One‐step latex compounding method for producing composites of natural rubber/epoxidized natural rubber/aminosilane‐functionalized montmorillonite: enhancement of tensile strength and oil resistance

Montmorillonite (Mt) was intercalated with cetyltrimethylammonium bromide and functionalized with three types of aminosilane (3‐aminopropyltrimethoxysilane, n‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane and 3‐[2‐(2‐aminoethylamino)ethylamino]propyltrimethoxysilane). The modified Mt was compounded with natural rubber (NR)/epoxidized natural rubber (ENR) via one‐step latex compounding. The effect of the modified Mt content on the oil resistance and mechanical properties of the NR/ENR/modified Mt composites was investigated. The X‐ray diffraction patterns of the composites showed partial intercalation/exfoliation of the modified Mt in the rubber matrix. Cryogenic fracture and X‐ray fluorescence results revealed highly dispersed modified Mt in the composites in the presence of 10 phr ENR. All three aminosilane groups slightly improved the oil resistance, with the long‐alkyl‐length group producing the greatest improvement. The addition of a small amount of modified Mt improved both oil resistance and tensile strength by increasing in the average diffusion path length in the NR matrix and enhancing the interaction between the modified Mt and the epoxide groups in ENR. The addition of 1.0 phr of modified Mt increased the tensile strength by 18% and decreased the elongation at break by 12% compared with a neat NR/ENR blend. © 2017 Society of Chemical Industry     

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     

溴化丁基橡胶/酚醛硫化树脂复合胶乳的制备与硫化

通过溶液乳化法制备了固含量为9.3%的溴化丁基橡胶/酚醛硫化树脂复合胶乳.以海藻酸钠为膏化剂对复合胶乳进行了膏化浓缩,研究了膏化剂用量对膏化时间、胶乳固含量和胶乳粒径的影响,结果表明膏化浓缩胶乳粒径较大,膏化周期较长,一般需半个月左右才能得到实用的浓缩胶乳.采用扫描电镜观察了复合胶乳干胶膜的断面形貌,发现大粒径的膏化胶乳成膜后胶粒间可以较好地融合.通过涂布、烘干和硫化等工艺制备了厚度为0.60 mm的复合胶乳硫化膜片,并测试了硫化膜片的力学性能和H2渗透性能,结果表明硫化膜片的力学性能较好,其H2渗透率较低,为天然橡胶的9.64%、氯丁橡胶的71.3%.     

Molecular-level dispersion of graphene into epoxidized natural rubber: Morphology,interfacial interaction and mechanical reinforcement

The interfacial interaction of composites dominates the properties of polymeric/inorganic nanocomposites. Herein, epoxy and hydroxyl groups are introduced into the natural rubber (NR) molecular chains to anchor oxygenous functional groups on the surface of graphene oxide (GO) sheets and therefore enhance the interfacial interaction between GO and rubber. From the morphological observation and interaction analysis, it is found that epoxidized natural rubber (ENR) latex particles are assembled onto the surfaces of GO sheets by employing hydrogen bonding interaction as driving force. This self-assembly depresses restacking and agglomeration of GO sheets and leads to homogenous dispersion of GO within ENR matrix. The formation of hydrogen bonding interface between ENR and GO demonstrates a significant reinforcement for the ENR host. Compared with those of pure ENR, the composite with 0.7 wt% GO loading receives 87% increase in tensile strength and 8.7 fold increase in modulus at 200% elongation after static in-situ vulcanization.     

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     

原位聚合法制备高透光率韧性PMMA复合树脂的研究

采用原位聚合法制备PMMA/P(BA-St)/PMMA三层韧性有机玻璃复合树脂,分子设计方法的使用,保持了材料的透明性。考察了韧性粒子粒径、橡胶相组成以及橡胶含量对材料力学和光学性能的影响。借助透射电镜、扫描电镜和动态光散射方法对复合胶乳粒子以及所制材料的形态结构进行了表征。结果表明:橡胶相的折光指数对材料的透光率有明显影响,橡胶相玻璃化温度越低,越有利于增韧。     

Thermoplastic natural rubber based on polyamide‐12: Influence of blending technique and type of rubber on temperature scanning stress relaxation and other related properties

Thermoplastic natural rubber based on polyamide‐12 (PA‐12) blend was prepared by melt blending technique. Influence of blending techniques (i.e., simple blend and dynamic vulcanization) and types of natural rubber (i.e., unmodified natural rubber (NR) and epoxidized natural rubber (ENR)) on properties of the blends were investigated. It was found that the simple blends with the proportion of rubber ～ 60 wt % exhibited cocontinuous phase structure while the dynamically cured blends showed dispersed morphology. Furthermore, the blend of ENR exhibited superior mechanical properties, stress relaxation behavior, and fine grain morphology than those of the blend of the unmodified NR. This is attributed to chemical interaction between oxirane groups in ENR molecules and polar functional groups in PA‐12 molecules which caused higher interfacial adhesion. It was also found that the dynamic vulcanization caused enhancement of strength and hardness properties. Temperature scanning stress relaxation measurement revealed improvement of stress relaxation properties and thermal resistance of the dynamically cured ENR/PA‐12 blend. This is attributed to synergistic effects of dynamic vulcanization of ENR and chemical reaction of the ENR and PA‐12 molecules. Furthermore, the dynamically cured ENR/PA‐12 blend exhibited smaller rubber particles dispersed in the PA‐12 matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Blends of Epoxidized Natural Rubber with Chloroprene Rubber

Blends of ENR (epoxidized natural rubber) with CR (chloroprene rubber) were prepared throughout the composition, and important properties of the vulcanizates, both unaged and aged (air and oil) rubber, were determined. Dynamic measurement showed a single tan δ peak for the blends, and the peak temperature monotonically decreased with increasing CR content, resulting also in an increase of resilience at room temperature. Flex crack resistance of CR above room temperature, and oil resistance of ENR were increased in the blends.     

Preparation and Properties of Siloxane-Modified Styrene-Acrylate Latex Particles with Core-Shell Structure

Siloxane-modified styrene-acrylate latex particles with core-shell structure were prepared by two-stage semicontinuous emulsion polymerization using a reactive surfactant. Effects of catalyst dosage, weight ratio of γ-methacryloxypropyltrimethoxysilane (MAPS) to hydroxyl silicone oil (HSO) and siloxane content on the grafting degree of siloxane were studied. The chemical components of the copolymer were characterized by Fourier transform infrared spectra. The micromorphology of latex particles was observed by transmission electron microscopy. The stability properties of emulsion were tested by Ca²⁺, centrifugal, and mechanical stability test. The latex film was studied by water contact angle, water absorption ratio and thermal gravimetric analysis. The results show that siloxane-modified styrene-acrylate latex with core-shell structure can be synthesized using reactive surfactant and the prepared emulsion presents excellent stability. By using hydroxyl silicone oil (HSO) to react with silane coupling agent MAPS during emulsion polymerization, HSO can be located in the side chain of the polymer and endow the latex film with excellent stabilities.     

Effect of the composition of structured rubber particles on the toughness of poly(methylmethacrylate)

Composite natural rubber (NR) and monodisperse poly(n-butylacrylate) (PBuA) based latex particles were tested as possible impact modifiers for a poly(methylmethacrylate) (PMMA) matrix. A continuous extrusion process was used for the incorporation of wet latexes directly into a twin-screw extruder. All latexes had been coated by a PMMA shell. Furthermore, polystyrene (PS) subinclusions were introduced into the NR core. The impact resistance of the prepared PMMA blends can be most effectively improved by NR particles containing a large weight fraction of compatibilising PMMA in the shell. The degree of crosslinking of the shell polymer has to be restricted. PBuA based latex particles of 180 nm in size are ineffective to toughen the PMMA matrix. The degree of grafting of the NR phase in core–shell particles containing PS subinclusions is not crucial. Scanning electron microscopy was used to analyse the failure processes in composite rubber particle toughened PMMA blends at fast (impact conditions) and slow (tensile testing) deformation speeds.     

就地反应法制备天然橡胶/二氧化硅复合材料

在天然胶乳与Na2SiO3水溶液的混合体系中滴加盐酸,就地生成SiO2粒子,并与天然橡胶(NR)同时发生凝聚共沉,获得了NR/SiO2透明复合材料。用扫描电子显微镜和分光光度计分析了材料的结构,测定了硫化胶的力学性能。结果表明,SiO2的粒径随混合体系中Na2SiO3投料量的提高而增大,并均匀分布于NR基体中;当复合材料中SiO2用量为25～54份时,SiO2的粒径为100～200nm;在SiO2用量适宜的条件下,复合材料硫化胶具有良好的力学性能;硫化胶片具有一定的透明性,在波长为600～800nm时,其透光率为50%～72%。     

Mechanical properties and blend compatibility of natural rubber –chlorosulfonated polyethylene blends

Natural rubber (NR) was blended with chlorosulfonated polyethylene (CSM) with various formulation and blend ratios (NR/CSM: 80/20 –20/80, wt/wt). Rubber blends were prepared by using a two‐roll mill and vulcanized in a compression mold to obtain the 2 mm‐thick sheets. Tensile properties, tear resistance, thermal aging resistance, ozone resistance, and oil resistance were determined according to ASTM. Compatible NR/CSM blends are derived from certain blends containing 20–30% CSM without adding any compatibilizing agent. Tensile and tear strength of NR‐rich blends for certain formulations show positive deviation from the rule of mixture. Thermal aging resistance depends on formulation and blend ratio, while ozone and oil resistance of the blends increase with CSM content. Homogenizing agents used were Stuktol®60NS and Epoxyprene®25. Stuktol®60NS tends to decrease the mechanical properties of the blends and shows no significant effect on blend morphology. Addition of 5–10 phr of epoxidized natural rubber (ENR, Epoxyprene® 25) increases tensile strength, thermal aging resistance, and ozone resistance of the blends. It is found that ENR acts as a compatibilizer of the NR/CSM blends by decreasing both CSM particle size diameter and α transition temperature of CSM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 127–140, 2006     

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.     

The effect of epoxidized natural rubber on mechanical properties of siliceous earth/natural rubber composites

Siliceous earth (SE) is a kind of mineral consisting of lamellar kaolinite, muscovite (aluminum silicate) and corpuscular silica. Natural rubber (NR) composites containing NR as matrix, epoxidized natural rubber (ENR) as compatibilizer and SE as filler were produced by latex coagulating process and cured using a conventional sulfuric system. Monsanto measurements have shown that the ENR accelerates the vulcanization reaction and gives rise to a marked increase of the torque. The results of physico-mechanical properties of NR vulcanizates show that, when SE modified by silane coupling agent and in the meanwhile adding 4 phr of ENR as compatibilizer, maximum tensile strength, elongation at break, reinforcing index (M300/100) of NR/SE vulcanizates were obtained. The dynamic-mechanical properties exhibit the addition of ENR can enhance wet grip characteristics and reduce rolling resistance by lowering tan δ values at 60 °C and increasing tan δ values at 0 °C of NR compounds. The overall results show that properties of SE-reinforced NR substantially improved by adding ENR as compatibilizer. The addition of silane coupling agent and combining an appropriate amount of ENR would be better choice to improve the properties of NR/SE compounds.     

Thermoplastic elastomers-based natural rubber and thermoplastic polyurethane blends

Thermoplastic elastomers based on the blends of thermoplastic polyurethane (TPU) and natural rubber were prepared by a simple blend technique. The influence of the two different types of natural rubber (i.e., unmodified natural rubber (NR) and epoxidized natural rubber (ENR)) on properties of the blends was investigated. The main aim of this study was to improve heat resistance and damping properties, and also to prepare the TPU material with low hardness by blending with various amounts of natural rubber. It was found that the TPU/ENR blends exhibited superior modulus, hardness, shear viscosity, stress relaxation behavior and heat-resistant properties compared to the blends with TPU and unmodified NR. This was attributed to higher chemical interaction between the polar functional groups of ENR and TPU by improving the interfacial adhesion. It was also found that the ENR/TPU blends exhibited finer grain morphology than the blends with unmodified NR. Furthermore, lower tension set, damping factor (Tan ??) and hardness, but higher degradation temperature, were observed in natural rubber/TPU blends compared to pure TPU. This proves the formation of TPU material with high heat resistance, low hardness and better damping properties. However, the blends with higher proportion of natural rubber exhibited lower tensile strength and elongation at break.     

环氧化天然橡胶复合材料性能研究

采用新方法制备环氧化天然橡胶(ENR)/白炭黑和天然橡胶(NR)/ENR/白炭黑复合材料,并对其性能进行研究。结果表明:ENR/白炭黑复合材料的热稳定性优于ENR;在NR/ENR并用胶中加入白炭黑和硅烷偶联剂KH-550,NR/ENR/白炭黑复合材料0℃时的损耗因子(tanδ)增大,65℃时的tanδ值减小,复合材料的抗湿滑性能提高,滚动阻力减小。     

Epoxidized natural rubber‐bonded para rubber wood particleboard

Para rubber wood particleboard (PB) was prepared using NR based adhesives and hot pressing processes. Two types of NR based adhesives were used; epoxidized natural rubber (ENR) and unmodified NR. The ENR latex was prepared using in situ performic epoxidation. Molecular weight of the ENR molecules was then reduced by incorporating of a reducing agent; sodium nitrite solution. A chain scission reaction and epoxidation simultaneous occurred via a chain‐scission parallel epoxidation mechanism. Sulphur and multifunctional amine (i.e., hexamethoxymethylmelamine) curing systems were used to cure the adhesives. It was found that the hexamethoxymethylmelamine gave the PB with higher tensile strength than that of the sulphur vulcanization system. Furthermore, the tensile strength increased with increasing concentration of citric acid in the compounding formulation. Adhesion of the ENR adhesive with Parawood sawdust was observed to imporve by reducing molecular weight of the ENR molecules. That is, the highest tensile strength of the PB was observed for the ENR adhesive with the lowest (i.e., 1.10 × 10⁵). This may be attributed to the adhesive with lower molecular weight exhibited greater ability to wet or cover the wood particle surfaces. As a consequence, greater chemical interaction between the adhesive and the wood particles was observed. POLYM. ENG. SCI., 47:421–428, 2007. © 2007 Society of Plastics Engineers.     

淀粉/天然橡胶复合材料的结构与热稳定性研究

将淀粉进行糊化改性,将改性淀粉在乳液状态下与天然胶乳共混,制备淀粉/天然橡胶复合材料。利用扫描电镜(SEM)和热重分析(TG)表征复合材料的结构,并测定了其力学性能。研究结果表明:淀粉经糊化后,淀粉粒子在天然橡胶中分散均匀,粒径明显减小,复合材料的热稳定性和力学性能明显提高。     

淀粉/天然橡胶复合材料的研究

将淀粉进行糊化改性,将改性淀粉在乳液状态下与天然胶乳共混,制备淀粉/天然橡胶复合材料。用X-射线衍射（XRD）、差示扫描量热仪（DSC）和扫描电镜（SEM）表征复合材料的结构,并测定了其力学性能。研究结果表明：淀粉经糊化后,复合材料中淀粉粒子的结晶结构消失,粒子在天然橡胶中分散均匀,粒径明显减小。随着淀粉含量的增加,复合材料的硬度、定伸应力、拉伸强度和撕裂强度随之提高,且当其质量分数在20%时,复合材料的综合力学性能最佳。     

Preparation and morphological characterization of two- and three-component natural rubber-based latex particles

Different emulsion polymerization processes allowed variation in the microstructure of composite natural rubber (NR)-based latex particles. A prevulcanized and a not-crosslinked natural rubber latex were coated with a shell of crosslinked poly(methyl methacrylate) (PMMA) or polystyrene (PS). The bipolar redox initiating system tert-butyl hydroperoxide/tetraethylene pentamine promoted a core–shell arrangement. Furthermore, PS subinclusions were introduced into the NR core. The initiators used for the subinclusion synthesis were azobisisobutyronitrile at high temperature and a redox initiation system consisting of tert-butyl hydroperoxide/dimethylaniline at low temperature. The morphology of the resulting latex interpenetrating networks (IPN) was characterized by transmission electron micros-copy (TEM) and scanning electron microscopy (SEM). Different staining methods allowed us to increase the contrast between the NR phase and the secondary polymers in the composite latex particles. A semicontinuous feeding process decreased the PS subinclusions size by a factor of 6 in comparison with a batch reaction. Depending on the NR/styrene swelling ratio, the crosslinking degree, and the polymerization temperature used, distinct differences of the phase arrangement of polymers in the latex particles were revealed. © 1996 John Wiley & Sons, Inc.