mol%, respectively. Glass transition temperature (T_g) of deproteinized natural rubber increased from ?62°C to ?46.7°C, when the phenyl group was introduced into the rubber.     

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.     

Structure and properties of isobutylene-isoprene rubber/swollen organoclay nanocomposites prepared by shear mixing

A new approach was developed to prepare high-performance isobutylene-isoprene rubber/swollen organoclay nanocomposites by shear mixing.Compared with traditional melt compounding method,better dispersion of nanoclay layers in rubber matrix was verified through transmission electron microscopy(TEM) and X-ray diffraction(XRD).The nanocomposites also exhibit significantly improved mechanical properties and gas barrier property.As a mechanism,the molecules of organic swelling agent play a vital role in accelerating the diffusion and intercalation of the matrix molecules.     

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.     

胶乳法氯化天然橡胶的光、热氧稳定性能

胶乳法氯化天然橡胶CNR经紫外光老化、热氧老化实验、化学分析、紫外光谱分析和热分析,结果表明：产品较溶液法光稳定性稍差,加入0．4％(质量百分比)的紫外线吸收剂AUI(二苯甲酮类)、AUII(苯并三唑类)和极少量的抗氧剂,可显著提高抗热氧老化性能。最佳配方为0．2％／0．5％(质量百分比)AOI(酚类抗氧剂)与AOIH(亚磷酸酯类抗氧剂)并用,或加入0．2％(质量百分比)的AOI。     

Morphology and mechanical and viscoelastic properties of natural rubber and styrene butadiene rubber latex blends

The morphology and mechanical and viscoelastic properties of a series of blends of natural rubber (NR) and styrene butadiene rubber (SBR) latex blends were studied in the uncrosslinked and crosslinked state. The morphology of the NR/SBR blends was analyzed using a scanning electron microscope. The morphology of the blends indicated a two phase structure in which SBR is dispersed as domains in the continuous NR matrix when its content is less than 50%. A cocontinuous morphology was obtained at a 50/50 NR/SBR ratio and phase inversion was seen beyond 50% SBR when NR formed the dispersed phase. The mechanical properties of the blends were studied with special reference to the effect of the blend ratio, surface active agents, vulcanizing system, and time for prevulcanization. As the NR content and time of prevulcanization increased, the mechanical properties such as the tensile strength, modulus, elongation at break, and hardness increased. This was due to the increased degree of crosslinking that leads to the strengthening of the 3‐dimensional network. In most cases the tear strength values increased as the prevulcanization time increased. The mechanical data were compared with theoretical predictions. The effects of the blend ratio and prevulcanization on the dynamic mechanical properties of the blends were investigated at different temperatures and frequencies. All the blends showed two distinct glass‐transition temperatures, indicating that the system is immiscible. It was also found that the glass‐transition temperatures of vulcanized blends are higher than those of unvulcanized blends. The time–temperature superposition and Cole–Cole analysis were made to understand the phase behavior of the blends. The tensile and tear fracture surfaces were examined by a scanning electron microscope to gain an insight into the failure mechanism. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2189–2211, 2000     

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.     

Rheology and thermal stability of polylactide/clay nanocomposites

Polylactide/clay nanocomposites (PLACNs) were prepared by melt intercalation. The intercalated structure of PLACNs was investigated using XRD and TEM. Both the linear and nonlinear rheological properties of PLACNs were measured by parallel plate rheometer. The results reveal that percolation threshold of the PLACNs is about 4 wt%, and the network structure is very sensitive to both the quiescent and the large amplitude oscillatory shear (LAOS) deformation. The stress overshoots in the reverse flow experiments were strongly dependent on the rest time and shear rate but shows a strain-scaling response to the startup of steady shear flow, indicating that the formation of the long-range structure in PLACNs may be the major driving force for the reorganization of the clay network. The thermal behavior of PLACNs was also characterized. However, the results show that with the addition of clay, the thermal stability of PLACNs decreases in contrast to that of pure PLA.     

Preparation and thermal stability of boron-containing phenolic resin/clay nanocomposites

In order to further improve thermal stability of the phenolic resins, we combined boron and clay with phenolic resins to prepare nanocomposites (BH-B, BP-B, and BE-B series). Boron-containing phenolic resin/clay (montmorillonite) nanocomposites were prepared using in situ polymerization of resol-type phenolic resins. Montmorillonite (MMT) was modified by benzyldimethylhexadecylammonium chloride (BH), benzyldimethyphenylammonium chloride (BP), and benzyltriethylammonium chloride (BE). X-ray diffraction measurements and transmission electron microscope (TEM) observations showed that clay platelets were partially exfoliated after complete curing of the phenolic resins. Thermogravimetric analysis showed that thermal decomposition temperatures (T_d) and residual weight at 790 °C of cured boron-containing nanocomposites were much higher than the corresponding nanocomposites without boron. For example, the rise in decomposition temperature of BE-B10% is about 42 °C (from 520 to 566 °C), whereas the increase in char yields is 6.4% (from 66.2% to 72.6%). However, the boron-containing composites were more prone to absorb moisture (ca. 9-14%) than boron-free ones (ca. 3-4%), which was attributed to unreacted or partially reacted boric acid during preparation process.     

Superhydrophobic and superoleophilic polyethylene aerogel coated natural rubber latex foam for oil-water separation application

The oil-water separation has made an attention due to over-increased production of oily water from the industrial process and everyday routine of humans. The current work reports on preparation and characterization of High-Density Polyethylene (HDPE) aerogel coated Natural Rubber Latex foam (NRLF) with superhydrophobic and superoleophilic character, good sorption capacity for oil-water separation application and were investigated. The HDPE aerogel and the coated NRLF material was prepared by a cooling process from a solution of HDPE in xylene solvent (HDPE sole, which resulted into thermally induced phase separation of the Polyethylene molecular network). The HDPE aerogel coated NRLF displayed a porous surface morphology with particle-like structural features. The HDPE aerogel coated NRLF showed superhydrophobicity with static water contact angle >150°. The effect and recyclability of the HDPE aerogel coated NRLF for oil-water separation was investigated using different model oil solvents to explore their repeatable application in oil spill clean-up process. Modified NRLF shows an excellent mechanical property (compressibility). The average modulus and average stiffness of the modified NRLF increased with the increase of the concentration of HDPE sol. The modified superhydrophobic sponge has good durability under acid and base conditions.     

The sensitizing effect of acrylates on radiation vulcanization of natural rubber latex

The sensitizing effect of acrylates on radiation vulcanization of natural rubber latex was studied. The results indicate that Gc value of crosslinking (Gc) will be higher at the same radiation dose when a sensitizer exists, and Gc value decreases with the increase of radiation dose (D) conforming to the formula Gc=KD^-α, where K and α are constants depending on sensitizers. The more sensitizers added, the greater the Gc value. However, the viscosity of the natural rubber latex also increases rapidly along with the increase of sensitizers added.Some sensitizers, such as TMPTA, can decrease the optimum dose from about 200 kGy to approximately 20 kGy according to our experiment. The tensile strength of the film can reach round 20 MPa. Other physical properties are comparable to those of unsensitized.     

Toughening of ethylene-propylene random copolymer/clay nanocomposites: Comparison of different compatibilizers

Ethylene/propylene-random-copolymer(PPR)/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers,including an ethylene-octene copolymer grafted maleic anhydride(POE-g-MA) and three maleic-anhydride-grafted polypropylenes(PP-g-MA) with different melt flow indexes(MFI),were used to improve the dispersion of organic clay in matrix.On the other hand,the effects of organic montmorillonite(OMMT) content on the nanocomposite structure in terms of clay dispersion in PPR matrix,thermal behavior and tensile properties were also studied. The X-ray diffraction(XRD) and transmission electron microscopy(TEM) results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites.Moreover,a PP-g-MA compatibilizer(compatibilizer B) having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers.With the introduction of compatibilizer D(POE-g-MA),most of the clays are dispersed into the POE phase,and the shape of the dispersed OMMT appears elliptic,which differs from the strip of PP-g-MA.Compared with virgin PPR,the Young’s modulus of the nanocomposite evidently increases when a compatibilizer C(PP-g-MA) with medium MFI is used.For the nanocomposites with compatibilizer B and C,their crystallinities(X_c) increase as compared with that of the virgin PPR. Furthermore,the increase of OMMT loadings presents little effect on the melt temperature(T_m) of the PPR/OMMT nanocomposites,and slight effect on their crystallization temperature(T_c).Only compatibilizer B can lead to a marked increases in crystallinity and T_c of the nanocomposite when the OMMT content is 2 wt%.     

Effect of rubber on properties of nylon-6/unmodified clay/rubber nanocomposites

Three nylon-6/unmodified clay/rubber nanocomposites with high toughness, high stiffness, high heat resistance and reduced flammability were studied in this paper, on basis of three compound powders of ultra-fine full-vulcanized powdered rubber (UFPR)/montmorillonite (UFPRM). It was found that all of the three UFPRs used in the study can help the silicate layers without organic treatment to be exfoliated in the nylon-6 matrix, despite some differences in compatibilities between them and nylon-6. Accordingly, the clay in different UFPRMs at the same loading content can lead to a similar improvement in stiffness and heat resistance of nanocomposites. In other words, UFPRs having different compatibilities with nylon-6 do not affect the stiffness and heat resistance of nanocomposites largely. However, the nylon-6 nanocomposites, modified with different UFPRMs, show different superior properties. Butadiene styrene vinyl-pyridine UFPRM (VP-UFPRM) is more effective in improving toughness of nylon-6. Nylon-6/silicone UFPRM (nylon-6/S-UFPRM) nanocomposite exhibits more reduced flammability, good flowability and high thermal stability. As for nylon-6/acrylate UFPRM (nylon-6/A-UFPRM) nanocomposite, it shows high toughness and thermal stability. Furthermore, the mechanism of unmodified clay exfoliation during the melt compounding and the effect of different UFPRs on the properties of the nylon-6/UFPRM nanocomposites are also discussed.     

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.     

Effect of epoxy resin on rheology of polycarbonate/clay nanocomposites

Polycarbonate/clay nanocomposites (PCNs) were prepared by melt intercalation using epoxy resin as a compatibilizer. The intercalated structure of PCNs was investigated using XRD and TEM. The linear and nonlinear dynamic rheological properties of PCNs were measured by the use of a parallel plate rheometer. The results reveal that the presence of epoxy influences rheological behavior of PCNs significantly. Addition of epoxy can improve dispersion of clay, enhancing the low-frequency viscoelastic responses; while high loadings of epoxy lead to a severe degradation of PC matrix, decreasing the high-frequency responses together with the plasticizing effect of excessive epoxy. Both of these two effects result in invalidity of time-temperature superposition. Moreover, all samples show high sensitivity to both the quiescent and large amplitude oscillatory shear (LAOS) deformation, despite enhanced percolation of tactoids due to the compatibilization of epoxy.     

Influence of four different types of organophilic clay on the morphology and thermal properties of polystyrene/clay nanocomposites prepared by using the γ-ray irradiation technique

Polystyrene (PS)/clay nanocomposites were successfully prepared by the γ-ray irradiation technique. Four different types of organophilic clays were used: three of the four contained a reactive group, while the other did not. Exfoliated PS/clay nanocomposites can be obtained by using reactive organophilic clay and intercalated PS/nanocomposites can be formed by using non-reactive ones, which was confirmed by X-ray diffraction (XRD) and by transmission electron microscopy (TEM). In the formation of exfoliated PS/nanocomposites, the effect of the double bond of the clay-intercalated agents is much more important than the alkyl chain length. The enhanced thermal properties of PS/nanocomposites were characterized by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). In particular, the enhancement of the thermal properties of PS/nanocomposites made using the reactive organophilic clay was much higher than that of the thermal properties of PS/nanocomposites incorporating non-reactive clay.     

Cytotoxicity and anticancer activity of natural rubber latex particles for cancer cells

To broaden the knowledge of cytotoxicity of natural rubber latex (NRL) nanoparticles we for the first time examined the latex biocompatibility in vitro against a panel of cancer cells (A549, A2780, and MDA-MB-231). Owing to fractionation of NRL nanoparticles by ultra-centrifuge, the effect of the non-rubber constituents (intermediate of 5.8 wt% and sediment of 0.2 wt%) on the cytotoxicity was clarified. For intermediate constituent, the half maximal inhibitory concentration (IC₅₀) values at 24 h was 1.05 mg/mL for A549 cells, which was one order of magnitude higher in toxicity as compared to that for A2780 (0.24 mg/mL) and MDA-MB-231 (0.36 mg/mL) cells. In addition, profound studies including cell cycle arrest abilities and apoptosis induction profiles against cancer cells were discussed in detail. It was found that the constituents exhibit some significant effect on the cell cycle arrest and trigger apoptosis for A2780 cells. This effective apoptosis induction profiles was more prominent in MDA-MB-231 cells incubated with NRL nanoparticles and sediment loading conditions. The percentage of apoptotic cells was ca. 6–8% of the total cells.     

Prevulcanisation of skim latex: morphology and its use in natural rubber based composite material

The prevulcanisation of skim latex, a by-product of field natural rubber (NR) latex concentrated by centrifugation, using sulphur and peroxide systems was investigated. Compared to the peroxide prevulcanisation, the lower swelling ratio of film casted from sulphur-prevulcanised skim (SPVS) latex was observed. The latter was then employed for preparation of NR/SPVS core–shell particles by using heterocoagulation technique whose driving force was an interpolymer complex between poly(ethylene oxide) (PEO) moieties of a non-ionic surfactant (Nonidet) adsorbed on small SPVS particles and the indigenous surfactant (protein–lipid) on a large NR particle. The value of zeta potential of heterocoagulated particle and the better oil resistance of films casted from the composite latex when compared to that of the NR film revealed the NR/SPVS core–shell structure.     

Polypropylene-clay nanocomposites: effect of compatibilizing agents on clay dispersion

In this work, polypropylene-clay nanocomposites are obtained and studied by using two different coupling agents, diethyl maleate and maleic anhydride. Two different clays, a commercial montmorillonite (Nanomer I30.TC) and a sodium bentonite purified and modified with octadecylammonium ions have also been used. The relative influence of each factor, matrix and clay modification, can be observed from structural analysis (SAXS, TEM) and mechanical properties. An explanation of the results is proposed according to the microstructure and chemical nature of the systems and the thermodynamic interactions operating during nanocomposite preparation.