Norbornylized soybean oil as a sustainable new plasticizer for rubbers with hybrid fillers

Carbon black (CB) and precipitated silica are two major reinforcing fillers in rubbers. CB/silica hybrid filler is also widely used in rubbers to provide balanced properties. CB/silica‐hybrid‐filler‐filled styrene‐butadiene rubber (SBR) containing naphthenic oil (NO), soybean oil (SO) and norbornylized SO (NSO) was investigated. The swelling and curing behavior and rheological, mechanical, thermal, aging and dynamic properties were studied and compared with earlier reported data on CB‐ or silica‐filled SBR. NSO provides better scorch safety and faster cure than SO. Compared with NO, the addition of SO and NSO enhances the thermal stability and aging resistance of SBR vulcanizates. SBR/NSO vulcanizates with hybrid filler exhibit a higher tensile and tear strength than SBR/NO and SBR/SO vulcanizates. A synergistic effect in the abrasion resistance of vulcanizates containing the hybrid filler is observed. An increase of sulfur content in the hybrid‐filler‐filled SBR/NSO vulcanizates provides further improvement in abrasion resistance, wet traction and rolling resistance. © 2017 Society of Chemical Industry     

Influence of rubber composition on change of crosslink density of rubber vulcanizates with EV cure system by thermal aging

Variation of the crosslink density of a rubber vulcanizate depending on the rubber composition after the thermal aging was studied with single rubber, biblend, and triblend vulcanizates of natural rubber (NR), butadiene rubber (BR), and styrene‐butadiene rubber (SBR). The efficient vulcanization (EV) system was employed to minimize the influence of free sulfur in the vulcanizate on the change of the crosslink density. Thermal aging was performed at 40, 60, and 80°C for 20 days with 5‐day intervals. The crosslink densities of the vulcanizates after the thermal aging increase. For the single rubber vulcanizates, variation of the crosslink density by the thermal aging has the order: SBR > BR > NR. For the biblend vulcanizates, variations of the crosslink densities of the NR/SBR and SBR/BR blends are larger than that of NR/BR blend. Variation of the crosslink density of the vulcanizate increases by increasing the SBR content in the vulcanizate. Variation of the crosslink density of the rubber vulcanizate depending on the rubber composition was explained by miscibility of the blends, combination reaction of the pendent groups, and mobility of the pendent group. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1378–1384, 2000     

Improvement of properties of silica‐filled natural rubber compounds using polychloroprene

Because silica has strong filler–filler interactions, a silica‐filled rubber compound is characterized by a poor dispersion of the filler. Properties of silica‐filled natural rubber (NR) compounds were improved using polychloroprene (chloroprene rubber [CR]). The bound rubber content of the compound increases and the filler dispersion is also improved by adding CR to the compound. Physical properties such as modulus, tensile strength, abrasion, and crack resistance are improved by adding CR. Elongation at break of the vulcanizates containing CR is longer than that of the vulcanizate without CR, although crosslink density of the former is higher than that of the latter. The improved physical properties are attributed to the good dispersion of silica by adding CR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2609–2616, 2002     

Influence of silica loading on the mechanical properties and resistance to oil and thermal aging of CR/NR blends

Blends of 75/25 chloroprene rubber(CR)/natural rubber (NR) filled with various loadings of precipitated silica were prepared and their processability and mechanical properties as well as their resistance to thermal aging and oil were determined. The blend morphology was also studied using the atomic force microscopy technique. The results reveal that the mixing energy and the Mooney viscosity of the compound are increased continuously with increasing silica loading. It is also found that both scorch and optimum curing times are shortened while the total crosslink density is increased with increasing silica loading. The positive effect on cure could be explained by the chemical reaction between the allylic chlorine atom of CR and the silanol group on silica surface. The tensile strength, modulus, and hardness of the blend vulcanizate are noticeably improved while the compression set at elevated temperature is impaired with increasing silica loading. The results also reveal that both thermal aging resistance and oil resistance of the blend vulcanizates, as represented by the relative properties, are enhanced with the addition of silica. The resistance enhancement is believed to arise from the combination of the dilution effect, the increased crosslink density and also the reduction of NR dispersed phase size. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of crosslinking on the conductivity of conductive silicone rubber

We investigated the effect of polyvinylsilicone oil (C gum) as a crosslinker and 2,5‐bis(tert‐butyl peroxy)‐2,5‐dimethyl hexane (DBPMH) as a curing agent on the conductivity of conductive silicone rubber with two different kinds of conducting mechanisms. The experimental results show that the volume resistivity of conductive silicone rubber changed with its degree of crosslinking. When the carbon black loading was 25 parts per hundred rubber (phr) and a completely continuous conducting network had not formed, the volume resistivity of the vulcanizates decreased with increasing crosslink density. The volume resistivity of the vulcanizate with a suitable amount of C gum decreased to 53%, and the tensile strength increased by 0.8 MPa compared to the vulcanizate without C gum. When the carbon black loading was 40 phr and a completely continuous conducting network had formed, the crosslink density of vulcanizates changed as the amount of DBPMH changed. The volume resistivity of vulcanizates first decreased and then increased with increasing crosslink density. There was a valley value in the resistivity–crosslink density curve. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3471–3475, 2003     

Cure characteristics and physical properties of ground‐rubber‐filled natural rubber vulcanizates: Effects of the curing systems of the ground rubber and rubber matrix

Recycling discarded rubber is important for both environmental and economic reasons. One of the most attractive methods of recycling rubber waste is to use ground rubber (GR) as a compounding ingredient or as a replacement for raw polymers. In this study, ground natural rubber was prepared with different curing systems and compounded into the parent compounds. The cure behaviors and physical properties of the GR‐filled vulcanizates were investigated, and they were largely affected by the curing systems of the rubber matrix and GR. GR‐filled vulcanizates with GR and the rubber matrix, having a conventional curing system, showed the largest changes in the cure characteristics. The greatest decrease in the physical properties was observed for peroxide‐cured‐GR‐filled vulcanizates. The addition of GR decreased the crosslink density of the GR‐filled vulcanizates. This was thought to be the main reason for the reduction of the mechanical properties of the GR‐filled vulcanizates. However, the adhesion between the GR and rubber matrix may also have caused the differences in the physical properties of the GR‐filled vulcanizates with respect to the curing systems of the rubber matrix and GR. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of 1,2‐polybutadiene on properties of dicumyl peroxide cured brominated butyl rubber

Peroxide curing of brominated butyl rubber (BIIR) is an attractive topic, but the degradation of BIIR during the curing is a drawback needed to be overcome. Coagent assisted peroxide curing system is an attractive and effective choice in order to increase the crosslink density of rubbers. 1,2‐polybutadiene (1,2‐PB) is used as a crosslinking coagent for the curing of BIIR by dicumyl peroxide (DCP), and the effect of 1,2‐PB on the curing characteristics, crosslink density, and mechanical properties is investigated. The addition of 1,2‐PB affects the curing characteristics of BIIR compound and significantly increases the crosslink density of BIIR vulcanizates. With increasing 1,2‐PB content, the tensile strength and stresses at a given extension of BIIR vulcanizates increase, but the elongation at break decreases. A stress‐softening effect of the carbon black filled BIIR vulcanizates is observed and becomes more pronounced with increasing 1,2‐PB content. The addition of 1,2‐PB increases the stress relaxation index of BIIR. GPC and ¹³C‐NMR results indicate 1,2‐PB participates in the crosslinking reaction, and the existence of 1,2‐PB component in the insoluble fraction of BIIR/1,2‐PB vulcanizates is confirmed by solid‐state ¹³C‐NMR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43280.     

Effect of carbon black on self‐crosslinking network structure of polychloroprene rubber and epoxidized natural rubber blends

The goal of this research is to improve poor network structure of polychloroprene rubber (CR)/epoxidized natural rubber (ENR) self‐crosslinking blends, which could substitute traditional vulcanizates in some application area. Carbon black (CB)–CR/ENR blends were prepared by reacting CR with ENR in the presence of CB. The structure of CR/ENR blends was characterized by attenuated total‐reflectance Fourier transform infrared spectroscopy (FTIR‐ATR). The effect of CB loading on curing characterization and mechanical properties of CR/ENR blends was investigated, and the interaction among CR, ENR, and CB was studied using differential scanning calorimetry. The effect of CB loading on the Payne effect of CR/ENR was investigated using rubber process analyzer. Scanning electron microscope was used to characterize the morphology of CB–CR/ENR blends. The results showed that CR/ENR blends were obtained by the ring‐opening reaction of epoxy groups in ENR and chlorine groups in CR. Mechanical properties of CR/ENR blends increased with the increase of CB loading. The Payne effect of CR/ENR became more remarkable with increasing CB loading. Morphology study indicated that interfacial compatibility between CR and ENR increased with the increase of CB loading because CB could strengthen the self‐crosslinking network structure of CR/ENR blends. The promoting effect of CB on self‐crosslinking reaction was verified by the assessment of crosslink density. POLYM. COMPOS., 38:463–471, 2017. © 2015 Society of Plastics Engineers     

Influence of internal strain on change of crosslink density of natural rubber vulcanizates by thermal ageing

Change of crosslink density of natural rubber (NR) vulcanizates by thermal ageing at 60 °C has been studied under swollen conditions in solvents to investigate the influence of internal strain applied to the vulcanizate on the crosslink density change. The internal strain was controlled by swelling with various solvents such as n‐hexane, toluene, tetrahydrofuran (THF), methanol and water. The order of degree of the swelling is toluene ≈ THF > n‐hexane > methanol > water. The influence of curing system has been investigated with the vulcanizates cured by the conventional and EV cure systems. After thermal ageing, the apparent crosslink densities of the swollen vulcanizates in n‐hexane, toluene and THF decrease irrespective of the cure systems, while that of the swollen vulcanizate in water increases. For the swollen vulcanizates in methanol, the apparent crosslink density of the vulcanizate with the conventional cure system after thermal ageing increases while that of the vulcanizate with the EV cure system decreases. The decrement of the apparent crosslink density of the vulcanizate after thermal ageing becomes larger and larger upon increasing the internal strain. © 2001 Society of Chemical Industry     

炭黑增强氯丁橡胶硫化胶压缩Mullins效应的强化

研究了炭黑增强氯丁橡胶硫化胶的力学性能和压缩Mullins效应的强化效应,探讨了炭黑用量对其压缩Mullins效应的增强机制。结果表明,炭黑增强后的氯丁橡胶硫化胶的屈服强度和模量均得到明显提高,且力学性能在炭黑用量为30份(质量)时达到最佳;在单轴循环压缩过程中,随着炭黑用量的增加,氯丁橡胶静态硫化胶的Mullins效应不断增强,并且在给定的压缩应变下,其最大压缩应力在首次加载-卸载循环压缩时达到峰值,在随后的4次循环压缩中仅发生不同程度的下降。此外,提高炭黑用量及增大压缩应变均可明显增强氯丁橡胶硫化胶的Mullins效应。     

环保型增塑剂腰果壳油对丁腈橡胶性能的影响

研究了腰果壳油(CNSL)用量对丁腈橡胶胶料的硫化特性和硫化胶性能的影响,并与使用邻苯二甲酸二辛酯和环氧大豆油作为增塑剂进行了对比。结果表明,在0～30份(质量)用量内,加入CNSL后胶料的焦烧时间和正硫化时间有所缩短。与加入相同用量的邻苯二甲酸二辛酯和环氧大豆油的胶料及硫化胶相比,使用CNSL的胶料在硫化曲线上的最小转矩和最大转矩以及硫化胶的硬度、定伸应力和耐ASTM1#标准油体积增加率较小;硫化胶的拉伸强度、撕裂强度、扯断伸长率和耐ASTM3#标准油体积增加率较大;硫化胶的耐热空气老化性能较好。     

三种微生物脱硫废乳胶及其填充天然橡胶的力学性能比较

利用三种微生物鞘氨醇单胞菌、脂环酸芽孢杆菌和酵母菌对废乳胶(WLR)进行了脱硫再生,考察了脱硫过程中微生物的生长情况以及脱硫前后WLR溶胀和交联密度的变化,并将WLR和脱硫WLR(DWLR)以不同份数填充到天然橡胶(NR)中,对比了DWLR/NR硫化胶和WLR/NR硫化胶的力学性能和交联密度。结果表明,利用鞘氨醇单胞菌脱硫的WLR溶胀值较高,交联密度较低。随着乳胶用量的增加,填充NR硫化胶的拉伸强度和交联密度逐渐降低,扯断生长率逐渐增加。DWLR/NR硫化胶的力学性能明显优于WLR/NR硫化胶,且鞘氨醇单胞菌脱硫的DWLR/NR的力学性能明显优于其它两种微生物脱硫的DWLR/NR硫化胶。     

不同牌号三元乙丙橡胶的结构与性能对比

对8个牌号三元乙丙橡胶(EPDM)的微观结构、硫化特性、物理机械性能、耐磨性能及耐老化性能进行了对比.结果表明,EPDM中第3单体亚乙烯基降冰片烯(ENB)质量分数影响了EPDM的硫化速率.8个牌号中EPDM 9950 C的硫化速率最快,EPDM 3722的硫化速率最慢;充油胶EPDM 3666的硫化速率与结构类似的E...     

Study on properties of natural rubber reinforced by poly(sodium‐4‐styrenesulfonate)‐decorated carbon black with a latex compounding technique

Natural rubber filled with poly(sodium‐4‐styrenesulfonate) (PSS)‐decorated carbon black (CB) by employing a latex compounding technique was prepared. The result of scanning electron microscope demonstrated that CB was uniformly dispersed in the matrix. Comparing to traditional dry compounding, an improvement in physical and mechanical properties was observed in the composites attributed to the homogeneous distribution of CB in matrix and an augment of bound rubber. Owing to the changes of the physical properties of CB surface, vulcanizate filled with oxidized CB via latex way exhibited higher mechanical properties. The resulting vulcanizates displayed a diminished interaction between fillers based on the consequence of strain dependence of storage modulus. Furthermore, a splendid wet‐skid resistance was obtained in vulcanizates fabricated by latex compounding technique in comparison with vulcanizates prepared by traditional dry compounding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42346.     

An investigation on the reinforcing potential of red earth as filler for natural rubber compounds

Locally sourced red earth (RE) was air‐dried, pulverized, and screened with a sieve of mesh size 75 nm. It was characterized in terms of its moisture content, loss on ignition, silica content, iodine adsorption number, oil absorption, pH, and metal oxide compositions. Natural rubber, standard Nigerian rubber used for this work was first characterized in terms of its dirt, ash and nitrogen contents, volatile matter, plasticity retention index, and Mooney viscosity. The RE was applied as filler wholly and in blends with standard carbon black, CB (N330) filler in the natural rubber compounding using efficient vulcanization system. The cure and the physicomechanical properties of the compounds and vulcanizates were, respectively, measured as function of filler loading. The results were compared with those of the standard carbon black (N330)‐filled natural rubber. It was found, that the RE‐filled natural rubber showed substantial reinforcement of the rubber, though inferior to carbon black (N330) filled vulcanizates, the tensile strength of the carbon black‐filled vulcanizates is about one half times that of the RE‐filled vulcanizates. The tensile properties of the RE‐filled vulcanizates improved markedly by blending the RE‐filler with the carbon black (N330). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Continuous ultrasonic devulcanization of carbon black‐filled NR vulcanizates

The continuous ultrasonic devulcanization of natural rubber (NR) filled with various concentrations of carbon black (CB) indicated a minimum of crosslink density and gel fraction at an intermediate amplitude, which is independent of CB content. An attempt was made to improve the efficiency of devulcanization by use of various chemicals (1,3 Diphenylguanidine, 2‐Mercaptobenzothiazole, Thianaphthene). However, these experiments did not indicate any improvement in comparison with devulcanization without chemicals. An idea of adding fresh CB into devulcanized compound, which has been shown to improve mechanical properties in the case of styrene–butadiene rubber (SBR), was tested in the present study for CB filled NR compound. The obtained result indicated that an addition of fresh CB to devulcanized CB‐filled NR did not lead to an improvement in mechanical properties upon revulcanization. The revulcanization recipe was optimized to improve the mechanical properties of revulcanized CB‐filled NR vulcanizates. It was found that CB‐filled NR upon revulcanization retained its strain‐induced cystallizability with the tensile strength and elongation at break at about 50 and 70% level of the virgin vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2340–2348, 2001     

钕系顺丁橡胶在全钢巨型工程机械子午线轮胎胎侧胶中的应用

试验研究两种钕系顺丁橡胶(NdBR)CB22和CB24在全钢巨型工程机械子午线轮胎胎侧胶中的应用。结果表明:与镍系顺丁橡胶相比,NdBR胶料具有较优的硫化平坦性,硫化胶具有较好的综合物理性能和耐屈挠性能及较低的压缩生热;CB22与CB24相比,CB22硫化胶具有较好的物理性能和较低的压缩生热,而CB24硫化胶具有较好的耐屈挠性能。     

Plasticization effect of transgenic soybean oil. I. on ethylene propylene diene monomer (EPDM), as substitute for paraffin oil

Ethylene propylene diene monomer (EPDM) compounds were prepared with different amounts of transgenic soybean oil (TSO), a renewable and reactive plasticizer. For comparison, similar compounds were prepared with petroleum‐based paraffin oil (PO), one of the most common plasticizers for EPDM. The plasticization effects of TSO and of PO were studied by Mooney viscometry, capillary rheometry, differential scanning calorimetry (DSC), and rubber processing analysis (RPA). The results showed that TSO has better plasticization effect than PO on EPDM. In addition, the curing characteristics of the EPDM compounds were studied. TSO was found to react with the curing agent dicumyl peroxide (DCP) during the curing process. Excessive amounts of TSO led to low crosslinking density, which was improved by adjusting the added amount of DCP. The mechanical properties, extraction resistance, and thermal stability of the EPDM vulcanizates plasticized with different amounts of TSO and PO were compared to determine the optimum amount of TSO to replace PO. At the same amount and no more than 15 phr of plasticizer, the TSO‐plasticized EPDM vulcanizate has higher tensile and tear strength, elongation at break, extraction resistance, and thermal stability, but lower Shore A hardness than the PO‐plasticized EPDM vulcanizate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4457–4463, 2013     

Interfacial Interactions of Silica and Natural Rubber Enhanced by Hydroxyl Telechelic Natural Rubber as Interfacial Modifier

The incompatibility between hydrophilic silica and hydrophobic rubber is an important problem on using silica in nonpolar rubber. In this study, hydroxyl telechelic natural rubber (HTNR) that contains hydroxyl‐terminated groups was introduced into silica‐reinforced natural rubber (NR) in order to improve the bonding strength between rubber and silica. The properties of silica‐reinforced NR compounds and vulcanizates as a function of varying silica contents were evaluated at a fixed HTNR concentration at 8% wt/wt of silica content. The results show that the improvement of silica dispersion and decreasing of filler–filler interactions (Payne effect) were obtained in the NR compounds and vulcanizates with HTNR addition. The enhancements in tensile properties, crosslink density, abrasion resistance, heat build‐up, and thermal properties of the silica‐reinforced NR vulcanizates with added HTNR confirmed that HTNR performed good as interfacial modifier of silica. In the study, the optimum properties of silica‐reinforced NR vulcanizate were achieved at 30 phr silica with 2.4 phr HTNR. However, HTNR still showed poorer efficiency than the synergy between commercial silane coupling agent, bis [3‐(triethoxysilyl) propyl] tetrasulphide (TESPT) and diphenylguanidine (DPG) when used in silica‐reinforced NR vulcanizate. J. VINYL ADDIT. TECHNOL., 26:291–303, 2020. © 2019 Society of Plastics Engineers     

乙烯-乙酸乙烯酯橡胶基吸油膨胀橡胶的制备与性能

采用低乙酸乙烯酯质量分数的乙烯-乙酸乙烯酯橡胶(EVM)制备吸油橡胶,考察硫化剂DCP用量、补强填料种类及用量对其吸油膨胀性能和物理性能的影响,并对其耐老化性能、饱和吸油后稳定性能和保油率进行研究。结果表明:当硫化剂DCP用量为1.5份时,EVM硫化胶的物理性能和吸油膨胀性能较好;与白炭黑填充的硫化胶相比,炭黑填充EVM硫化胶的吸油膨胀性能较优;EVM吸油膨胀材料在酸、碱、盐环境中具有优异的耐老化性能和稳定性能,且保油率高。