Identification of rubber polymers in rubber blends

Abstract

Solid phase extraction (SPE) was used to separate pyrolysates of rubber blends. Then each rubber polymer in rubber blends was identified, based on interpreting infrared spectrum of separated pyrolysates. By using this method, nature–ethylene–propylene, ethylene–propylene–silicone, butyl–styrene–butadiene and ethylene–propylene–butadiene–acrylonitrile rubber blends were analysed. The analytical results show that each characteristic pyrolysate of polymer in rubber blend pyrolysate can be separated by SPE. The method for identification of rubber polymers in rubber blends by infrared coupled with SPE is flexible, rapid and low cost, compared with the method by pyrolysis gas chromatography coupled with infrared spectroscopy or mass spectroscopy.     

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.     

Compatibilization of SBR/NBR blends using chemically modified styrene‐co‐butadiene rubber Part 2. Effect of compatibilizer loading

The present work focuses on the compatibization of styrene‐co‐butadiene rubber (SBR)/acrylonitrile‐co‐butadiene rubber (NBR) blends with dichlorocarbene modified styrene‐co‐butadiene rubber (DCSBR) as a function of concentration of compatibilizer and composition of the blend. FTIR studies, differential scanning calorimetry and dynamic mechanical analysis reveal molecular level miscibility in the blends in the presence of compatibilizer. The formation of interfacial bonding is assessed by analysis of swelling behaviour, cure characteristics, stress–strain data and mechanical properties. These studies show that the compatibilizing action of DCSBR becomes more prominent as the proportion of NBR in the blend increases. The resistance of the vulcanizate towards thermal and oil ageing improved with compatibilization. The change in technological properties is correlated with the crosslink density of the blends assessed from swelling and stress–strain data. © 2001 Society of Chemical Industry     

Investigation of rubber–rubber blends miscibility

Polybutadiene rubber, poly(styrene‐co‐butadiene) rubber, natural rubber, and their blends were investigated to estimate the degree of miscibility of components in the blends. The morphology of a rubber–rubber blend controls its rheological properties and glass transition behavior. Therefore, two different measuring techniques were used: rheological characterization of blends by the rubber process analyzer (RPA) and temperature modulated differential scanning calorimetry (TMDSC). To study the dependence of complex viscosity on blend composition, two commonly used empirical mixing rules were applied: the log‐additivity mixing rule and the quadratic mixing rule. Viscoelastic properties of the examined samples were described by mechanical and relaxation spectra. Since the RPA measurements cannot be performed in a wide frequency range, the experimental results cannot offer a complete overview. Also, the quantitative analysis using the differential of the heat capacity, dC_p/dT, versus the temperature signal from TMDSC did not allow to calculate the weight fraction of the interface for all types of the blends under investigation. However, the combination of the two techniques applied provided complementary information on blend morphology and rubber–rubber miscibility. POLYM. ENG. SCI. 46:1649–1659, 2006. © 2006 Society of Plastics Engineers.     

Styrene–butadiene block copolymer with high cis‐1,4 microstructure

The sequential block copolymerization of styrene (St) and butadiene (Bd) was carried out with an activated rare earth catalyst composed of catalyst neodymium tricarboxylate (Nd), cocatalyst Al(i‐Bu)₃ (Al), and chlorinating agent (Cl). The microstructure, composition, and morphology of the copolymer were characterized by FTIR, ¹H NMR, ¹³C NMR, and TEM. The results show that styrene–butadiene diblock copolymer with high cis‐1,4 microstructure of butadiene units (～ 97 mol %) was synthesized. The cis‐selectivity for Bd units was almost independent on the content of styrene units in the copolymer ranging from 18.1 mol % to 29.8 mol %. The phase‐separated morphology of polystyrene (PS) domains of about 40 nm tethered by the elastomeric polybutadiene (PB) segments is observed. The PS‐b‐cis‐PB copolymer could be used as an effective compatilizer for noncompatilized binary PS/cis‐PB blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Retardation of cold flow in immiscible rubber blends by tailoring their microstructures

Cold flow is a well‐known characteristic and also an unresolved drawback for uncured rubber materials. In this paper, a simple approach of retarding the cold flow of cis‐1,4‐polybutadiene rubber (BR) elastomer is reported by controlling the phase separation and crystallization that occurs in immiscible BR/trans‐1,4‐polyisoprene (TPI) blends. The BR/TPI blends showed an untypical phase diagram below 150 ^oC. Upon crystallization the amorphous BR facilitates the nucleation of TPI. The higher the BR content is, the less the surface roughness of the TPI crystals, and then a larger dendritic pattern that resulted from the cold flow of BR was observed in the microstructure. BR/TPI blends with the highest resistance to cold flow were obtained by optimizing the composition and thermal treatment in such a way that small soft amorphous BR domains were entrapped in the rigid TPI crystalline phase. It is expected that this study could provide a simple way for the prevention of cold flow of rubber materials. © 2017 Society of Chemical Industry     

Styrene–butadiene rubber membranes for the pervaporative separation of benzene/cyclohexane mixtures

Styrene–butadiene rubber membranes with methylene bridges, stemming from the concomitant in situ Friedel–Crafts alkylation during a chloromethylation reaction, were prepared and used in the pervaporative separation of benzene/cyclohexane mixtures. A set of four membranes with different crosslinking extents was achieved by the variation of the [Trimethylchlorosilane (TMCS)]/[Paraformaldehyde (PF)] molar ratios with respect to the styrene (St) unit. Study of the swelling of membranes by the mixture components individually and by their feed mixture compositions, 1 : 1 and 1 : 9, was conducted. The total flux (J) and the separation factor (α) were assessed as a function of the feed composition, temperature, and [St unit]/[TMCS]/[PF] molar ratios. The highest J and α measured in this study were 1401 g m^?2 h^?1 and 28.50, respectively. The diffusion selectivity was found to depend on the crosslinking extent of the membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the processing conditions and the addition of trans-polyoctenylene rubber on the properties of natural rubber/styrene–butadiene rubber blends

In this study, the influence of the processing conditions and the addition of trans-polyoctenylene rubber (TOR) on Mooney viscosity, tensile properties, hardness, tearing resistance, and resilience of natural rubber/styrene–butadiene rubber blends was investigated. The results obtained are explained in light of dynamic mechanical and morphological analyses. Increasing processing time produced a finer blend morphology, which resulted in an improvement in the mechanical properties. The addition of TOR involved an increase in hardness, a decrease in tear resistance, and no effect on the resilience. It resulted in a large decrease in the Mooney viscosity and a slight decrease in the tensile properties if the components of the compounds were not properly mixed. The results indicate that TOR acted more as a plasticizer than a compatibilizer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

1,3‐butadiene polymerization using Co/Nd‐based Ziegler/Natta catalyst: Microstructures and properties of butadiene rubber

Among Ziegler‐Natta catalysts used for 1,3‐butadiene (1,3‐BD) polymerization, the advantage of a neodymium (Nd)‐based catalyst is that it provides butadiene rubber (BR) with a high content of cis?1,4 configuration and a low amount of vinyl?1,2 units. Whereas, a cobalt (Co)‐based catalyst can produce BR with a low content of trans?1,4 configuration. Thus, this research was aimed to prepare BR containing a high content of cis?1,4 configuration with low amounts of both trans?1,4 and vinyl?1,2 units using a combination of Nd‐ and Co‐based Ziegler/Natta catalysts with triethyl aluminum (TEAL) and diethyl aluminum chloride (DEAC) acting as a co‐catalyst and a chlorinating agent, respectively. The effects of the molar Co/Nd ratio, TEAL concentration, DEAC loading, 1,3‐BD content, solvent type, and reaction temperature on % conversion, microstructures, molecular weight, and molecular weight distribution of the obtained BR (Co/Nd‐BR) were evaluated. The Co/Nd‐BR having >97% of cis?1,4 configuration, <2% of trans?1,4 structure, and <1% of vinyl?1,2 unit with >80% conversion was achieved when 3.01 M of 1,3‐BD concentration was treated in a toluene/cyclohexane mixture (7/3 [w/w]). The Co/Nd‐BR exhibited no gel formation with high mechanical performance, which was equivalent to commercial BR produced from a Nd‐based catalyst system. POLYM. ENG. SCI., 55:14–21, 2015. © 2014 Society of Plastics Engineers     

Characterization of sulfur-cured styrene–butadiene copolymer rubbers and their polybutadiene blends

Dissolution of sulfur-cured, carbon black-loaded copolymers and their blends with cis-1,4-polybutadiene (PBD) are brought about by boiling with o-dichlorobenzene which contains a small amount of 2,2′-dibenzamidodiphenyl disulfide. The resulting slurries are subjected to a sequence of separations which include high-speed centrifugation to remove solids, and solvent precipitation followed by filtration to isolate the precipitates. The precipitates are washed with solvent to remove soluble organic materials followed by carbon disulfide washing to dissolve the polymers. Cast films of the polymers are obtained by evaporating the carbon disulfide washings onto sodium chloride discs. The infrared spectra of the cast films of these preparations are very similar to those of their respective polymers prior to loading and curing. Calculations for relative concentrations of bound styrene and PBD microstructures permit nominal identification of the kinds of styrene–butadiene rubber and the amounts of cis-1,4-PBD used in a cured rubber formulation. Absorption bands used are near 3.35 μ for cis-1,4-PBD, 6.65μ for bound styrene, 10.35 μ for trans-1,4-PBD; and 11.0 μ for vinyl-1,2-PBD. Efforts are being made to improve the data by using a grafting infrared instrument and also to extend the calibrations to include other rubber blends.     

A study about the structure of vulcanized natural rubber/styrene butadiene rubber blends and the glass transition behavior

A study of the thermal behavior of cured elastomeric blends of natural rubber (NR) and styrene butadiene rubber (SBR) prepared by solution blending in toluene is presented. Binary blends with different compositions of NR/SBR were produced using a conventional cure system based on sulfur and TBBS (n-t-butyl-2-benzothiazole sulfonamide as accelerator. The compounds were vulcanized at 433 K up to an optimum time of cure determined by rheometric tests. From swelling tests, the crosslink densities of the compounds were obtained and compared with those obtained in similar blends prepared by mechanical mixing. The results were analyzed in terms of the disentangling of the chain structures of the SBR and NR phases and the achieved cure state of the blend. Using differential scanning calorimetry, the glass transition temperature T_g of each blend was measured. In most compounds, the value of T_g corresponding to each phase of the blend was determined, but in some blends a single value of T_g was obtained. The variation of T_g with the composition and cure level in each phase was analyzed. On the other hand, a physical mixture of two equal parts of NR and SBR vulcanized was measured and the results were compared to those of the NR50/SBR50 cured blend. Besides, to analyze the influence of the network structure, pure NR and SBR unvulcanized samples were measured. On the basis of all the obtained results, the influence of the interphase formed in the blend between SBR and NR phases is discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dynamic mechanical properties of styrene butadiene rubber and poly (ethylene-co-vinyl acetate) blends

The dynamic mechanical behaviour of uncrosslinked and crosslinked styrene butadiene rubber/poly (ethylene-co-vinyl acetate) (SBR/EVA) blends was studied with reference to the effects of blend ratio, crosslinking systems, a compatibilizer viz. maleic-anhydride grafted poly [styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS-g-MA), frequency and temperature. The two separate tan δ peaks, obtained during DMA, indicated the immiscibility of SBR/EVA system. The damping properties increased with SBR content for uncrosslinked and crosslinked blends. In the case of crosslinked systems, depending upon the type of crosslinking agent used, the glass transition temperature (T _g) of SBR phase has been found to be shifted to higher temperatures. The damping characteristics of the blends were observed to be affected by the variations in frequency. The addition of the compatibilizer improved the storage modulus and reduced the damping properties. These results have been correlated with the morphology of the blends, attested by scanning electron micrographs. The activation energy for glass transition has been computed. The experimental data on storage modulus were compared with theoretical predictions.     

Synthesis,by reactive extrusion,of high molar mass epoxy prepolymers containing rubber preformed particles

High molar mass epoxy prepolymers containing rubber dispersions based on carboxyl-terminated butadiene-acrylonitrile random copolymer (CTBN) were prepared from initially miscible solution of low molar mass epoxy prepolymers, bisphenol A and CTBN-based rubber. During chain extension inside a twin-screw extruder due to epoxy-phenoxy and epoxy-carboxy reactions, a phase separation process occurs. Epoxy-phenoxy and epoxy-carboxy reactions were catalyzed by the triphenyl phosphine. The effect of reaction parameters (temperature, catalyst, reactant stoechiometry) on the reactive extrusion process were analyzed. The structure of the prepolymers showed low branching reactions (2–5%). Low molar mass prepolymers have a Newtonian rheological behavior. Cloud-point temperature of different reactive liquid butadiene acrylonitrile random copolymer (RLP)/epoxy resin blends were measured for different RLP concentrations. It was shown that rubber particles remain insoluble in a range of temperature from room temperature to 180°C, typical of temperatures used for epoxy curing reactions. Prepolymers containing different rubber concentrations were cured using dicyandiamide as the hardener. The practical adhesion of the issued networks to an aluminium alloy increased with rubber concentration. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2447–2456, 1997     

Mechanical and sorption properties of poly(ethylene-co-vinyl acetate)(EVA) compatibilized acrylonitrile butadiene rubber/natural rubber blend systems

Poly (ethylene-co-vinyl acetate) (EVA) has been used as a compatibilizer for heterogeneous natural rubber/acrylonitrile butadiene rubber (NR/NBR) blends. NR/NBR (50/50) blends were compatibilized with varying amounts, from 0 to 10 parts per hundred rubber (phr), of EVA. The compatibility of the blend components in presence of EVA has been evaluated in terms of mechanical and sorption characteristics. The mechanical properties were found to be improved by the addition of EVA upto 6 phr. The solvent resistance of the compatibilized samples has been observed to be higher compared to the uncompatibilized blends; attributed to the increased interfacial adhesion between the blend components. DSC studies showed a shift of glass transition temperatures of the blend components towards higher temperatures indicating increased rigidity of the matrix in presence of EVA.     

Influence of rubber composition on migration behaviors of antiozonants in carbon black‐filled rubber vulcanizates composed of NR,SBR, and BR

Migration behaviors of antiozonants in carbon black‐filled rubber vulcanizates with different rubber compositions of natural rubber (NR), styrene–butadiene rubber (SBR), and butadiene rubber (BR) were studied at constant temperatures of 40–100°C and outdoors. Three single rubber‐based vulcanizates, three biblends, and three triblends were used. N‐Phenyl‐N′‐isopropyl‐p‐phenylenediamine (IPPD) and N‐phenyl‐N′‐(1,3‐dimethylbutyl)‐p‐phenylenediamine (HPPD) were employed as antiozonants. Migration rates of the antiozonants became faster with increasing the temperature. The order of the migration rates in the single rubber‐based vulcanizates was BR > NR > SBR. The migration rates in the vulcanizates containing SBR, on the whole, increased with decreasing the SBR content, while those in the vulcanizates containing BR decreased with decreasing the BR content. Difference in the migration behaviors of the antiozonants depending on the rubber composition was explained both by the intermolecular interactions of the antiozonants with the matrix and by interface formed between dissimilar rubbers in the blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 237–242, 2001     

A Study of FTIR,Thermal Properties and Natural Weathering Test on NBRVirgin/Recycled with SBR Blends

The effects of styrene butadiene rubber/virgin acrylonitrile butadiene rubber (SBR/NBRv) blends and styrene butadiene rubber/recycled acrylonitrile butadiene rubber (SBR/NBRr) blends on properties such Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were carried out. Results indicated that, based on intensity of amine peak from FTIR at 85/15 blend ratio (R15) revealed optimum formation of crosslink between SBR and NBR either using virgin or NBRr. TG thermograms of SBR/NBRv blends of all ratios showed better onset thermal stability than SBR/NBRr blends. The change in the horizontal baseline from high to low energy level occurred in virgin NBR blends because the amount of reactive sites available in virgin NBR is higher compared to NBRr. Meanwhile NBRr blends showed T_c because the amount of crosslink occurred in these blends were slightly lower than NBRv blends. Up to 25 phr of NBRr, the tensile strength and elongation at break (E_b) retention of SBR/NBRv blends was better than SBR/NBRr blends after 6 months' weathering test except for M100. The scanning electron microscopy on the surface of both blends after 6 months exposure indicated that the severity of the crack was minimal for SBR/NBRr blends compared to SBR/NBRv particularly at 50/50 blend ratio designated the SBR/NBRr blends that contained more NBRr particles could reduce the degradation towards natural weathering.     

Interpenetrating polymer networks: High molecular weight natural rubber and poly(2,6-dimethyl-1,4 phenylene oxide)

Simultaneous interpenetrating polymer networks (IPNs) of high molecular weight natural rubber (NR) from Manihot glaziovii and poly(2,6-dimethyl-1,4 phenylene oxide) were prepared and characterized. A number of pseudo IPNs and blends of these materials were also studied. A single phase morphology is found in full IPNs with either high or low weight percent of NR. The intermediate composition full IPNs, pseudo IPNs, and blends all exhibited microphase separation, as seen by both DSC and SEM studies with domains sizes in the range of 1000–4000 nm. In the discussion we briefly compare these IPNs with the other previously prepared IPNs of poly(2,6-dimethyl-1,4-phenylene oxide).     

Devulcanization of nitrile butadiene rubber in nitrobenzene

Sulfur‐crosslinked nitrile butadiene rubber (s‐NBR) was found to be devulcanized when it was heated with nitrobenzene at 200°C for 3 h. The tetrahydrofuran (THF)‐soluble fraction from s‐NBR heated with nitrobenzene was purified by reprecipitation with THF/n‐hexane, chloroform/n‐hexane, and THF/n‐hexane systems and was then characterized by means of Fourier transform infrared (FTIR) spectroscopy, ¹H‐NMR, gel permeation chromatography, dynamic thermogravimetry/differential thermal analysis (DTA), and differential scanning calorimetry (DSC). FTIR and ¹H‐NMR results revealed that the THF‐soluble fraction contained aromatic rings derived from nitrobenzene. Furthermore, the molecular weight of the THF‐soluble fraction was much lower than that of the parent noncrosslinked poly(acrylonitrile‐co‐butadiene). Although the weight loss of THF‐soluble fraction began at a lower temperature than that of the nonheated original nitrile butadiene rubber, the residual weight at 700°C tended to be higher for the former. This tendency became more marked with increasing time of heat treatment with nitrobenzene. The DSC‐determined glass‐transition temperature of the THF‐soluble fraction was higher than that of the original s‐NBR. To elucidate the devulcanization mechanism, we investigated two types of model reactions; one was the reaction of diphenyl disulfide with nitrobenzene, and the other was the reaction of polybutadiene with nitrobenzene. The former reaction, carried out at 250°C in diphenyl ether, yielded diphenyl sulfide with a loss of diphenyl disulfide and nitrobenzene. The use of a higher molar ratio of nitrobenzene to diphenyl disulfide resulted in a depression of diphenyl sulfide formation. The reaction of p‐chloronitrobenzene with diphenyl disulfide also gave diphenyl sulfide. The reaction of polybutadiene with nitrobenzene at 200°C resulted in the backbone scission of the polymer. The THF‐soluble solid product of the latter model reaction was found by FTIR and ¹H‐NMR to contain aromatic rings derived from nitrobenzene. The devulcanization mechanism is discussed on the basis of a comparison of the results of the model reactions with those of the s‐NBR devulcanization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3342–3353, 2004     

Effect of epoxidised liquid natural rubber on nitrile/butadiene rubber based mixes

Abstract

Epoxidised liquid natural rubber (ELNR) constitutes a new family of polymers chemically derived from natural rubber. It is a highly viscous rubber of low molar mass generally used as plasticiser or processing aid, especially during processing of natural rubber and styrene/butadiene rubber stocks.

The effect of incorporating this polymer rather than a standard plasticiser in a nitrile/butadiene rubber based mix has been investigated. The retention in mechanical properties following air and oil aging of the vulcanisates was also studied. Satisfactory processability of compounded stocks, mechanical properties, and aging resistance was maintained following incorporation of ELNR into nitrile/butadiene rubber formulations even at the lowest plasticiser concentrations. The improvement in aging behaviour was more pronounced when 25 mol-% ELNR was used at concentrations above 15 pphr.     

Microstructure and miscibility of acrylonitrile–butadiene rubber/ethylene–propylene–diene monomer blends studied by positron annihilation spectroscopy

The free‐volume properties and miscibility of ethylene–propylene–diene monomer/acrylonitrile–butadiene rubber blends with poly(vinyl chloride) used for compatibilization were investigated with positron annihilation lifetime spectroscopy and Doppler broadening of annihilation radiation. The results showed that the ortho‐positronium annihilation lifetimes and intensities as well as the S parameter had a linear relationship with a negative slope as a function of the weight percentage of acrylonitrile–butadiene rubber, which indicated the miscibility of the blend. The filling effect of silica on the free‐volume properties of an ethylene–propylene–diene monomer/acrylonitrile–butadiene rubber (75/25) blend was also examined. On the other hand, a correlation between the size and concentration of the free‐volume holes and the electrical and mechanical properties of the aforementioned blends was established. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007