A study of dynamic vulcanization for polyamide‐12 and chlorobutyl rubber

Polyamide‐12 and chlorobutyl rubber were blended by dynamic vulcanization in a high shear environment using curing systems based on sulfur, dithiocarbamate/ZnO, and 4,4‐methylenebiscyclohexylamine/MgO. As expected, all blends with curing agents show increased tensile strength and elongation at break in comparison to blends without curing agents. Maximum mechanical properties are obtained at relatively low levels of curing agent in all systems. Hexane extraction of the mixtures and measurement of percentage of insolubles along with the swelling index of the rubber phase confirm that a high level of cure is achieved at low levels of curing agent. Although the curatives are designed for the rubber phase, differential scanning calorimetry results indicate that both phases are affected during the dynamic vulcanization process, with polyamide‐12 showing a reduced melting temperature that is indicative of molecular weight reduction, structure changes, or reaction with the rubber phase. Scanning electron microscopy results indicate that phase size is reduced with increased blending time and level of curing agent. Rheological studies indicate that blends containing curing agents exhibit non‐Newtonian behavior to a greater extent than polyamide or nonvulcanized polyamide/chlorobutyl rubber blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 871–880, 2003     

溴化丁基橡胶特性及其应用

溴化丁基橡胶(BIIR)是卤化丁基橡胶的一种,它既保持了丁基橡胶原有的特性,又增添了许多优异的性能,如硫化速度快,硫化方式多样等.本文主要论述了溴化丁基橡胶的结构与性能、硫化体系、生产现状及应用情况.在将溴化丁基橡胶与丁基橡胶(IIR)、氯化丁基橡胶(CIIR)比较的基础上,阐述溴化丁基橡胶的优异特性及广阔的应用前景.     

Solvent resistance and mechanical properties in thermoplastic elastomer blends prepared by dynamic vulcanization

Dynamic vulcanization was used to prepare thermoplastic elastomer blends of nylon (polyamide), polypropylene (PP) and polybutylene terephthalate thermoplastics with chlorobutyl (CIIR) and nitrile (NBR) rubbers. Mechanical properties of the blends were correlated against composition. Although hardness and tensile strength increase with increasing thermoplastic content for all blends, elongation at break values initially decrease and then increase in the range of 20–40% thermoplastic. For various blend compositions, the swelling behavior was evaluated with solvents that are able to dissolve the uncured rubber portion but not the thermoplastic component of the mixtures. All five systems showed swelling index values that were substantially less than the calculated “theoretical” values of swelling index. This was attributed to a caging effect of the thermoplastic component on the rubber phase, which restricts access of solvent and swelling of the rubber phase. In turn, this affects the solvent resistance of the blend. Some of the blends were evaluated by differential scanning calorimetry to assess the compatibility of the components in the blend. scanning electron microscopy was also used to determine the degree of compatibility of the two phases generated in the mixing process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

丁基橡胶及卤化丁基橡胶阻尼材料的研究进展

介绍了丁基橡胶的阻尼性能及应用,阐述了丁基橡胶、氯化丁基橡胶及溴化丁基橡胶阻尼材料的研究进展。指出提高损耗因子和拓宽阻尼温域是丁基橡胶基高性能阻尼材料的研究方向,丁基橡胶与其他橡胶共混、开发合适的硫化体系和填料是提高丁基橡胶基阻尼材料性能的重要手段。     

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

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

动态硫化橡胶／橡胶共混物的制备及性能

综述了橡胶／橡胶共混物动态硫化的研究进展，介绍了并用橡胶采用动态硫化技术时，橡胶品种及硫化体系的选择原则，对动态硫化共混橡胶的性能进行了描述。     

Dynamically vulcanized polypropylene/styrene–butadiene rubber blends: The effect of a peroxide/bismaleimide curing system and composition

Polypropylene (PP)/styrene–butadiene rubber blends were studied with special attention given to the effects of the blend ratio and dynamic vulcanization. Dicumyl peroxide (DCP) was used as the curing agent in combination with N,N′‐m‐phenylene bismaleimide (BMI) as the coagent for the curing process. Outstanding mechanical performance, especially with regard to the elongation at break, and better resistance to compression set were achieved with the dynamic vulcanization; this indicated that the DCP/BMI system also acted as a compatibilizing agent. This phenomenon was also confirmed by Fourier transform infrared spectroscopy of the insoluble material, the crystallinity degree of the PP phase (as investigated by X‐ray diffractometry), and scanning electron microscopy. The dynamic mechanical properties of the nonvulcanized and vulcanized blends were also investigated. The aging resistance of the blends was also evaluated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of butyl rubber nanocomposites in presence and absence of compatibiliser

Abstract

Chlorobutyl rubber nanocomposites containing organically modified nanoclay (CI-C) were prepared by solution mixing. The nanoclay used in this study was Cloisite 20A. The obtained nanocomposites were incorporated in butyl rubber (IIR) with sulphur as a curing agent. Morphology, curing characteristics, mechanical and gas barrier properties of the nanocomposites were analysed. The morphological studies proved the partial exfoliation along with agglomeration of nanoclay platelets in chlorobutyl rubber, and further incorporation of CI-C in IIR matrix enhance the exfoliation of the nanoclay platelets. Curing study demonstrated shorter scorch time, cure time and increase in maximum torque for the nanoclay loaded IIR compound in the presence of chlorobutyl rubber as a compatibiliser compared to pure and IIR-nanoclay compound without compatibilisers. Dynamic mechanical thermal analysis results showed tremendous improvement in storage modulus and decrease in tan?δ value for the one containing a compatibiliser. This particular compound exhibited substantial improvement in mechanical and gas barrier properties.     

The effects of compatibility on the mechanical properties and fatigue resistance of butyl/EPDM rubber blends

In this study, compatibility of butyl/ethylene‐propylene‐diene rubbers in different ratios was investigated byviscometric technique. For evaluating polymer compatibility, the parameters Δb suggested by Krigbaum&Wall, ΔB and μ that were suggested by Chee were calculated. Data obtained from viscometric study were used for preparing new compound recipe. Mechanical and rheological properties of the new compounds were measured and the changes in the properties before and after thermal aging were determined. Replacement of ethylene‐propylene‐diene rubber with butyl rubber in appropriate ratio improved the fatigue resistance of the vulcanizates. Improvement of dynamic mechanical properties of polymer blends is expected only in the case of blending compatible polymers in appropriate ratios. The compatibility of blends in different ratios has been studied by viscometric technique and mechanical measurements and obtained very similar results. It has been concluded that viscometric determination of butyl/ethylene‐propylene‐diene rubbers compatibility could be used as a simple technique for predicting the mechanical properties of the same rubber blend that was related with solid phase compatibility. POLYM. COMPOS., 31:1869–1873, 2010. © 2010 Society of Plastics Engineers.     

The effect of adding devulcanized rubber on the thermomechanical properties of recycled polypropylene

This work aims to investigate the effect of adding vulcanized or partially devulcanized rubbers on recycled polypropylene (PPr), considering thermomechanical and morphological properties. The study proposes to better understand how structural changes underwent by rubber (after the devulcanization) contributed to improving the mechanical properties of the PPr. The PPr/rubber blends were prepared by a co-rotating twin-screw extruder and then were injected. The blends composed of the most devulcanized rubbers by microwaves with refined microstructure showed higher values of elongation at break and toughness. Data showed that the devulcanization process applied to the rubber interfered positively in its adhesion to the PPr. Data from dynamic mechanical analysis and atomic force microscopy indicated that the most devulcanized rubbers presented an interface more connected to PPr. These chemical interactions possibly impacted the mechanical properties of the PPr. Moreover, dilatation processes favored the fracture mechanisms of the PPr when rubber was added to it.     

Toughening of polylactide with natural rubber grafted with poly(butyl acrylate)

Natural rubber grafted with poly(butyl acrylate) (NR‐g‐PBA) in an attempt to toughen polylactide (PLA) was prepared by grafting butyl acrylate onto natural rubber (NR) through emulsion polymerization. The purified NR‐g‐PBA was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. NR‐g‐PBA/PLA blend and NR/PLA blend were prepared with a Haake internal melt mixer. The morphology and mechanical properties of the blends were investigated as a function of rubber content. Observations by scanning electron microscopy showed that the spherical‐particle‐dispersed phase appearing in the NR/PLA blend was not found in the NR‐g‐PBA/PLA blend, which showed that NR grafted with PBA is compatible with PLA, and accounted for the efficient toughening effect on PLA. The elongation at break and the impact strength were significantly improved with an increase in NR‐g‐PBA content. The thermal stability of PLA decreased when blended with NR but was retained with NR‐g‐PBA. Copyright © 2011 Society of Chemical Industry     

Morphology and mechanical properties of ethylene‐vinyl acetate rubber/polyamide thermoplastic elastomers

High performance thermoplastic elastomers based on ethylene‐vinyl acetate rubber (EVM) and ternary polyamide copolymer (tPA) were prepared through a dynamic vulcanization process in the presence of dicumyl peroxide (DCP). The morphology, crystallization, and mechanical properties of the EVM/tPA blends were studied. A phase transition of EVM/tPA blend was observed at a weight ratio of 60/40. The presence of EVM increased the melting enthalpy at the high temperature of tPA, ascribing to the heterogeneous nucleating effect of EVM. The tensile strength of EVM/tPA (70/30) blends was increased up to 20.5 MPa as the DCP concentration increased to 3.5 phr, whereas the elongation at break of the blends kept decreasing as the DCP concentration increased. The addition of ethylene‐acrylic acid copolymer (EAA) or maleic anhydride‐grafted EVM (EVM‐g‐MAH) to the EVM/tPA blends both induced finer dispersion of the EVM particles in the tPA phase and improvement in the tensile strength and elongation at break of the blends, which were ascribed to the compatibilization of EAA or EVM‐g‐MAH. Finally, a high performance EVM/tPA (70/30) thermoplastic elastomer with Shore A hardness of 75, tensile strength of 24 MPa, elongation at break of 361%, and set at break of 20% was obtained by adding 5 wt % of EVM‐g‐MAH and 3.5 phr DCP. It has great potential in automotive and oil pipeline applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of the self‐crosslinked acrylic rubber via gamma ray initiated emulsion polymerization

In this study, a series of self‐crosslinked acrylic rubbers were prepared by gamma ray initiated emulsion copolymerization. Acrylic acid and N‐hydroxymethl acrylamide were used as the cure‐site monomers. The vulcanizing properties, tensile properties, and dynamic mechanical analysis of the self‐crosslinked acrylic rubbers were investigated. It was found that the curing characteristics could be influenced significantly by the content and species of the cure‐site monomers. Improvement in mechanical properties like tensile strength, modulus and elongation at break was observed in the prepared self‐crosslinked rubber. The structure‐property correlation of the self‐crosslinked acrylic rubber was discussed. POLYM. ENG. SCI. 46:1748–1753, 2006. © 2006 Society of Plastics Engineers.     

Cure characteristics,morphology, mechanical properties,and aging characteristics of silicone rubber/ethylene vinyl acetate blends

Silicone rubber/ethylene vinyl acetate (SR/EVA) rubber mixes with different ratios were prepared by using dicumyl peroxide (DCP) and benzoyl peroxide (BP) as curing agents. The vulcanization characteristics such as cure kinetics, activation energy, and cure rate of the blends were analyzed. The effects of blend ratio and curing agents on the mechanical properties such as stress–strain behavior, tensile strength, elongation at break, tear strength, relative volume loss, hardness, flex crack resistance, and density of the cured blends have been investigated. Almost all the mechanical properties have been found to be increased with increase in EVA content in the blends particularly in DCP‐cured systems. The increment in mechanical properties of the blends with higher EVA content has been explained in terms of the morphology of the blends, attested by scanning electron micrographs. Attempts have been made to compare the experimental results, from the evaluation of mechanical properties, with relevant theoretical models. The aging characteristics of the cured blends were also investigated and found that both the DCP‐ and BP‐cured blends have excellent water and thermal resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1069–1082, 2006     

Preparation of thermoplastic vulcanizates based on waste crosslinked polyethylene and ground tire rubber through dynamic vulcanization

An environmental‐friendly approach called high‐shear mechanical milling was developed to de‐crosslink ground tire rubber (GTR) and waste crosslinked polyethylene (XLPE). The realization of partial devulcanization of GTR and de‐crosslinking of XLPE were confirmed by gel fraction measurements. Fourier transform infrared spectral studies revealed that a new peak at 1723.3 cm^?1 corresponds to the carbonyl group (? C?O) absorption was appeared after milling. The rheological properties showed that the XLPE/GTR blends represent lower apparent viscosity after mechanical milling, which means that the milled blends are easy to process. Thermoplastic vulcanizates (TPVs) could be prepared with these partially de‐crosslinked XLPE/GTR composite powders through dynamic vulcanization. The mechanical properties of the XLPE/GTR composites increased with increasing cycles of milling. The raw XLPE/GTR blends could not be processed to a continuous sheet. After 20 cycles of milling, the tensile strength and elongation at break of XLPE/GTR (50/50) composites increased to 6.0 MPa and 185.3%, respectively. The tensile strength and elongation at break of the composites have been further improved to 9.1 MPa and 201.2% after dynamic vulcanization, respectively. Re‐processability study confirmed the good thermoplastic processability of the TPVs prepared. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New gasoline and gas barrier from plasticized carbon black reinforced butyl rubber/high‐density polyethylene blends

The effects of the high‐density polyethylene volume fraction on the curing characteristics and network structure of rubber blends have been studied in terms of the torque, scorch time, optimum curing time, Mooney viscosity, number of elastically effective chains, viscosity, interfacial tension, glass‐transition temperature, scanning electron microscopy, internal friction, sound velocity, acoustic attenuation, polymer–solvent interaction parameter, swelling index, and gel fraction. The applicability of the blends for gasoline barriers has been examined through the changes in the electrical resistance and volumetric swelling in gasoline versus time at room temperature. The transport mechanism of the solvent through the crosslinked butyl rubber/high‐density polyethylene blends is governed by Fickian diffusion law. The transport coefficients, namely, the diffusion coefficient, intrinsic diffusion, and permeation coefficient, have been computed. The experimental data for the permeation coefficient are in good agreement with the values calculated by Maxwell's model and far from those of Robeson's model. In addition, some thermodynamics parameters, namely, the standard entropy, standard enthalpy, and standard Gibbs free energy, have been estimated as functions of the high‐density polyethylene concentration of the butyl rubber blends. Furthermore, the applicability of butyl rubber/high‐density polyethylene composites for Freon gas barriers and antistatic charge dissipation has been examined. Finally, the mechanical properties, such as the tensile strength, hardness, stiffness, and elongation at break, of butyl rubber composites with different high‐density polyethylene concentrations have been evaluated. The increase in the mechanical properties is due to the increase in the crosslinking density and the interfacial adhesion of the blend. This proves that these new blends have important technological applications as gasoline and Freon barriers and for antistatic charge dissipation with good mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1237–1247, 2006     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of epoxide levels in ENR molecules

Epoxidized natural rubbers (ENR) with various levels of epoxide groups were prepared. Thermoplastic vulcanizates based on 75/25 ENRs/PP blends with Ph‐PP compatibilizer were later prepared by dynamic vulcanization using sulfur curing system. Influence of various levels of epoxide groups on rheological, mechanical morphological properties, and swelling resistance of the TPVs was investigated. It was found that the mixing torque, apparent shear stress, apparent shear viscosity, tensile strength, and hardness properties increased with increasing levels of epoxide groups in the ENR molecules. This may be attributed to increasing level of chemical interaction between the methylol groups of the Ph‐PP molecules and polar functional groups of the ENR molecules. Also, the PP segments in the Ph‐PP molecules are capable of compatibilizing with the PP molecules used as a blend composition. In SEM micrographs, we observed finer dispersion of vulcanized rubber domains as increasing levels of epoxide contents. This corresponds to increasing trend of strength and hardness properties of the TPVs. An increasing trend of tension set and a decreasing trend of elongation at break were observed as increasing levels of epoxide groups in the ENR molecules. This is because of higher rigidity of the vulcanized ENR phase with higher epoxide groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3046–3052, 2006     

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.     

聚苯乙烯增强室温硫化硅橡胶的制备及表征

以过氧化苯甲酰为引发剂,使苯乙烯在α,ω-羟基聚(二甲基-甲基乙烯基)硅氧烷(PDM-MVS)中进行自由基聚合,制备了PDM-MVS/聚苯乙烯(PS)共混物。将该共混物在室温下进行硫化,获得了PS增强的室温硫化硅橡胶,并对硅橡胶的力学性能和微观形态进行了表征。结果表明,目标硅橡胶的拉伸强度和扯断伸长率均随PDM-MVS中乙烯基质量分数的增加而增大,当乙烯基质量分数为1.50%时,其拉伸强度达3.9 MPa,扯断伸长率达416%,PS的增强效果明显;目标硅橡胶具有微相分离结构,PS作为分散相均匀分布于PDM-MVS连续相中,两相的相容性随着PDM-MVS中乙烯基质量分数的增加而增强。     

有效硫化体系下对MPU/NBR共混胶性能的研究

探究了在有效硫化体系下,聚醚型混炼型聚氨酯橡胶(MPU)与丁腈橡胶(NBR)并用比对共混胶性能的影响。研究表明,NBR的加入使得共混胶硫化速度变快,随着NBR份数的增加,拉断强度和扯断伸长率不断下降,表观交联密度先减小后增大,不同伸长率下的定伸应力呈现不同的变化规律。共混胶耐热空气老化性能和耐热油老化性能优异,在80℃高温拉伸中,MPU的拉断强度折损率要高于NBR。在动态力学性能研究中发现,20份NBR的加入使得共混胶动态生热明显增大。