Effects of rubber curing ingredients and phenolic-resin on mechanical,thermal, and morphological characteristics of rubber/phenolic-resin blends

This article examines the physical and mechanical characteristics of mixtures of two different synthetic rubbers, namely styrene-butadiene rubber (SBR) and nitril-butadiene rubber (NBR), with novolac type phenolic-resin (PH). According to Taguchi experimental design method, it is shown that the addition of PH increases the crosslinking density of rubber phase probably due to its curative effects. Thermal analysis of the blends indicates that, contrary to NBR/PH blend, thermal stability of SBR/PH blend is dependent on sulfur content due to predominant polysulfidic crosslinks formed in SBR. Slight shift in glass-transition temperature (T_g) of pure SBR and NBR vulcanizates by the addition of PH suggests that both SBR/PH and NBR/PH are incompatible blends with a partially soluble PH in the rubber phase. Two-phase morphology of the mixtures is also evidenced by scanning electron microscopy. Correlation of the rubber/PH modulus versus PH concentration by Halpin-Tsai model shows a deviation from the model. Presence of PH in the rubber phase is thought to vary the mechanical properties of the rubber phase by changing both the crosslinking density and rigidity of the molecular network of the rubber, leading to misuse of modulus of pure rubber in Halpin-Tsai equation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adhesive tack and green strength of EPDM rubber

Measurement of tack of EPDM (ethylene-propylenediene terpolymer) rubber with natural rubber (NR) of four different molecular weights, styrene-butadiene rubber (SBR), butadiene rubber (BR), bromobutyl rubber (BIIR), and polychloroprene rubber (CR) was done over a range of rates of testing, contact times, and temperatures of contact. The effect of different additives, namely carbon black, phenol-formaldehyde resin, coumarone-indene resin, and methyl methacrylate is also reported. Green strength of all the rubbers was measured. Tack strength increases with increase in contact time for all the rubbers. Adhesive tack between EPDM and low-molecular-weight NR is much higher than that between EPDM and NR of high molecular weight. Tack strength of EPDM with BIIR is the highest among the tack values obtained for synthetic rubbers. The adhesive tack between EPDM and natural/ synthetic rubber passes through a maximum when plotted against temperature of contact. It increases with testing rate. All these phenomena could be explained in terms of interdiffusion of rubber chains under different conditions and solubility parameter of two contacting rubbers. It was observed that tack strength varies with (contact time)^1/2 and (rate)^1/2 in accordance with the reptation theory. Phenol-formaldehyde resin (PF) or coumarone-indene (CI) resin in EPDM improves the tack strength quite significantly. The resin in the NR phase does not have a marked effect. The presence of carbon black decreases adhesive tack strength between EPDM and NR. The surface of EPDM, however, becomes smoother with the addition of the additives. Peel tests and commercial tack tests give similar results in the tack strength between EPDM/NR and EPDM/SBR.     

Morphology and mechanical properties of layered silicate reinforced natural and polyurethane rubber blends produced by latex compounding

Natural rubber (NR), polyurethane rubber (PUR), and NR/PUR‐based nanocomposites were produced from the related latices by adding a pristine synthetic layered silicate (LS; sodium fluorohectorite) in 10 parts per hundred parts rubber (phr). The dispersion of the LS latices in the composite was studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Further information on the rubber/LS interaction was received from Fourier transform infrared spectroscopy (FTIR) and dynamic mechanical thermal analysis (DMTA). Tensile and tear tests were used to characterize the performance of the rubber nanocomposites. It was found that LS is more compatible and thus better intercalated by PUR than by NR. Further, LS was preferably located in the PUR phase in the blends, which exhibited excellent mechanical properties despite the incompatibility between NR and PUR. Nano‐reinforcement was best reflected in stiffness‐ and strength‐related properties of the rubber composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 543–551, 2004     

Molecular orientation and structural development in vulcanized polyisoprene rubbers during uniaxial deformation by in situ synchrotron X-ray diffraction

Molecular orientation and strain-induced crystallization of vulcanized natural rubbers (by sulfur and peroxide) and synthetic polyisoprene rubber (by sulfur) during uniaxial deformation at 0 °C were studied by in situ synchrotron wide-angle X-ray diffraction. The high intensity of synchrotron X-rays and new image analysis methods made it possible to estimate the mass fractions of strain-induced crystals and amorphous chains in both oriented and unoriented states. Most of the polymer chains (∼75%) were found to be in the random coil state even at large strains (>5.0). Only about 5% the amorphous chains were oriented, whereas the rest of the chains (∼20%) were in the crystalline phase. Sulfur vulcanized and peroxide vulcanized natural rubbers did not exhibit notable differences in structure and property relationships. In contrast, synthetic polyisoprene rubber showed a different behavior of deformation-induced structural changes, which can be attributed to the difference in cross-link topology. Our results indicated that strain induces a network of microfibrillar crystals in both natural and synthetic polyisoprene rubbers due to the inhomogeneity of cross-link distribution that is responsible for their elastic properties.     

我国合成橡胶工业现状及发展建议Ⅱ.发展建议

我国合成橡胶工业经过40余年的快速发展,已形成七大主要产品系列、年产量位居世界第三的重要产业。目前,我国合成橡胶总消费量约占国内橡胶消费总量的59%,合成橡胶产量的增长仍不能满足国内市场的需求,合成橡胶市场有较大的发展空间。在分析了国内外合成橡胶发展态势的基础上提出了国内合成橡胶工业的发展建议。     

Polyisoprene matrix inhomogeneity studied by nitroxide spin probe motion

Summary The spin probe ESR method was applied to study natural rubber and synthetic polyisoprenes with different content of cis-configuration over a wide temperature range. The ESR spectra of natural rubber near and above the glass transition indicate the existence of two distinctly different mobilities as a consequence of the spin probe distribution in sol and gel phase. The results show that the spin probe method can yield information about the inhomogeneity of the polyisoprene matrix and the character of gel phase.     

The influence of cure conditions on the morphology and phase distribution in a rubber-modified epoxy resin using scanning electron microscopy and atomic force microscopy

In this paper, we consider the effect of cure conditions on the morphology and distribution of the rubber in a phase separated rubber-modified epoxy resin, which in effect is a two phase composite. Novel aspects of this study were measuring the elastic modulus of the dispersed rubber phase particles by atomic force microscopy (AFM) and verifying the presence of nano-dispersed rubber.The purpose of introducing dispersed rubber particles into the primary phase in these systems is to enhance their toughness. It is known that both the rubber particle size and volume fraction affect the degree to which the epoxy is toughened. It is not known, however, how the specific mechanical properties of the rubber phase itself affect the toughness.The objectives of this study were to: (1) use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to determine the morphology and phase distribution of the rubber particles and (2) to measure the mechanical properties of the rubber particles using AFM. Ultimately, we would like to develop a clear understanding of how the changes in morphology and mechanical properties measured at the micro and nano-scales affect both the elastic modulus and fracture toughness of rubber-modified epoxy polymers.The epoxy system consisted of a diglycidyl ether of bisphenol-A, Epon 828, cured with piperidine and incorporating a liquid carboxyl-terminated acrlonitrile-butadiene rubber (CTBN). The carboxyl groups of the rubber are capable of reacting with the epoxy. The cure conditions considered were based on a statistically designed full factorial curing matrix, with the variables selected being cure temperature, initiator (piperidine) concentration, and rubber acrylonitrile concentration.Each of these primary variables was found to affect the phase distribution that resulted during cure. A statistical analysis of the effect of these variables on the phase morphology showed that the acrylonitrile content (%) of the rubber affected both the rubber particle size and volume fraction. The cure temperature strongly influenced the rubber particle volume fraction and modulus. Volume fractions of the rubber phase of up to 24% were obtained even though the amount of rubber added was only 12.5%. The rubber particle modulus varied from 6.20 to 7.16 MPa. Both the volume fraction and modulus of the rubber particles were found to influence the macroscopic mechanical properties of the composite. While larger volume fractions favor improved toughness, we note that that the toughness is greatest when the particle modulus values do not exceed ∼6.2 MPa. Thus, increased volume fraction by itself may not always result in increased toughness. The particles also must be sufficiently ‘soft’ in order to improve toughness. In the system of interest here, the processing conditions are a key factor in achieving the most appropriate material properties. By inference, this is likely to be the case as well in other rubber-modified thermosets.     

Protein‐polyisoprene rubber composites

Hydrolyzed proteins previously shown to aggregate in aqueous solution were compounded into synthetic polyisoprene rubber (IR). Modulus increases of up to 232% resulted from protein reinforcement of IR. Increased hydrogen bonding on amine groups and the presence of β‐sheets in the protein phase were observed via Fourier transform infrared (FTIR) spectroscopy. The total β‐sheet amount relative to the IR content strongly correlated to the modulus and varied with the protein concentration, protein aggregation state, and compounding conditions. Isotropic protein aggregates on the order of hundreds of nanometers were observed by scanning electron microscopy with energy dispersive x‐ray spectroscopy (SEM‐EDX). The aggregates were evenly dispersed throughout the rubber matrix after compounding. The composite glass transition temperature (T_g) was unchanged from the control, which indicated that the protein and rubber existed as two discrete phases. Remarkably, protein β‐sheet structures were observed in FTIR even after rubber compounding under harsh conditions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46026.     

Migration of MWCNTs during melt preparation of ABS/PC/MWCNT conductive composites via PC/MWCNT masterbatch approach

The migration of multi-walled carbon nanotubes (MWCNTs) from the thermodynamically favored polycarbonate (PC) phase to the acrylonitrile-butadiene-styrene (ABS) phase is observed when PC/MWCNT masterbatch is diluted with PC and ABS by melt mixing for 5 min with 70% of ABS having relatively high rubber content. The migration is explained by a combination of the morphology evolution, high rubber content and higher affinity of MWCNTs to polybutadiene (PB) than to PC. The high rubber content increases the probability of the contact between MWCNTs and elongated rubber particles during the morphology evolution, most MWCNTs are dragged out of the PC phase to the ABS phase by the surrounding rubber particles because of the better affinity of MWCNTs to PB than to PC. As a result of the selective localization of most MWCNTs in the continuous ABS phase, the resulting ABS/PC/MWCNT composites are conductive. However, with a long mixing time of 60 min, most MWCNTs come back to the PC phase due to the change in the structure of PB chains which decreases the interaction between MWCNTs and rubber particles, resulting in non-conductive materials.     

Hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber catalyzed by [Ir(COD)py(PCy3)]PF6

In the presence of chlorinated solvents, the catalytic complex [Ir(COD)py(PCy₃)]PF₆ (where COD is 1,5‐cyclooctadiene and py is pyridine) was an active catalyst for the hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber. Detailed kinetic and mechanistic studies for homogeneous hydrogenation were carried out through the monitoring of the amount of hydrogen consumed during the reaction. The final degree of olefin conversion, measured with a computer‐controlled gas‐uptake apparatus, was confirmed by Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy. Synthetic cis‐1,4‐polyisoprene was used as a model polymer for natural rubber without impurities to study the influence of the catalyst loading, polymer concentration, hydrogen pressure, and reaction temperature with a statistical design framework. The kinetic results for the hydrogenation of both synthetic cis‐1,4‐polyisoprene and natural rubber indicated that the hydrogenation rate exhibited a first‐order dependence on the catalyst concentration and hydrogen pressure. Because of impurities inside the natural rubber, the hydrogenation of natural rubber showed an inverse behavior dependence on the rubber concentration, whereas the hydrogenation rate of synthetic rubber, that is, cis‐1,4‐polyisoprene, remained constant when the rubber concentration increased. The hydrogenation rate was also dependent on the reaction temperature. The apparent activation energies for the hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber were evaluated to be 79.8 and 75.6 kJ/mol, respectively. The mechanistic aspects of these catalytic processes were discussed on the basis of observed kinetic results. The addition of some acids showed an effect on the hydrogenation rate of both rubbers. The thermal properties of hydrogenated rubber samples were determined and indicated that hydrogenation increased the thermal stability of the hydrogenated rubber but did not affect the inherent glass‐transition temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4219–4233, 2006     

21世纪世界合成橡胶发展趋势与建议

介绍了２１世纪世界合成橡胶总的发展趋势以及主要合成橡胶品种的发展趋势并提出了发展我国合成橡胶工业 打应对策与建议。     

我国合成橡胶工业现状及发展建议Ⅰ.现状分析

分析了我国合成橡胶工业的现状。阐述了我国合成橡胶现有七大品种的供需现状,指出了合成橡胶工业与国外相比存在的差距及我国合成橡胶产品的发展趋势。虽然我国合成橡胶工业有了持续快速增长,合成橡胶的产量仍不能满足国内市场需求,合成橡胶市场仍有较大发展空间。     

Effects of modified silica on the co-vulcanization kinetics and mechanical performances of natural rubber/styrene–butadiene rubber blends

Rubber blends are widely used for combining the advantages of each rubber component. However, to date, how to determine and distinguish the vulcanization kinetics for each single rubber phase in rubber blends during the co-vulcanization process is still a challenge. Herein, high-resolution pyrolysis gas chromatography–mass spectrometry (HR PyGC-MS) was employed for the first time to investigate the vulcanization kinetics of natural rubber (NR) and styrene–butadiene rubber (SBR) in NR/SBR blends filled with modified silica (SiO₂). The reaction rates of crosslinking of each rubber phase in NR/SBR were calculated, which showed that the crosslinking rates of NR were much lower than those of SBR phase in the unfilled blends and blends filled with unmodified and silane modified silica. Interestingly, the vulcanization rates of NR and SBR phase were approximately same in the vulcanization accelerator modified silica filled blends, showing better co-vulcanization. In addition, the vulcanization accelerator modified silica was uniformly dispersed and endowed rubber blends with higher mechanical strength compared to the untreated silica. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48838.     

Controlled degradation in tailor-made macromolecules elaboration. Controlled chain-cleavages of polydienes by oxidation and by metathesis

A chain cleavage reaction allowing the transformation of high molecular weight polymers in well-defined oligomers can be considered as a step in a synthetic scheme. The control of oligomers with respect to their average molecular weights, their molecular weights distributions and their chain-end microstructures implies the control of the cleavage reaction with respect to its yield, its regiospecificity and its chemiospecificity. Among several examples of efficient uses of this principle for the preparation of liquid oligomers from unsaturated polymers, attention is focused (I) on controlled oxidative degradation of rubber and (II) on metathetical controlled degradation of 1,4-polydienes and polyakenamers. (I.a) The mechanism of the phenylhydrazine accelerated oxidation of rubber in the latex phase is described according to accurate structural studies on molecular model molecules. (I.b) The epoxidation of rubber and periodic acid cleavages of epoxides in the latex phase are interpretated referring to the influence of the biphasic medium. The results are in agreement with interfacial blocky epoxidation by the water-soluble reagent and interfacial arrangement of the epoxidized block to be cleaved. Finally the metathetical degradations resulting from back-bitting cyclisation and cross metathesis with acyclic alkenes are presented as preparative methods to get (II.a) well-defined cyclic oligomers and (II.b) telechclic oligomers (i.e. terminally functionalized oligomers).     

Compatibility studies on some polymer blend systems by electrical and mechanical techniques

Systematic electrical and mechanical studies were carried out on natural rubber (NR) blended with different types of synthetic rubber such as styrene‐butadiene rubber (SBR), polybutadiene rubber (BR), and ethylene‐propylene‐diene monomer (EPDM) as nonpolar rubbers and nitrile‐butadiene rubber (NBR) and chloroprene rubber (CR) as polar rubbers. The NR/SBR, NR/BR, NR/EPDM, NR/NBR, and NR/CR blends were prepared with different ratios (100/0, 75/25, 50/50, 25/75, and 0/100). The permittivity (ε′) and dielectric loss (ε″) of these blends were measured over a wide range of frequencies (100 Hz–100 kHz) and at room temperature (∼ 27°C). The compatibility results obtained from the dielectric measurements were comparable with those obtained from the calculation of the heat of mixing. These results were confirmed by scanning electron microscopy and showed that NR/SBR and NR/BR blends were compatible while NR/EPDM, NR/NBR, and NR/CR blends were incompatible. To overcome the problem of phase separation (incompatibility) between NR and EPDM, NBR, or CR, a third component such as SBR or poly(vinyl chloride) (PVC) was added as a compatibilizing agent to these blends. The experimental data of dielectric and mechanical measurements showed that the addition of either SBR or PVC could improve the compatibility of such blends to some extent. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 60–71, 2001     

Effects of rubber‐rich domains and the rubber‐plasticized matrix on the fracture behavior of liquid rubber‐modified araldite‐F epoxies

The fracture behavior of a bisphenol A diglycidylether (DGEBA) epoxy, Araldite F, modified using carboxyl‐terminated copolymer of butadiene and acrylonitrile (CTBN) rubber up to 30 wt%, is studied at various crosshead rates. Fracture toughness, K_IC, measured using compact tension (CT) specimens, is significantly improved by adding rubber to the pure epoxy. Dynamic mechanical analysis (DMA) was applied to analyze dissolution behavior of the epoxy resin and rubber, and their effects on the fracture toughness and toughening mechanisms of the modified epoxies were investigated. Scanning electron microscopy (SEM) observation and DMA results show that epoxy resides in rubber‐rich domains and the structure of the rubber‐rich domains changes with variation of the rubber content. Existence of an optimum rubber content for toughening the epoxy resin is ascribed to coherent contributions from the epoxy‐residing dispersed rubber phase and the rubber‐dissolved epoxy continuous phase. No rubber cavitation in the fracture process is found, the absence of which is explained as a result of dissolution of the epoxy resin into the rubber phase domains, which has a negative effect on the improvement of fracture toughness of the materials. Plastic deformation banding at the front of precrack tip, formed as a result of stable crack propagation, is identified as the major toughening process.     

Toughening of poly(L‐lactide) by melt blending with rubbers

Poly(L ‐lactide) (PLA) was melt‐blended with four rubber components—ethylene–propylene copolymer, ethylene–acrylic rubber, acrylonitrile–butadiene rubber (NBR), and isoprene rubber (IR)—in an effort to toughen PLA. All the blend samples exhibited distinct phase separation. Amorphous PLA constituted a topologically continuous matrix in which the rubber particles were dispersed. According to Izod impact testing, toughening was achieved only when PLA was blended with NBR, which showed the smallest particle size in its blend samples. In agreement with the morphological analysis, the value of the interfacial tension between the PLA phase and the NBR phase was the lowest, and this suggested that rubber with a high polarity was more suitable for toughening PLA. Under the tensile stress conditions for NBR and IR blend samples, these rubbers displayed no crosslinking and showed a high ability to induce plastic deformation before the break as well as high elongation properties; this suggested that the intrinsic mobility of the rubber was important for the dissipation of the breaking energy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Global Synethetic Rubber Industrial Outlook

This paper is to compile and analyze the statistical data of synthetic rubber capacity and consumption to understand its impact of supply/demand on the global synthetic rubber market.Some forecasted consumption data were generated and published by the joint efforts of both IISRP(International Institute of Synthetic Rubber Producers)and IRSG(International Rubber Study group).The report also covers the observed industrial trends as well as some emerging issues in the synthetic rubber industry.     

发展合成橡胶延伸加工技术

从我国合成橡胶企业单一原料型生产模式的转型目标出发，重点对丁腈橡胶、乙丙橡胶和热塑性弹性体等的延伸加工技术以及废橡胶的综合利用技术作了文献调研，并根据国内橡胶制品的市场需求，对延伸加工技术系列的开发提出了相应的建议。     

Kinetics of the phase selective localization of silica in rubber blends

The Fourier transformed infrared (FTIR) spectroscopy on the rubber‐filler gel has been used as a tool for the quantitative characterization of the phase selective silica localization in styrene butadiene rubber (SBR)/natural rubber (NR) blends. The so‐called rubber‐layer L was introduced to describe the selective wetting behavior of the rubber phases to the filler. SBR/NR blends filled with silica were the focus of the experimental investigation. NR shows a higher wetting rate than SBR. Silane addition does not affect the wetting of NR but slowdowns the wetting of SBR. With increasing chamber temperature the value of the rubber‐layer L of all mixtures increases owing to the different thermal activated rubber‐filler bonding processes. Using the wetting concept the kinetics of silica localization in the phases of heterogeneous rubber blends was characterized. Because of the higher wetting rate of the NR component, in the first stage of mixing of NR/SBR blends more silica is found in the NR phase than in the SBR phase. In the next stage, silica is transferred from the NR phase to the SBR phase until the loosely bonded components of NR rubber‐layer are fully replaced by SBR molecules. POLYM. COMPOS., 31:1701–1711, 2010. © 2010 Society of Plastics Engineers.