Processability characteristics and physico‐mechanical properties of natural rubber modified with rubber seed oil and epoxidized rubber seed oil

The processability characteristics and physico‐mechanical properties of natural rubber (NR) modified with raw rubber seed oil and epoxidized rubber seed oil have been studied. The modified mixes showed higher scorch time and lower cure rate, crosslink density, and ultimate state of cure compared to an unmodified mix. The thermal stability of the vulcanizates was practically unaffected by the modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1413–1418, 2000     

Curing Characteristics,Fatigue and Hysteresis Behaviour of Feldspar Filled Natural Rubber Vulcanizates

Curing characteristics, fatigue, and hysteresis behaviour of feldspar filled SMR L vulcanizates and feldspar filled ENR 50 vulcanizates were studied. Two different types of natural rubber, SMR L and ENR 50 having 0 and 50 mol% of epoxide groups were used. The feldspar filled natural rubber vulcanizates were compared at similar filler loading which were used at 0, 10, 20, and 30 phr of filler loading. The curing characteristics such as scorch time (t ₂) and cure time (t ₉₀) slightly increased with increasing feldspar loading for both rubber vulcanizates. Besides t ₂ and t ₉₀, maximum torque (M _HR) significantly increased for both rubbers with increasing feldspar loading. The fatigue test showed that fatigue life decreased with increasing extension ratio, strain energy and filler loading. As the filler loading increased, the poor wetting of the feldspar by the rubber matrix gave rise to poor interfacial adhesion between filler and rubber matrix. Results also indicate that the vulcanizates with the highest feldspar loading exhibited the highest hysteresis. The feldspar filled SMR L vulcanizates showed higher fatigue life and lower hysteresis compare to feldspar filled ENR 50 vulcanizates.     

用甲基丙烯酸原位改性纳米碳酸钙填充三元乙丙橡胶Ⅰ.交联剂和甲基丙烯酸用量的影响

用甲基丙烯酸(MAA)原位改性纳米碳酸钙填充三元乙丙橡胶(EPDM),制备了纳米碳酸钙增强EPDM硫化胶。考察了过氧化二异丙苯(DCP)用量和MAA用量对EPDM硫化性能和物理机械性能的影响,研究了硫化胶的应力弛豫行为。结果表明,MAA的引入降低了EPDM的焦烧时间,但未对硫化速率产生明显影响;EPDM硫化胶具有较好的物理机械性能,当MAA用量为1.2质量份时,其拉伸强度可达25.6 MPa。此外,EPDM硫化胶的应力弛豫程度和速率都随着MAA的加入而增大。     

Reinforcement of peroxide‐cured styrene–butadiene rubber vulcanizates by mathacrylic acid and magnesium oxide

Through the neutralization of magnesium oxide (MgO) and methacrylic acid (MAA), magnesium methacrylate [Mg(MAA)₂] was in situ prepared in styrene–butadiene rubber (SBR) and used to reinforce the SBR vulcanizates cured by dicumyl peroxide (DCP). The experimental results show that the mechanical properties, dynamic mechanical properties, optical properties, and crosslink structure of the Mg(MAA)₂‐reinforced SBR vulcanizates depend on the DCP content, Mg(MAA)₂ content, and the mole ratio of MgO/MAA. The formulation containing DCP 0.6–0.9 phr, Mg(MAA)₂ 30–40 phr, and MgO/MAA mole ratio 0.50–0.75 is recommended for good mechanical properties of the SBR vulcanizates. The tensile strength of the SBR vulcanizates is up to 31.4 MPa when the DCP content is 0.6 phr and the Mg(MAA)₂ content is 30 phr. The SBR vulcanizate have good aging resistance and limited retention of tensile strength at 100°C. The SBR vulcanizates are semitransparent, and have a good combination of high hardness, high tensile strength, and elongation at break. The T_g values of the SBR vulcanizates depend largely on the DCP content, but depend less on the Mg(MAA)₂ content and the MgO/MAA mole ratio. The contents of DCP, Mg(MAA)₂, and the MgO/MAA mole ratio have also great effects on the E′ values of the vulcanizates. The salt crosslink density is greatly affected by the Mg(MAA)₂ content and MgO/MAA mole ratio, but less affected by the DCP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2667–2676, 2002     

Polymethacrylic acid/Na-montmorillonite/SiO<Subscript>2</Subscript> nanoparticle composites structures and thermal properties

In this article, polymethacrylic acid/Na-montmorillonite/SiO₂ nanoparticle (PMAA/Na-MMT/SiO₂) composites were prepared via in situ polymerization. Fourier transform infrared spectroscopy (FTIR) indicated that the polymerization of SiO₂ nanoparticle and MAA have been taken place. X-ray diffraction (XRD) results suggest that Na-MMT layers are exfoliated during the polymerization process. As evidenced by the transmission electron microscopy (TEM), the Na-MMT layers and SiO₂ nanoparticles exhibit good dispersion in the polymer matrix. It was found that the PMAA/Na-MMT/SiO₂ composite exhibit considerably enhanced thermal properties compared with the PMAA/Na-MMT.     

Preparation of high PMMA grafted particle SiO2 using surface initiated free radical polymerization

In this work, a convenient surface-initiated free radical graft-polymerization method, by which polymethacrylic acid (PMAA) with a high grafting density was grafted on silica gel particles, was put forward, and it was feasible and effective. The coupling agent γ-aminopropyltrimethoxysilane (AMPS) was first bound onto the surfaces of silica gel particles, obtaining the modified particles AMPS-SiO₂. So a redox initiation system was constituted with the amino groups on the surfaces of AMPS-SiO₂ particles and ammonium persulphate in the solution. A great deal of primary free radicals on the surfaces of AMPS-SiO₂ particles is produced via the redox initiating reaction, so that the surface-initiated free radical graft- polymerization of methacrylic acid (MAA) on the silica gel particles was realized, giving the grafted particles PMAA/SiO₂ with a high grafting degree (about 30 g/100 g) of PMAA. The effects of the main factors on the surface initiated graft polymerization were examined and the corresponding mechanism was investigated in depth. The experimental results show that for this surface-initiated free radical graft-polymerization of MAA, the suitable temperature is 40 °C. If the temperature is over 40 °C, the graft polymerization will be affected negatively, and the grafting degree of PMAA will decline because of the intense heat decomposition of ammonium persulphate. During the graft polymerization, the grafted polymer layer that has formed is a hindrance to the subsequent graft polymerization. The used amount of initiator and the monomer concentration affect the graft polymerization greatly. The appropriate reaction conditions are as follows: reaction time of 10 h, initiator persulphate amount of 1.1% (it implies the mass percent of the monomer), and monomer MAA concentration of about 5% (it drives at the mass percent of the solution).     

用甲基丙烯酸原位改性纳米碳酸钙填充三元乙丙橡胶Ⅲ.应力软化效应和应力弛豫

用甲基丙烯酸(MAA)原位改性纳米碳酸钙填充三元乙丙橡胶(EPDM),制备了纳米碳酸钙增强EPDM硫化胶。考察了MAA对纳米碳酸钙增强EPDM硫化胶的应力软化效应及应力弛豫行为,并与未改性纳米碳酸钙、炭黑及白炭黑增强EPDM硫化胶的应力软化效应和应力弛豫行为进行了比较;用并联的Maxwell模型对应力弛豫行为进行了数学模拟。结果表明,MAA加剧了纳米碳酸钙增强EPDM的应力软化效应和应力弛豫行为。与其他3种填料相比,MAA原位改性纳米碳酸钙增强EPDM的应力软化效应更为显著,且其应力在室温停放后不能像其他填料增强EPDM那样得到明显恢复;MAA原位改性纳米碳酸钙增强EPDM的应力弛豫速率更快,应力弛豫程度也更大;并联Maxwell模型可以模拟未改性纳米碳酸钙、MAA原位改性纳米碳酸钙、炭黑及白炭黑增强EPDM的应力弛豫行为。     

A Comparative Study on Curing Characteristics,Mechanical Properties,Swelling Behavior,Thermal Stability,and Morphology of Feldspar and Silica in SMR L Vulcanizates

Abstract

Comparison studies on effects of feldspar and silica (Vulcasil C) as a filler in (SMR L grade natural rubber) vulcanizates on curing characteristics, mechanical properties, swelling behavior, thermal analysis, and morphology were examined. The incorporation of both fillers increases the scorch time, t ₂, and cure time, t ₉₀, of SMR L vulcanizates. At a similar filler loading, feldspar exhibited longer t ₂ and t ₉₀ but lower values of maximum torque, M_HR, and torque difference, M_HR–M_L than did silica-filled SMR L vulcanizates. For mechanical properties, both fillers were found to be effective in enhancing the tensile strength (up to 10 phr), tensile modulus, and hardness of the vulcanizates. However, feldspar-filled SMR L vulcanizates showed lower values of mechanical properties than did silica-filled SMR L vulcanizates. Swelling measurement indicates that swelling percentages of both fillers-filled SMR L vulcanizates decrease with increasing filler loading whereas silica shows a lower swelling percentage than feldspar-filled SMR L vulcanizates. Scanning electron microscopy (SEM) on fracture surface of tensile samples showed poor filler–matrix adhesion for both fillers with increasing filler loading in the vulcanizates. However, feldspar-filled SMR L vulcanizates showed poorer filler–matrix adhesion than did silica-filled SMR L vulcanizates. Thermogravimetric analysis (TGA) results indicate that the feldspar-filled SMR L vulcanizates have higher thermal stability than do silica-filled SMR L vulcanizates.     

Effects of Sm3+/PMAA on mechanical and thermal properties of natural rubber latex film

Samarium carbonate [Sm₂(CO₃)₃] was taken as the source of Sm³⁺, and methyl acrylic acid (MAA) was employed as the precursor to prepare polymethacrylic acid (PMAA). The mixture of Sm₂(CO₃)₃ and PMAA was marked as “SmP.” The SmP prepared under different conditions was added to natural rubber (NR) latex to prepare NR/SmP films. The influence of the polymerization temperature of MAA and the amount of SmP on the mechanical properties and structure of NR/SmP films were analyzed. The results show that polymerization temperature has significant effect on the mechanical properties of NR/SmP film; lower temperature is benefit to improve modulus and rigidity, whereas higher temperature helps maintain good elasticity. Compared with neat NR, addition of 5-phr Sm₂(CO₃)₃ results in a 30%–37% increase of tensile strength. Furthermore, the glass transition temperature (T_g) can also be increased by the addition of SmP; and the tan δ curves of all samples exhibit only one transition peak and indicate no phase separation between SmP and NR matrix. The influence of SmP on the structure and morphology of NR was explored by Fourier transform infrared, X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy analysis; and the results show that SmP can be dispersed uniformly in the NR latex when loading of Sm₂(CO₃)₃ is lower than 20 phr.     

Designing and preparing of quercetin surface‐imprinted material and its molecular recognition characteristics

Quercetin is an important compound of flavonoids. In this work, quercetin molecule surface‐imprinted material with high performance was prepared using a novel surface‐imprinting technique of “synchronously graft‐polymerizing and imprinting.” The modified micron‐sized silica gel particles containing amino groups were used as matrix, methacrylic acid (MAA) was used as functional monomer, and N,N′‐Methylenebisacrylamide (MBA) was used as crosslinker. In dimethyl formamide solution of quercetin, MAA molecules arranged automatically around the template quercetin molecule by right of hydrogen bonding interactions of two type, ordinary hydrogen bond and π‐type hydrogen bond. By initiating the surface‐initiating system of – , the graft/cross‐linking polymerization of MAA on SiO₂ particles and the quercetin molecule surface‐imprinting were simultaneously carried out, forming quercetin molecule surface‐imprinted material MIP‐PMAA/SiO₂. With another two flavonoids, rutin and genistein, as contrasting substances, the molecule recognition character of the quercetin molecule surface‐imprinted material MIP‐PMAA/SiO₂ was investigated with batch and column methods. The experimental results show that the imprinted material MIP‐PMAA/SiO₂ possesses special recognition selectivity and excellent binding affinity for quercetin molecule. The binding capacity of MIP‐PMAA/SiO₂ for quercetin is 0.325 mmol/g, and its selectivity coefficients for quercetin relative to rutin and genistein are 7.69 and 4.40, respectively. The main conditions of imprinting process affect the property of MIP‐PMAA/SiO₂ greatly, and the optimal molar ratio of monomer MAA to crosslinker MBA is 7 : 1 and appropriate molar ratio of monomer MAA to template quercetin is equal to 6 : 1. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41112.     

Fatigue resistance of silica‐filled natural rubber vulcanizates: comparative study of the effect of phosphorylated cardanol prepolymer and a silane coupling agent

The fatigue resistance of silica‐filled natural rubber (NR) mixes modified with phosphorylated cardanol prepolymer (PCP) was studied in comparison with similar compositions without PCP and with those containing the same dosage of a silane coupling agent (Si‐69). Considerable improvement in the fatigue resistance was observed for the PCP‐modified NR vulcanizate containing 20 phr of silica compared with the unmodified and Si‐69 modified vulcanizates. In addition, the tear strength of the PCP‐modified NR vulcanizate was higher than that of the others. Atomic force microscopy and the scanning electron microscopy of the vulcanizates showed better dispersion of silica particles in the NR matrix in the presence of PCP than in the unmodified and Si‐69‐modified NR vulcanizates. It is assumed that, at a dosage of 5 phr, PCP functions as a coupling agent between NR and the silica particles thereby improving the filler dispersion and consequently the mechanical properties of the vulcanizate. Copyright © 2005 Society of Chemical Industry     

Effect of fillers and additives on the properties of SBR vulcanizates

Methacrylic acid (MAA) and methyl methacrylate (MMA) were used as additives for peroxide‐cured styrene–butadiene rubber (SBR) filled with three inorganic fillers with different particle sizes and surface activity, for example, MgO, Mg(OH)₂, and BaSO₄. The experimental results show that the introduction of MAA can improve the mechanical properties of SBR vulcanizates filled with MgO, Mg(OH)₂, or BaSO₄. A small amount of MAA leads to significant increases in the modulus, tensile strength, and tear strength. MMA has little effect on the mechanical properties of the SBR vulcanizates. The SEM micrographs show that MAA can improve the interfacial bonding between SBR and the three kinds of fillers. The SBR–filler interaction was studied by Kraus plots. The relationship between the SBR–filler interaction and the mechanical properties was explored. m, a characteristic constant of a filler–SBR matrix, represents the interfacial bonding between fillers and SBR and the accumulated structure of the fillers. At a given ?, a high value of m means a strong interaction between SBR and the filler and, therefore, strong mechanical properties. The Payne effect of the SBR vulcanizates was observed, and the vulcanizates have low storage moduli at high strains and high storage moduli at low strains, and the moduli are nonlinear and increase the nonlinearity as the filler content increases. The loss moduli and loss factor reach their maximums at moderate and high strain amplitudes, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 775–782, 2003     

Thermal aging properties and chemical resistance of blends of natural rubber and epoxidized low molecular weight natural rubber

Studies into solvent resistance and aging properties of blends of natural rubber and epoxidized low molecular weight natural rubber were carried out. Vulcanization of the blends using the semi‐efficient vulcanization (semi‐EV) system was found to have curing advantages over conventional vulcanization (CV) and efficient vulcanization (EV) systems. The rheological properties (cure time, t₉₀, and scorch time, t₂), solvent resistances, and aging properties of the vulcanizates were found to improve as the level of epoxidized low molecular weight natural rubber in the blends increases. The mechanical properties of the blends were also found to be within the accepted level for NR vulcanizates. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1733–1739, 2005     

抗湿滑轮胎胎面胶配方的研究

研究羧基改性溶聚丁苯橡胶(SSBR)、丁腈橡胶(NBR)和高性能橡胶助剂Nanoprene在抗湿滑轮胎胎面胶中的应用。结果表明:在胎面胶配方中,以SSBR等量替代ESBR,胶料的门尼焦烧时间和t90延长,硫化胶的300%定伸应力和撕裂强度增大,湿抓着性提高,压缩生热降低,耐磨性能变化不大;加入20份Nanoprene,胶料的门尼焦烧时间和t90延长,硫化胶的300%定伸应力增大,湿抓着性提高,压缩生热降低,耐磨性能下降;加入5份NBR,胶料的硫化特性、硫化胶的物理性能和压缩生热变化不大,湿抓着性提高,耐磨性能下降。     

Improving oxidation stability and mechanical properties of natural rubber vulcanizates filled with calcium carbonate modified by gallic acid

A novel technique to modify the surface of calcium carbonate (CaCO₃) nanoparticles, used as an antioxidant and reinforcing filler, by gallic acid is disclosed. The new properties of the modified CaCO₃ could make it more useful and practical for the rubber industry. Thermal gravimetric (TGA), Fourier transform infrared spectroscopy, and transmission electron microscopy analyses showed that the gallic acid was bound onto the surface of CaCO₃. The gallic acid modified CaCO₃ exhibited a significant antioxidation property, as revealed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) analysis. The mechanical properties of natural rubber vulcanizates filled with the gallic acid modified CaCO₃ showed an enhanced reinforcement with increasing loading levels, and increased resistance to ozonolysis over that seen with the unmodified CaCO₃ mixed with Irganox 1010 as the commercial antioxidant.     

甲基丙烯酸固态原位接枝改性炭黑对天然橡胶和顺丁橡胶性能的影响

考察了固态原位接枝改性制备的甲基丙烯酸接枝改性炭黑对天然橡胶(NR)和顺丁橡胶。(BR)静态力学性能、动态力学性能的影响。结果表明。甲基丙烯酸改性炭黑比普通商品炭黑填充的NR硫化胶具有更好的静态力学性能;甲基丙烯酸改性炭黑曼有利于降低NR和BR硫化胶的滚动阻力。同时,有利于提高NR硫化胶的抗湿滑性。     

Effect of tetramethylthiuram disulphide on bis(triethoxysilylpropyl)tetrasulphane as coupling agent for silica in polyisoprene

Abstract

Polyisoprene was compounded with 30 phr unmodified silica and with silica in the presence of modifiers bis(triethoxysilylpropyl)tetrasulphane (TESPT) and the unsymmetric polysulphide formed on reaction of TESPT with tetramethylthiuram disulphide. The modifiers improved bound rubber formation and the green strength characteristics of compounds compared with compounds with unmodified silica. However, the use of the unsymmetric polysulphide, part of which could react with hydroxy groups on the silica surface and part of which contains an accelerator moiety, gave only a marginal improvement in bound rubber formation and green strength, compared with compounds in which silica is modified with TESPT alone. Heating at 150°C is essential to improve bound rubber formation and it ensures that essentially all of the bound rubber, formed in the presence of modifiers, is firmly held to the surface, swelling in an ammonia atmosphere giving no further solublisation of rubber compared with normal swelling. Chain end radicals, formed during mixing, play no role in bound rubber formation.     

On the potential of organoclay with respect to conventional fillers (carbon black,silica) for epoxidized natural rubber compatibilized natural rubber vulcanizates

Onium modified montmorillonite (organoclay) was compounded with natural rubber (NR) in an internal mixer and cured by using a conventional sulfuric system. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) in 10 parts per hundred rubber (phr) was used as a compatibilizer in this study. For comparison purposes, two commercial fillers: carbon black (grade N330) and silica (grade vulcasil‐S) were used. Cure characteristics were carried out on a Monsanto MDR2000 Rheometer. Organoclay filled vulcanizate showed the lowest values of torque maximum, torque minimum, scorch, and cure times. The kinetics of cure reaction showed organoclay could behave as a cocuring agent. The mechanical testing of the vulcanizates involved the determination of tensile and tear properties. The improvement of tensile strength, elongation at break, and tear properties in organoclay filled vulcanizate were significantly higher compared to silica and carbon black filled vulcanizates. In terms of reinforcing efficiency (RE), organoclay exhibited the highest stiffness followed by silica and carbon black filled vulcanizates. Scanning electron microscopy revealed that incorporation of various types of fillers has transformed the failure mechanism of the resulting NR vulcanizates compared to the gum vulcanizates. Dynamic mechanical thermal analysis (DMTA) revealed that the stiffness and molecular relaxation of NR vulcanizates are strongly affected by the filler–rubber interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2438–2445, 2004     

Properties of EVM vulcanizates reinforced by in situ prepared sodium methacrylate

Ethylene–vinyl acetate copolymer (EVM) vulcanizates with good mechanical properties and high transparency were obtained using sodium methacrylate (NaMAA) as a reinforcing agent. Sodium methacrylate was in situ prepared through the neutralization of sodium hydroxide (NaOH) and methacrylic acid (MAA) in an EVM and used to reinforce the EVM cured by dicumyl peroxide (DCP). Different factors such as the DCP content, NaMAA content, and the mol ratio of NaOH/MAA were included to study their effects on the mechanical properties, optical properties, stress‐relaxation behavior, and crosslink structure of the EVM vulcanizates. The rheological behavior of the EVM compounds was also investigated and compared with that of the high abrasion furnace carbon black (HAF)/EVM compounds. The experimental results show that with an increase of the NaMAA content the curing rate index (C_R) of the EVM compounds is greatly speeded up, while the Mooney viscosities of the compounds remain nearly unchanged. The mechanical properties and optical properties of the NaMAA‐reinforced EVM vulcanizates depend on the NaMAA content and the mol ratio of NaOH/MAA. The formulation of DCP of 3 phr and a NaOH/MAA mol ratio of 1.0 is recommended for the EVM vulcanizate with high mechanical properties. At a given NaOH/MAA mol ratio of 1.0, all the EVM vulcanizates are transparent and the light transmission is over 76% in the NaMAA content range of 10–50 phr. The NaMAA/EVM vulcanizates show faster stress relaxation and more obvious stress‐softening effects than those of the HAF/EVM vulcanizates. Crosslink density analysis indicated that the EVM vulcanizates contain both covalent and ionic bonds. The ionic crosslink densities greatly increase with an increasing NaMAA content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2192–2200, 2003     

Effect of chemically modified waste rubber powder as a filler in natural rubber vulcanizates

Waste rubber powder (RP) was subjected to chemical modification by using different concentrations of oxidizing agents such as nitric acid and 30% hydrogen peroxide solution. This treatment leads to introducing some functional groups onto the surface of RP. The chemically modified RP was incorporated in natural rubber mixes either alone or in combination with carbon black (HAF). The physicomechanical properties of NR vulcanizates obtained were studied and compared to NR vulcanizates filled with untreated RP. It was found that the chemically modified RP improves tensile strength and aging resistance of NR vulcanizates compared with untreated RP. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 30–36, 2004