Creaming skim natural rubber latex for encapsulation of urea fertiliser

Abstract

Skim natural rubber latex has been characterised before crosslinking with γ-radiation. Micrographs of γ-vulcanised skim particles embedded in polystyrene revealed a semi-interpenetrating polymer network morphology of fine rubber–polystyrene particles surrounded by membrane layer. Creamed skim latex was prepared by addition of 15–45 phr sodium alginate and further used for encapsulation of urea fertiliser. Non-spherical capsules containing an homogeneous urea dispersion were obtained.     

Noncatalytic hydrogenation of natural rubber latex

Hydrogenation is an important method of chemical modification, which improves the physical, chemical, and thermal properties of diene‐based elastomers. Natural rubber latex (NRL) could be hydrogenated to a strictly alternating ethylene–propylene copolymer using diimide generated in an in situ system. The diimide generated using the in situ technique for hydrogenation of NRL was accomplished by thermolysis of p‐toluenesulfonyl hydrazide (TSH). A molar ratio of TSH to double bonds equal to 2 : 1 was found to be the optimum ratio to provide a high percentage of hydrogenation. 95% Degree of saturation of NRL was achieved in o‐xylene. Hydrogenated products are characterized by FTIR and NMR spectroscopy. The thermal stability of hydrogenated rubber was improved as shown from the results of thermogravimetric analysis. From the differential scanning calorimetry measurement, the glass transition temperature of the hydrogenated product did not appear to change. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2885–2895, 2007     

Extraction of protein from skim natural rubber latex using PEG as a surfactant via low speed centrifugation and continuous flow

Protein extractions from skim natural rubber latex using 3 %w/v polyethylene glycol (PEG6000) via both low speed centrifugation and continuous flow were investigated. In centrifugal extraction, when the speed was 1000 rpm, the extractable protein (EP) content in serum increased with processing time from 5 to 30 min and when the time was fixed at 5 min, EP content increased with centrifugal speed. In addition, further washing deproteinized chips with 2 %w/v SDS solution could remove proteins with efficiencies corresponding to the efficiencies of protein removals in latex phase, implying the role of PEG in protein reduction in both steps. In continuous flow extraction, EP content increased with increasing Reynolds number or increasing mean residence time of the flow to a maximum and then dropped. The efficiencies of the centrifugal extraction and continuous flow extraction were 55.2 and 33.7%, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39900.     

Study of chitosan and its derivatives as preservatives for field natural rubber latex

In this study, the chitosan and its derivatives were tested for their preservative activities for field natural rubber (NR) latex. A series of chitosans with different molecular weights were obtained by nitrous acid depolymerization. The chemically modified chitosans, N‐carboxymethyl chitosan (NCMCh), N‐sulfated chitosan (NSCh), and N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (NHTACh), were prepared from high and low‐molecular weight chitosans. Preservative activities for field NR latex of these chitosans were investigated based on the measurement of volatile fatty acids (VFA) number of the treated latex. The preservative activities of chitosan increased with decreasing molecular weights. The low‐ molecular weight NSCh and NHTACh exhibited good preservative activity for the latex. By the use of low‐molecular weight NHTACh in combination with octylphenol poly (ethyleneglycolether) (Nonidet P40), the latex was successfully preserved for more than 1 month in the low‐ammonia condition. The results showed an attractive feature to develop the preservative system, which was possible to reduce the concentrations of ammonia and carcinogenic nitrosamine in the NR latex. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of biodegradable natural rubber latex composites by employing corn derivative bio-fillers

This study aims to investigate the viability of employing corn-based fillers (powdered corn grain [CG], corn flour [CF] and cornstarch [CS]) to improve the biodegradability of natural rubber latex (NRL) composites by varying filler loading from 0 to 50 phr. Notable variation in both physical and mechanical properties were observed for the different filler types, with CG-filled NRL demonstrating the better adhesion with NRL. Thus, CG-filled composites were selected for investigation of biodegradability. Increased CG loading in NRL compounds enhanced biodegradation; with over 70% degradation observed for 50 phr CG loading upon 15 weeks of soil burial. However, the trade-off between mechanical properties and biodegradability limits the CG loading in the NRL matrix to 20 phr for manufacturing NRL-based products. It was observed that NRL with CG filler loading of 20 phr conforms to the ASTM D3578 standard for manufacturing rubber gloves; with 50% biodegradation upon 15 weeks of soil burial.     

天然胶乳改性研究进展

介绍了天然胶乳的特点,综述了天然胶乳填料改性（纳米粒子改性和非纳米粒子改性）及化学改性（氯化、环化、环氧化、接枝聚合）的研究进展,分析了目前天然胶乳改性存在的问题,并展望了未来的发展趋势。     

Preparation and characterization of organoclay‐rubber nanocomposites via a new route with skim natural rubber latex

Skim natural rubber latex (SNRL) is a protein rich by‐product obtained during the centrifugal concentration of natural rubber (NR) latex. A new method to recover rubber hydrocarbon and to obtain nanocomposites with organoclay (OC) was investigated. The approach involved treatment of SNRL with alkali and surfactant, leading to creaming of skim latex and removal of clear aqueous phase before addition of OC dispersion. Clay mixed latex was then coagulated to a consolidated mass by formic acid, followed by drying and vulcanization like a conventional rubber vulcanizate. X‐ray diffraction (XRD) studies revealed that NR nanocomposites exhibited a highly intercalated structure up to a loading of 15 phr (parts per hundred rubber) of OC. Transmission electron microscopy studies showed a highly exfoliated and intercalated structure for the NR nanocomposites at loadings of 3–5 phr organically modified montmorillonite (OMMT). The presence of clay resulted in a faster onset of cure and higher rheometric torque. The rubber recovered from skim latex had a high gum strength, and a low amount of OC (5 phr) improved the modulus and tensile strength of NR. The high tensile strength was supported by the tensile fractography from scanning electron microscopy. Thermal ageing at 70°C for 6 days resulted in an improvement in the modulus of the samples; the effect was greater for unfilled NR vulcanizate. The maximum degradation temperature was found to be independent of the presence and concentration of OC. The increased restriction to swelling with the loading of OC suggested a higher level of crosslinking and reinforcement in its presence. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3277–3285, 2006     

Maillard reaction in natural rubber latex: Improvement of concentration process

Maillard reaction in natural rubber (NR) latex was studied by treating fresh latex with formaldehyde and glutaraldehyde. Volatile fatty acid number of the treated latex could be lower than acceptable limit (< 0.08) for more than 20 days. Attenuated total reflectance infrared spectroscopy and sodium dodecyl sulfate polyacrylamide gel electrophoresis revealed the occurrence of protein crosslinks in the treated latex. NR treated with glutaraldehyde has much higher nitrogen content than NR treated with formaldehyde and untreated NR, respectively. Colloidal stability of rubber particles, represented by pH, zeta potential, viscosity, and particle size distribution information, were unchanged after treating the latex with formaldehyde. Treatment of the fresh latex with glutaraldehyde 100 and 200 mmol/kg of latex led to the aggregation of rubber particles. Interestingly, the Maillard crosslinking of proteins in fresh latex could efficiently promote the transfer of rubber particles from the serum phase into the cream phase during centrifugation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45224.     

无氨保存胶清及胶清胶性能的研究

采用水溶性、不挥发性的广谱抗菌剂——三嗪衍生物(HY)作为鲜胶乳的新型无氨保存剂,研究了HY对胶清凝固总用酸量、胶清胶及胶清胶硫化胶片性能的影响。结果表明,HY保存胶清凝固总用酸量大大减少,除氮含量略微超标外,胶清胶的各项指标均达到1级胶清胶的标准,胶清胶的塑性保持率(PRI)明显提高。HY胶清胶硫化胶片的拉伸强度和耐热氧老化能力均优于氨胶清胶硫化胶片。热解重量分析(TGA)结果表明,HY和氨胶清胶硫化胶片热氧降解均为2步反应,耐热氧降解能力基本相同。     

Mechanical properties of thermoplastic elastomeric blends of chitosan and natural rubber latex

Thermoplastic chitosan/natural rubber blends (Cs/NR) were prepared from natural rubber latex and chitosan by solution casting technique. The blends were characterized by mechanical analysis (stress–strain) and the mechanical properties were found to vary with chitosan/natural rubber ratios. Experimental values were compared with different theoretical models. Effect of thermal aging on mechanical properties was also investigated. Dicumyl peroxide was used as the crosslinking agent. The effect of crosslinking on mechanical properties of Cs/NR has also been studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Antibacterial Polyelectrolytic chitosan derivatives conjugated natural rubber latex films with minimized bacterial adhesion

Water soluble polyelectrolytic derivatives of chitosan (CDs) with carboxyl (COO⁻) and quaternary ammonium (NH₄⁺) groups were synthesized and characterized by NMR, FT-IR, TGA and zeta potential analyses; while degree of substitution was determined by potentiometric titrations. Both CDs in the as-synthesized form exhibited antibacterial zones against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The CD conjugated vulcanized natural rubber latex (NRL) films were investigated for understanding the level of bacterial adhesion and bactericidal properties as a function of the polyelectrolytic groups present. NRL Films modified at ambient conditions were found effective against Pseudomonas aeruginosa (P. aeruginosa). The biofilm assay results demonstrate that CD conjugated samples exhibit significantly reduced adhesion (63.8%) against P. aeruginosa. Further, alterations observed in cellular morphology of attached bacteria indicate that the modified surface of films is bacteriocidal while presence of significantly higher level of extra cellular polymer substances (EPS) were detected on control NRL films.     

Comparative study of the elasticity and permeability of vulcanized films made with skim and cream natural rubber latex

The purpose of this study was to gain a clearer picture of the structure and properties of vulcanized films made with skim and cream latex from Hevea brasiliensis. The two properties targeted for this study were the elasticity of the films and their permeability to acetone. Surface characterization by atomic force microscopy revealed that vulcanization substantially modified the structure of the films compared to unvulcanized films. Unlike unvulcanized films, particle identity was retained in the vulcanized films made with cream latex, even after 4 weeks of aging. In addition, skim latex gave vulcanized films with greater elasticity than those obtained with cream latex. On the basis of the structural characterization carried out on the latex and films and information from the literature, the greater elasticity of the skim films arose from more entanglements between polyisoprene chains and associations between proteins. Despite differences in the structure, the acetone permeability was very similar for skim and cream vulcanized films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel method for toughening of polystyrene based on natural rubber latex

γ‐Radiation vulcanized natural rubber latex/phase transfer/bulk polymerization is a novel process for the preparation of toughened polystyrene based on natural rubber latex. The negatively charged γ‐radiation vulcanized natural rubber latex was first titrated with benzyldimethylhexadecylammonium chloride in the presence of a styrene monomer. At a critical transfer concentration, the crosslinked rubber particles transferred from the aqueous phase into the styrene phase in which they swelled, depending on the irradiation dose used. By bulk polymerization of the styrene phase containing transferred particles, the polymer blends exhibited two‐phase morphology similar to that of commercial high‐impact polystyrene that was microscopically obtained. The final product showed an increase in the unnotched Izod impact energy over the unmodified polystyrene. The effect of irradiation dose, rubber content, and initiator concentration on the impact property and morphology of toughened polystyrene prepared was investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1333–1345, 1999     

热裂解气相色谱法测定天然胶乳中的干胶含量

研究热裂解气相色谱法测定天然胶乳中的干胶含量。试验结果表明,干胶含量与裂解主要产物峰面积呈现良好的线性关系,采用标准曲线法测定天然胶乳中的干胶含量,重复测定的相对标准偏差为0.14%,与国标法的平均相对误差为1.51%,定量分析结果准确,操作简便。     

Biopolymers as effective fillers in natural rubber: Composites versus biocomposites

Biocomposites of natural rubber (NR) blends were prepared with a variety of fillers obtained from renewable resources by a mastication technique. They were characterized for their mechanical properties and morphologies and compared with composites of the conventional filler carbon black (c‐black). The biopolymers exhibited an interesting trend and imparted strength to NR that was quite comparable to c‐black. Up to 30 phr of the fillers could be successfully incorporated; this led to enhancements in the mechanical strength. The properties were found to vary with the type and ratio of filler, namely, starch, cellulose, and chitin. The optimum mechanical strength of the biocomposites was observed at 10 phr. The results were interpreted on the basis of the morphology by scanning electron microscopy, which revealed strong filler–polymer interactions. The moisture‐uptake characteristics of the composites were studied. It was found that addition of biofillers did not lead to a significant increase in the moisture absorption. Furthermore, as the adhesion between the polymer matrix and fillers increased, the water uptake decreased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Oil resistance and physical properties of in situ epoxidized natural rubber from high ammonia concentrated latex

Epoxidized natural rubber (ENR) was prepared via in situ epoxidation from high ammonia concentrated natural rubber latex with formic acid and hydrogen peroxide in the presence of a surfactant at 50°C for 4, 8, and 12 h. The obtained ENRs containing 20, 45, and 65 mol % of expoxide groups were denoted ENR20, ENR45, and ENR65, respectively. The differential scanning calorimetric study revealed that they exhibited higher glass transition temperatures than that of natural rubber (?62.4°C), at ?38.2°C for ENR20, ?27.8°C for ENR45, and ?19.7°C for ENR 65. It was clearly seen that their glass transition temperatures increased as the amount of epoxide groups increased. The prepared ENRs were compounded and vulcanized to prepare test specimens for determination of oil resistance and various physical properties. It was found that the swelling of ENRs in oils was substantially less than that of natural rubber. The oil resistance of ENR65 was comparable to that of nitrile rubber, commonly used as oil resistant rubber. ENR65 also showed higher hardness than other ENRs. Contrarily, ENR20 possessed superior tensile strength and compression set when compared with other ENRs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3948–3955, 2006     

Diimide hydrogenation of natural rubber latex

Hydrogenation is one important method of chemical modification, which improves the physical, chemical and thermal properties of diene‐based elastomers. Natural rubber latex (NRL) could be hydrogenated to a strictly alternating ethylene‐propylene copolymer using a diimide reduction system. The diimide reduction technique of NRL was accomplished by using hydrazine hydrate/hydrogen peroxide and Cu²⁺ as catalyst. The hydrogenated products are characterized by FTIR and NMR spectroscopy. It has been found that cupric acetate is a highly active catalyst for the reaction and the addition of a controlled amount of gelatin demonstrated a beneficial effect on the degree of hydrogenation, whereas, sodium dodecyl sulfate (SDS) acted as a stabilizer of the latex particle in the reaction system and reduced the degree of hydrogenation. In the presence of SDS, a longer reaction time and a higher amount of hydrazine hydrate was required for hydrogenation of NRL. Gel formation during hydrogenation does not significantly affect the degree of hydrogenation. Gel inhibitors such as hydroquinone also decrease the degree of hydrogenation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nanocapsules embedded in natural rubber latex gloves

To prepare medical gloves containing disinfectant agent, poly(methyl acrylate) (PMA) with _w of 550 K was synthesized via the iniferter technique and then used for encapsulating disinfectant agent, i.e., chlorhexidine digluconate (CHD), droplets. The CHD‐PMA nanocapsules suspended in a sodium dodecyl sulfate aqueous solution having 93% encapsulation efficiency were successfully embedded between the outermost and inner layers of γ‐radiation vulcanized natural rubber (RVNR) latex films by the coagulant dipping process. A RVNR/CHD‐PMA nanocapsules/RVNR three‐layer structure was revealed by the contact angle measurement, ATR‐FTIR and SEM. Both the tensile strength and elongation at break of the three‐layer film were also measured. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

弱酸铵盐保存天然鲜胶乳的研究

通过对弱酸铵盐性质的分析，探索弱酸铵盐对鲜天然胶乳的保存效果及其性能的影响。实验结果表明，浓度越高的碳酸铵盐溶液的保存体系，其缓冲能力越大．越能很好地中和细菌代谢产生的脂肪酸．以防止天然胶乳的迅速凝固，保存效果越好。综合考虑经济和社会效益，碳酸铵可作为天然胶乳的保存剂，最佳质量分数为1．8％，其硫化胶力学性能得到部分改善，可以代替传统的氨水保存剂，降低污染，提高经济效益，改善工厂作业环境。     

Preparation and thermal stability of brominated natural rubber from latex

The effects of pH value of reaction system, reaction time, reaction temperature, bromine concentration, and amount of potassium persulfate on the bromination reaction in the preparation of brominated natural rubber (BNR) from natural rubber latex were discussed. It has been found from the thermal analysis, that is, the thermal degradation of BNR in nitrogen is a two‐step reaction, and 16% carbonide with a stable structure remained at 470–650°C. The thermo‐oxidative degradation of BNR in air is also a two‐step reaction, and the percentage of degraded BNR reaches to nearly 100% at 600°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010