Natural rubber latex LbL films: Characterization and growth of fibroblasts

The recent biomedical applications of natural rubber (NR) latex, mostly in dry membranes, have motivated research into novel, more noble uses of this low-cost biomaterial. In this article, we provide the first report on the fabrication of layer-by-layer (LbL) films of NR alternated with the polyelectrolytes polyethylenimine (PEI) and polyallylamine hydrochloride (PAH). Stable (PAH/NR)_n and (PEI/NR)_n LbL films displayed similar physicochemical properties, but differed in terms of film morphology according to atomic force microscopy (AFM) and scanning electron microscopy (SEM) data. Most significantly, (PEI/NR)₅ LbL films were made of smaller and flattened particles, which were not efficient for the growth and proliferation of normal human fibroblasts (NHF). In contrast, efficient NHF proliferation could be obtained with (PAH/NR)_n LbL films, with the fibroblasts exhibiting the expected elongated morphology. Furthermore, cell growth did not occur for cast films of NR, thus demonstrating the suitability of the LbL method for this biologically related application. The differences between the two polyelectrolytes illustrate the importance of the film architecture and morphology, which open the way for exploiting the molecular control inherent in the LbL technique for further applications of NR-containing films. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Green strength of natural rubber: The origin of the stress–strain behavior of natural rubber

The variation of the green strength of natural rubber (NR) with the preparation method of the film was studied to elucidate the origin of the stress–strain behavior characteristics of NR in connection with the structure of branch points in NR. A rubber film prepared via casting from NR latex showed the highest modulus and green strength in comparison with films prepared via casting from a toluene solution and via the hot pressing of dry rubber. The modulus and green strength of the NR latex‐casting film decreased after the hot‐press treatment of the film. On the other hand, no difference was observed for synthetic cis‐1,4‐polyisoprene rubber with the preparation method of the film or the heat treatment. This stress–strain behavior characteristics of NR can be ascribed to the changes in the branch points of the NR film with the casting method, which may result in differences in entanglement and crystallizability on stretching. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Bending of Layer-by-Layer Films Driven by an External Magnetic Field

We report on optimized architectures containing layer-by-layer (LbL) films of natural rubber latex (NRL), carboxymethyl-chitosan (CMC) and magnetite (Fe₃O₄) nanoparticles (MNPs) deposited on flexible substrates, which could be easily bent by an external magnetic field. The mechanical response depended on the number of deposited layers and was explained semi-quantitatively with a fully atomistic model, where the LbL film was represented as superposing layers of hexagonal graphene-like atomic arrangements deposited on a stiffer substrate. The bending with no direct current or voltage being applied to a supramolecular structure containing biocompatible and antimicrobial materials represents a proof-of-principle experiment that is promising for tissue engineering applications in biomedicine.     

Composite natural rubber based latex particles: a novel approach

The oil resistance of natural rubber (NR) film could be effectively improved by using the heterocoagulation of large NR particle with small polychloroprene (CR) particles. In the preparation of NR/CR composite particle with a core-shell structure, a nonionic surfactant whose molecule bears poly(ethylene oxide) (PEO) was adsorbed on CR particles and allowed to form complexes between PEO and indigenous surfactant (protein-lipid) on the NR particle surface. Composite latex particle obtained was characterised by particle size, zeta potential and glass transition temperature measurements and the data indicated the presence of CR on the outer layer of composite particle. Better oil resistance of film casted from heterocoagulated latex when compared to that of NR film confirmed the NR/CR core-shell structure. The epoxidised natural rubber (ENR), crosslinked ENR and/or skim latex particles were investigated in order to replace the use of CR in the heterocoagulation process.     

Acetoacetoxy functionalized natural rubber latex capable of forming cross-linkable film under ambient conditions

This work demonstrates that natural rubber (NR) latex particles containing acetoacetoxy (AcAc) groups are able to undergo cross-linking upon film formation at ambient temperature by reaction with glutaraldehyde (GTA). Natural rubber latex grafted with poly(acetoacetoxyethyl methacrylate) (NR-g-PAAEM) was synthesized by seeded emulsion polymerization, using benzoyl peroxide (BPO) as an initiator in free radical polymerization. The degree of grafting of PAAEM in the graft copolymers was evaluated by ¹H NMR technique. Transmission electron microscope (TEM) was used for investigation the particle morphology of the grafted NR latex. Since the AcAc groups are intentionally attached to the NR particles providing sites of cross-linking at ambient temperature, the cross-linking ability of these sites by reaction with GTA was then investigated. The results revealed that the latex film of NR-g-PAAEM with the addition of GTA had a much higher tensile strength in comparison with the film without GTA. The surface morphology of the NR-g-PAAEM latex film formed in the absence and presence of the GTA cross-linker was also investigated using atomic force microscopy (AFM). By GTA addition into the NR-g-PAAEM latex before film formation, an increase in the root-mean-square (RMS) roughness of the surface of the latex film was observed. Moreover, it was also observed that the NR-g-PAAEM films with the addition of GTA had higher activation energy for thermal degradation than that without the cross-linker. This confirms that the cross-linking reaction took place in the NR-g-PAAEM latex film as a result of its reaction with the GTA.     

Improving blood compatibility of natural rubber by UV‐induced graft polymerization of hydrophilic monomers

Natural rubber (NR) latex films surface‐grafted with hydrophilic monomers, poly(ethylene glycol) methacrylate (PEGMA), N‐vinylpyrrolidone (VPy), and 2‐methacryloyloxyethyl phosphorylcholine (MPC), were prepared by UV‐induced graft polymerization using benzophenone as a photosensitizer. The grafting yield increases of vulcanized NR latex films as a function of time and monomer concentration were of lesser magnitude than those of the unvulcanized NR latex films. This can be explained as a result of the crosslinked network generated during vulcanization acting as a barrier to the permeation of the photosensitizer and the monomer. The appearance of a characteristic carbonyl stretching in the attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR) spectra of NR latex films after the surface grafting of PEGMA and MPC indicates that the modification has proceeded at least to the sampling depth of ATR‐FTIR (∼ 1–2 μm). According to the water contact angle of the modified NR latex films, the surface grafting density became higher as the grafting time and monomer concentration increased. The complete absence of plasma protein adsorption and platelet adhesion on the surface‐modified NR latex films having grafting yield above 1 wt % is a strong indication of improved blood compatibility. Results from tensile tests suggest that graft polymerization does not cause adverse effects on the mechanical properties of vulcanized NR latex films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Photo-vulcanization using thiol-ene chemistry: Film formation,morphology and network characteristics of UV crosslinked rubber latices

The photo-vulcanization with versatile thiol-ene chemistry represents an innovative approach to crosslink diene-rubber materials both in latex and in solid film state. In this work, the structure of elastomer-based thiol-ene networks and the morphology after film formation are studied in detail using electron microscopic techniques, atomic force microscopy and multiple-quantum solid-state NMR spectroscopy. Additionally, film formation properties and corresponding macroscopic properties of photo-vulcanized natural rubber (NR) latex and its synthetic counterpart, isoprene rubber (IR) latex, are determined in dependence on the curing procedure (pre- and post-vulcanization). The results reveal that thiol-ene cured elastomers comprise homogenously distributed crosslinks with a low amount of short chain defects. Whilst photochemically pre-cured NR latex particles provide coherent films, the film formation and mechanical properties of IR are strongly governed by the crosslink density of the latex particles. In film state, photo-vulcanization promotes narrow crosslink distributions and excellent tensile properties of both NR and IR.     

Chitin nanocrystals reticulated self-assembled architecture reinforces deproteinized natural rubber latex film

Natural rubber (NR) latex was initially deproteinized, then, the interactions between chitin nanocrystals (ChNCs) and deproteinized natural rubber (DNR) latex particles in an aqueous system and the properties of DNR/ChNCs composites were investigated. Composite films were obtained by casting and evaporating off the prevulcanized DNR/ChNCs complexation rather than simply mixing of DNR latex and ChNCs suspension. The results of DLS and TEM confirmed that this kind of complexation was formed between negative charged DNR and positively charged ChNCs by self-assembly. The tensile strength of composite films containing 4 wt% ChNCs was 25.00 ± 1.42 MPa, which was 3.11 multiples of the pure pre-vulcanized DNR. DNR/ChNCs composite films could provide excellent mechanical properties and avoid allergies caused by proteins in NR latex.     

Thiol Addition to Epoxidized Natural Rubber: Effect on the Tensile and Thermal Properties

Epoxidized natural rubber (ENR) samples of various epoxidation degrees were synthesized from natural rubber (NR) latex, and 25 mole% epoxide of ENR was used to prepare ENR room temperature-curable films for coating applications. The films were prepared from rubber solutions. Trimethylolpropane tris(2-mercaptoacetate) (TMP-SH) was used as a curing agent. The effect of the thiol additive on the tensile and thermal properties of epoxidized natural rubber (ENR) was investigated. For the sake of comparison, NR and TMP-SH-containing formulations were also prepared.

It was observed that the addition of TMP-SH improved the tensile, thermal and swelling properties of ENR, indicating the formation of crosslinks. On the other hand, the addition of TMP-SH didn't improve the properties of NR, indicating the absence of reaction with TMP-SH. On the basis of data on the properties of the ENR films of this work it is demonstrated that these are appropriate for coating applications.     

氯化石蜡共混改性天然胶乳的研究

分别采用氯化石蜡、氯化石蜡／Sb2O3共混改性天然胶乳．考察了改性胶乳硫化胶膜的力学性能及阻燃性能．并进行了TG·DTG和DSC分析。结果表明：改性胶乳的阻燃效果比未改性天然胶乳的高．且氯化石蜡／Sb2O3共混改性天然胶乳可产生协同阻燃效果；随Sb2O3用量的增加．硫化胶膜撕裂强度增加．而拉伸强度下降。氯化石蜡／Sb2O3改性胶乳的热降解过程为二步反应．且起始热降解温度比天然胶乳的低．玻璃化转变温度提高。     

Improvements in morphology,mechanical and thermal properties of films produced by reactive blending of poly(lactic acid)/natural rubber latex with dicumyl peroxide

The effect of dicumyl peroxide (DCP) as a free-radical cross-linking agent on the morphology, thermal and mechanical properties, and gas permeation of blown films prepared by reactive blending of poly(lactic acid) (PLA) and natural rubber latex was investigated. In comparison to the blown films without DCP, SEM micrographs revealed that the amount of debonded rubber domains from the cryofractured surface reduced considerably. This was when DCP at 0.003 phr was incorporated and the free radicals from thermally decomposed DCP reacted with PLA and NR chains, generating PLA–NR copolymers and cross-linked NR as confirmed by FTIR spectra. These PLA–NR copolymers acted as compatibilizers, which increased the strength at the PLA/NR interfaces, leading to the improvement in tensile strength, elongation at break, tensile toughness, impact strength, and tear strength. Although DCP did not influence the cold crystallization of PLA, TGA thermograms showed that thermal stability slightly increased owing to the enhanced interfacial adhesion. However, the addition of DCP at 0.005 and 0.010 phr resulted in a high content of cross-linked NR gel, by consuming the free radicals instead in copolymer formation. Therefore, the compatibilization efficiency was significantly reduced and the mechanical properties of reactive PLA/NR blown films finally dropped. Also, this poor interfacial adhesion facilitated the microvoid formation at the polymer–rubber interface as a result of mechanical stretching upon the film blowing process, increasing the permeation of water vapor and oxygen molecules. According to our study, it can be summarized that to optimize the morphology, mechanical properties, and gas permeation property of the free radical-assisted reactive blends, it is of great concern to carefully balance reactive compatibilizer formation and gel formation by adjusting the DCP content.     

Carbon black filled powdered natural rubber: Preparation,particle size distribution,mechanical properties,and structures

Carbon black (HAF) filled powdered natural rubber (P(NR/HAF)) was prepared and the particle size distribution, mechanical properties, and micromorphology of P(NR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black filled free‐flowing, noncontact staining NR powders with particle diameter less than 0.9 mm. A powdering mechanism model was put forward to describe the powdering process, which shows that the key technical points consist in the surfactant with good emulsification properties and the polymer coating resin with good film forming properties. SEM analysis shows that carbon black and rubber matrix have formed a macroscopic homogenization in the P(NR/HAF) particles without contact staining, and carbon black particles are well dispersed in rubber matrix with diameter of about 50–150 nm. P(NR/HAF) vulcanizate showed better mechanical properties than bale natural rubber/carbon black blends (NR/HAF) and simple NR latex/carbon black blends (NRL/HAF), which depends primarily upon the absence of free carbon black, the fine dispersion of filler on the rubber matrix, and the better interaction between carbon black and rubber matrix due to the proper preparation condition of noncontact staining carbon black filled powdered NR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1763–1774, 2006     

Green preparation and physical properties of maleated sulfur-prevulcanized natural rubber

The maleated sulfur-prevulcanized natural rubber (M-SPNR) was prepared from grafting maleic anhydride (MA) onto SPNR latex particle by using benzoyl peroxide as an initiator. Natural rubber latex particle was vulcanized first, and then it was maleated to M-SPNR. The average particle size of M-SPNR was greater than that of SPNR possibly due to the formation of aggregate after addition of MA. The symmetric (strong) and asymmetric (weak) carbonyl stretching vibrations of succinic anhydride rings were confirmed by ATR–FTIR at 1,780–1,784 and 1,854?cm^?1, respectively. The swelling ratios of M-SPNR latex film decreased with increasing MA contents. The tensile strength, modulus, hardness, and elongation at break of SPNR latex film dramatically increased after grafting with MA. Due to the reduction of double bond, the thermal stability of M-SPNR film was better than that of SPNR. The environmental friendly M-SPNR would be further applied as a compatibilizer between NR and biopolymer.     

用作载重子午线轮胎胎面胶的炭黑填充粉末NR结构与性能研究

以天然胶乳和炭黑N234为原料,采用凝聚共沉法制备炭黑填充型粉末NR[P(NR/CB)],研究炭黑用量和不同配方对胶料硫化特性、物理性能、交联密度、微观结构、Payne效应及动态力学性能的影响,并与采用传统机械混炼法制备的炭黑/NR(CB/NR)进行对比.结果表明,与CB/NR硫化胶相比,P(NR/CB)硫化胶具有较高的拉伸强度、撕裂强度、回弹值和抗湿滑性能以及较低的滚动阻力,耐屈挠性能和耐磨性能大致相当,而动态压缩生热和压缩永久变形则降低了近50%.     

Simple dispersion of graphene incorporated rubber composite for resistive pressure sensor application

We developed a resistive pressure sensor based on stand-alone film graphene incorporated natural rubber latex (NR/G) composite fabricated in a simple solution casting method. The graphene dispersion had multilayer properties and an average lateral size of ~60 nm successfully incorporated into the NR matrix to form bilayer graphene composite with the I_2D/I_G calculated ratio of 1.301. The pressure sensor shows high sensitivity (~ 0.2 kPa⁻¹), high cycle stability, and selective response to the applied pressure with a linear relationship of ~6.0 kPa. This work shows that graphene incorporated natural rubber latex pressure sensors with applicable potentials for smart wearable devices to allow pressure detection.     

不同改性方法对天然胶乳的性能影响

分别采用氯化石蜡与Sb2O3共混改性天然胶乳、用三氯溴甲烷卤化加成改性天然胶乳、以3-溴丙烯接枝共聚改性天然胶乳,对3种不同工艺所制备的改性天然胶乳与未改性天然胶乳进行了胶体性能、阻燃性及耐溶剂性能的比较。研究结果表明：3种改性胶乳的粘度比未改性天然胶乳的要高,且接枝改性胶乳和卤化改性胶乳变化较大,共混改性胶乳的变化较少;3种改性胶乳的阻燃性能高于未改性天然胶乳的;卤化改性天然胶乳和接枝改性天然胶乳的耐溶剂性较好,而共混改性天然胶的耐溶剂性较差。     

Optimizing natural rubber blends for examination gloves: Vacuum radiation for mechanical strength and solvent barrier

Natural rubber (NR) is emblematic of sustainability compared to synthetic rubber. However, the tradition of adding sulfur as a vulcanization ingredient results in the release of toxic substances and the potential for health issues. In this study, a feasible strategy was proposed to replace sulfur and discover a safe bulk modification process for NR films. The results have shown that the NR particle size was disintegrated to below 10 nm by gamma irradiation. High tension strength up to 24.45 MPa was observed in the vulcanized NR blend film, which could be elongated up to 800% strain after exposure to an optimum dose of 14 kGy. In comparison to commercial NR latex and nitrile gloves, the vulcanized NR/ SIS films exhibited better chemical resistance ability against hexane, methanol, toluene, and acetone, as revealed by the permeation test. The appearance of amorphous regions and highly oriented NR crystallites was observed through transmission electron microscopy. Findings from this study propose the vacuum radiation strategy that can replace conventional vulcanization methods, resulting in NR films with high mechanical and barrier performance. Furthermore, the emission of toxic substances is reduced by this green process, making it practically useful for potential chemical-resistant examination glove applications.     

Degradability testing of radiation-vulcanized natural rubber latex films

The degradability under various conditions of five kinds of radiation-vulcanized natural rubber latex (RVNRL) films was studied. The treatments were leaching in methanol, leaching in 1% ammonia solution, mixing with tris(nonylated phenyl)phosphite (TNP) antioxidant, blending with poly(methyl methacrylate) (PMMA), and grafting with PMMA, Comparisons were made with sulfur-vulcanized natural rubber latex (SVNRL) film. RVNRL films SVNRL film can be kept for a long time when indirectly exposed to sunlight at room temperature. However, the former degraded much more rapidly than did the latter. TNP was found to be very suitable as an antioxidant to prolong the life of RVNRL films under dry conditions. PMMA, either blended or grafted with RVNRL, was ineffective in the prevention of deterioration of RVNRL films. The rapid degradation of RVNRL products could be an advantage over SVNRL products in environmental and wildlife conservation. © 1994 John Wiley & Sons, Inc.     

硫化NR胶乳胶膜的结构与性能研究

对不同硫化体系和硫化方式硫化的ＮＲ胶乳胶膜的结构与性能进行研究。结果表明：采用不同硫化体系的硫化胶乳所形成的硫交联键主要的为多硫键,硫化胶乳胶膜的结构对性能的影响因硫化方式不同而有差异。     

Blends of natural rubber and polyurethane latices studied by 1H wideline and 13C MAS solid‐state NMR

¹H wideline and ¹³C magic‐angle spinning NMR have been used to study the morphology and dynamics of latex‐cast and solution‐cast film blends of natural rubber (NR) and a polyurethane (PU) based on poly(?‐caprolactone) diol and isophorone di‐isocyanate. ¹H T₁ and T_1ρ relaxation times have been measured, and the extent of interpenetration of the NR and PU constituents has been monitored using the Goldman–Shen technique. The NMR spectra and relaxation properties indicated that the NR and PI constituents largely occupy separated domains on a distance scale of >10 nm. The Goldman–Shen experiments indicated that there was slightly greater contact between NR and PU in the solution‐cast samples than in the latex‐cast. The tensile properties of the films have been measured. The tensile strength and initial Young's modulus pass through a maximum at a PU content of about 50 wt%. © 2002 Society of Chemical Industry