Preparation of conductive polyaniline‐sulfonated EPDM ionomer composites from in situ emulsion polymerization and study of their properties

The composites of polyaniline (PAn) and zinc sulfonated ethylene–propylene–diene rubber (EPDM) ionomer were made by polymerization of aniline in the presence of the ionomer by using a direct, one‐step in situ emulsion polymerization technique. The ionomers were prepared by sulfonation of EPDM rubber with acetyl sulfate in petroleum ether, followed by neutralization with zinc acetate solution. The ionomers with sulfonate contents of 10, 24, and 42 mmol SO₃H/100 g were used for preparation of PAn/ionomer composites. The in situ polymerization of aniline was carried out in an emulsion comprising water and xylene containing the ionomer in the presence of dodecyl benzene sulfonic acid, acting as both a surfactant and a dopant for PAn. The composite was characterized by IR and WAXD. The composite obtained can be processed by melt method. The conductivity of the composite with lower sulfonate content was higher than that with higher sulfonate content. Conductivity of the composites exhibits a percolation threshold at about 13 wt % PAn. When the sulfonated content is 10 or 24 mmol SO₃H/100 g and PAn content is 4–10 wt %, the composites behave as a thermoplastic elastomers with high ultimate elongation and low permanent set. The conductivity of the composite after secondary doping with m‐cresol is higher than the composite before secondary doping by about one order. Addition of zinc stearate as an ionic plasticizer lowers both the conductivity and the mechanical strength of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2211–2217, 2004     

Preparation of an ionomer elastomer by continuous sulfonation in an extruder and neutralization in static mixers

Rapid and efficient sulfonation of ethylene-propylene terpolymer elastomer (EPDM) was achieved in a continuous melt mixing process. A mixture of sulfuric acid and acetic anhydride was used as the sulfonating agent. The reaction of EPDM polymer and the sulfonating agent was carried out in an extruder. It was shown that the continuous melt sulfonation of EPDM polymer may be used as an alternative to the batch solution methods previously reported for the preparation of sulfonated EPDM polymer. The extruder-reactor method offers advantages of shorter process time, elimination of solvent handling hazards, and abatement of solvent removal and recovery problems.     

Preparation,characterization, and some properties of ionomers from a sulfonated styrene–butadiene–styrene triblock copolymer without gelation

The conditions for the sulfonation of a highly unsaturated styrene–butadiene–styrene triblock copolymer (SBS) in cyclohexane containing a small amount of acetone with acetyl sulfate made by sulfuric acid and acetic anhydride without gelation were studied. After neutralization with metallic ions, the ionomers were characterized with IR spectrophotometry, dynamic mechanical analysis, and transmission electron microscopy. The melt flow, solution properties, and mechanical properties of the ionomers were studied. The results showed that gelation occurred during the sulfonation of SBS in cyclohexane at a 5–10% concentration without acetone, whereas in the presence of 5–10 vol % acetone, sulfonation proceeded smoothly without gelation. Transmission electron microphotographs of the lead ionomer indicated the presence of ionic domains. A dynamic mechanical spectrum showed the presence of three transition temperatures: ?82.9, 68, and 96.5°C. The melt viscosity of the ionomer increased with the sulfonate content. The melt viscosity of the different ionomers neutralized with different cations seemed to decrease with decreasing ionic potential for both monovalent cations and divalent cations The solution viscosity of the sodium‐sulfonated ionomer increased with increasing sulfonate content. The ionomer still behaved as a thermoplastic elastomer and showed better mechanical properties than the original SBS. The tensile strength of the different ionomers decreased as follows. For the monovalent cations, it decreased with decreasing ionic potentials: Li⁺ > Na⁺ > K⁺. For the divalent cations, it decreased with increasing ionic potentials: Pb²⁺ > Zn²⁺ > Mg²⁺. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1398–1404, 2005     

A Study on Morphology and Properties of IPP/Zinc-Neutralized Sulfonated EPDM Blends

The effect of zinc-neutralized sulfonated EPDM (Zn-SEPDM) on the compatibility and the crystallizing behavior of isotactic polypropylene (IPP), and also the morphology of the blend were studied through WAXD, DSC, TEM, and mechanical properties test. The results show that addition of Zn-SEPDM decreases both the melting point and the crystallizing temperature of IPP. The widths at half-height of the melting peak and the crystallizing peak become narrower; the d-spacings of the crystal planes are unchanged, revealing the existence of interactions between Zn-SEPDM and the amorphous region of IPP. The higher the sulfonation level, the smaller the average distances across the IPP phase and the EPDM phase. As Zn-SEPDM content exceeds 20%, Zn-SEPDM in the blend becomes continuous and an abrupt change in impact strength is incurred therefrom. Owing to the incorporation of ionic groups into EPDM, the strong interactions between the chains make both the impact and the tensile strength of IPP remarkably higher.     

充油及充填料的磺化SBR离子聚合体的性能

将自制的磺化丁苯橡胶离子聚合体（简称离聚体）在硬脂酸锌存在下于１６０～１７０℃在开炼机上与直链烃油及炭黑或超细ＣａＣＯ３混炼，并热压成型。考察了不同阳离子中和的离聚体的吸油率及直链烃油、炭黑或超细ＣａＣＯ３的填充量对离聚体力学性能的影响，以及对离聚体在Ｂｒａｂｅｎｄｅｒ密炼机上平衡扭矩的影响。结果表明，该离聚体填充５０％（质量，下同）左右炭黑及４０％左右直链烃油后其产物成为拉伸强度大于１４ＭＰａ、     

不同金属离子及胺中和的磺化丁基橡胶离聚体的性能

研究了不同金属离子及胺中和的磺化丁基橡胶离聚体的熔融流动性及力学性能。结果表明,随着硬脂酸锌加入量的增加,锂离聚体的熔融黏度降低,拉伸强度增大;随离聚体中磺酸基含量的增加,锂离聚体的熔融黏度和拉伸强度增大。对于一价金属离子中和的离聚体,其熔融黏度及拉伸强度随着离子电位的降低而减小;对于二价金属离子中和的离聚体,随着离子电位的下降及共价性的增加,熔融黏度下降而拉伸强度增大。用胺中和的离聚体,硬脂酸锌的影响较小,未加硬脂酸锌的离聚体具有较高的扯断伸长率及较低的永久变形,是良好的热塑性弹性体;随离聚体中磺酸基含量的增加,乙胺离聚体的拉伸强度增大。对于不同胺中和的离聚体,其拉伸强度按下列顺序依次降低：乙胺,三乙胺,二乙胺;乙胺,己胺,十二胺,十八胺。     

Structure and Properties of Zn-SEPDM/Modified Glyptal Resin Blends

The structure and properties of zinc-neutralized sulfonated EPDM (Zn-SEPDM) plasticized with modified glyptal resin (GR) were studied through mechanical property tests, capillary rheometry, differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). The results show that GR can considerably reduce the glass transition temperature as well as the apparent melt viscosity of Zn-SEPDM, and that the mechanical properties of Zn-SEPDM plasticized with GR are much better than those of Zn-SEPDM plasticized with traditionally used zinc stearate (ZnSt).     

Melt flow and mechanical properties of sulfonated butyl rubber ionomers

Study of melt flow properties and mechanical properties of sulfonated butyl rubber ionomers showed that in the case of lithium ionomers addition of zinc stearate lowered obviously the melt viscosity, represented by torque value of a Brabender rheometer, and enhanced tensile strength of the ionomer up to 25% of zinc stearate, while in the case of ethylamine neutralized ionomer addition of zinc stearate lowered the melt viscosity not so obviously as in the case of lithium ionomer and slightly affected the tensile strength. Amine neutralized ionomers exhibited very low permanent sets, while the lithium ionomer showed much higher permanent set, which increased with sulfonate group and amount of zinc stearate added. Increase of neutralization degree below equivalent ratio of 1 significantly raised the melt viscosity and tensile strength. For monovalent cation ionomer, melt viscosity and tensile strength diminished with decreasing ionic potentials, but for divalent cation ionomers with increasing ionic potentials and with decreasing covalent character tensile strength decreased and melt viscosity increased. For different amine neutralized ionomers tensile strength decreased in the following orders: ethylamine > triethylamine > diethylamine; isopropylamine > ethylamine > tertiary butylamine > methylamine; ethylamine > hexylamine > dodecylamine > octadecylamine.     

热塑性橡胶—磺化丁苯橡胶离聚体的性能及其共混

丁苯橡胶（SBR）作为高不饱和度的橡胶被成功地用硫酸乙酸酐作为磺化剂在石油醚及丁酮混合溶剂配成的溶液中磺化，并用乙酸盐中和成离聚体。研究了离聚体及其他聚合物的共混物的熔融流动及力学性能。结果表明，SBR离聚体能很容易在硬脂酸锌存在下熔融加工，其行为象热塑性橡胶，硬脂酸锌能降低布拉本特(Brabender)混和机的扭矩所表示的熔融粘度，并增加流动活化能和离聚体的拉伸强度。离聚体的磺酸基含量能增加熔融粘度及拉伸强度。用于中和的阳离子的种类明显地影响离聚体的性能。离聚与聚丙烯或SBS的共混物在拉伸强度上表现出协同效应，而它与聚苯乙烯或顺－1，4聚丁二烯则呈现抵消效应。     

Morphology and properties of HDPE/zinc-neutralized sulfonated EPDM blends

The compatibility of zinc-neutralized sulfonated EPDM (Zn-SEPDM) and its effect on crystallizing behavior of high-density polyethylene (HDPE) as well as the morphology of the blend were studied through wide-angle X-ray diffractomer (WAXD), differential scannign calorimetry (DSC), transition electron micrography.(TEM), scanning electron micrography (SEM), a capillary rheometer, and mechanical property test. The results show that addition of Zn-SEPDM decreases both the melting point and the crystallizing temperature of HDPE. The apparent viscosity of the blend decreases with increasing of shear rate and stress. As Zn-SEPDM content exceeds 20%, Zn-SEPDM in the blend becomes continuous and an abrupt change in impact strength occurs. Owing to the incorporation of ionic groups into EPDM, the strong interaction between the chains make the impact strength of HDPE incredibly increased without sacrificing much of its tensile strength.     

Physicomechanical and dielectric properties of magnesium and barium ionomers based on sulfonated maleated styrene‐ethylene/butylene‐styrene block copolymer

Ionomers, containing both carboxylate and sulfonate anions on the polymer backbone, based on metal cations like Mg⁺² and Ba⁺² were prepared by sulfonating maleated styrene‐ethylene/butylene‐styrene block copolymer, hereafter referred to as m‐SEBS, followed by its neutralization by metal acetates. Infrared spectroscopic studies reveal that sulfonation reaction takes place in the para position of the benzene rings of polystyrene blocks and metal salts are formed on neutralization of the precursor acids. Dynamic mechanical thermal analyses show that sulfonation causes increase in T_g of the rubbery phase of m‐SEBS and decrease in tan δ at T_g of the hard phase, along with formation of a rubbery plateau. The changes become more pronounced on neutralization of the sulfonated maleated SEBS, and the effect is greater in the case of Ba salt. Dielectric thermal analyses (DETA) show that incorporation of ionic groups causes profound changes in the dielectric constant (ϵ′) of m‐SEBS. In addition to the low temperature glass–rubber transition, the plot of ϵ′ vs. temperature shows occurrence of a high‐temperature transition, also known as the ionic transition. Activation energy for the dielectric relaxation could be determined on the basis of frequency dependence of the ionic transition temperature. Two values of the activation energy for the dielectric relaxation refer to the presence of two types of ionic aggregates, namely multiplets and clusters. Incorporation of the ionic groups causes enhancement in stress–strain properties as well as retention of the properties at elevated temperatures (50° and 75°C), and the effect is more pronounced in the case of Ba ionomer. Although sulfonated ionomers show greater strength than the carboxylated ionomers, the sulfonated maleated ionomers show higher stress–strain properties in comparison to both sulfonated and carboxylated ionomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 816–825, 2000     

Toward Largely Enhanced Toughness and Balanced Strength in PA1012/EPDM Blends via Synergistic Effect of Sacrificial Bonds and Network Structure

Here, zinc-neutralized ethylene propylene diene monomer (EPDM) ionomers with different neutralization levels are prepared through melt blending, and are then incorporated with polyamide 1012 (PA1012) to fabricate PA1012/EPDM ionomer blends. Interestingly, complex crosslinking networks are formed in the blends due to the construction of sacrificial bonds (Zn²⁺-carboxyl, Zn²⁺-amide). The as-formed network structure and sacrificial bond endow the PA/EPDM blends with largely enhanced toughness (16 times higher than that of neat PA), as well as balanced strength and stiffness. Meanwhile, the rheological behaviors of PA1012/EPDM ionomer blends indicate their relative low melting viscosity, which can avoid the processing shortcomings of plastics toughened with rubber. Moreover, PA1012/EPDM ionomer blends show obvious gelation behavior, and a maximum notched Izod impact strength exhibited at the gel point, in which unique double network structure can be observed obviously, indicating that there is a corresponding correlation between the rheological and mechanical parameters. Furthermore, the supper-toughening mechanism of PA1012/EPDM ionomer blends at gel point is explored, which origins from the large deformation and cavitation of rubber particles and the destruction of special double network morphologies. This study provides a novel and effective strategy to fabricate PA materials with outstanding toughness and excellent strength simultaneously.     

Preparation and properties of high‐performance recyclable ethylene propylene diene rubber

To obtain high‐performance recyclable ethylene propylene diene rubber (EPDM), EPDM was chemically functionalized as follows: EPDM was grafted with citraconic acid (CCA) by radical melt polymerization to produce a grafted EPDM (EPDM‐g‐CCA), and EPDM‐g‐CCA was reacted with various amino acids by melt condensation reaction to give amidated copolymers (EPDM‐g‐CCA‐2‐Am, EPDM‐g‐CCA‐7‐Am, and EPDM‐g‐CCA‐12‐Am, where the n indicates the carbon number of amino acid), and then ionomers (EPDM‐g‐CCA/n‐Am/Io) were prepared by melt reaction of EPDM‐g‐CCA/n‐Ams with Zinc oxide (ZnO)/zinc stearate (ZnSt). The mechanical properties/compression set (CS) resistance (elasticity)/recyclability of pristine EPDM, EPDM‐g‐CCA, EPDM‐g‐CCA/n‐Am, and ionomers sheet samples were compared. The tensile strength/modulus, tear strength, and elasticity of samples were mostly increased in the order of ionomers>EPDM‐g‐CCA/n‐Ams>EPDM‐g‐CCA>pristine EPDM. The properties of ionomers increased significantly with increasing the carbon number in amino acid up to seven, and then levelled off or decreased a little. The tensile strength/elasticity (compression set resistance) of recyclable ionomer (EPDM‐g‐CCA/7‐Am/Io) was found to be ～9.42/～2.31 times of pristine EPDM, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42718.     

Sulfonation degree determination of polystyrene ionomers by using adiabatic bomb calorimeter

Sulfonation degree determination of sulfonated polystyrene and the corresponding ionomers are performed by adiabatic bomb calorimeter. The theoretical calculations from the band energies for the combustion enthalpy values (calorific values) and the experimental values are compared, and a linear relation between the values is found. Sulfonation and neutralization processes are examined by elemental sulfur analysis and atomic absorption spectroscopy (AAS). It was obvious that increasing sulfonation degree yields a decrease in the combustion enthalpy values, as it is expected from the theoretical calculations. In addition, metal ion incorporation to the structure deviates the experimental combustion enthalpy values especially for the ionomers which have higher sulfonation degrees. This is due to the formation of a higher degree aggregation. © Wiley Periodicals, Inc. J Appl Polym Sci 100: 4684–4688, 2006     

A Study on Morphology and Properties of HDPE/Zn-SEPDM/GR Blends

The morphology and properties of HDPE blends with zinc-neutralized sulfonated EPDM (Zn-SEPDM) and glyptal resin (GR) were studied through SEM, TEM, and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an interpenetrating polymer network in structure, and that a rather high impact and tensile strength of HDPE may be obtained after blending. The antistatic effect, the softening point, and heat distortion temperature of the blend are higher as compared to HDPE/Zn-SEPDM/ZnSt (zinc stearate).     

Effects of acid neutralization on the properties of K+ and Na+poly(ethylene-co-methacrylic acid) ionomers

The effects of the degree of neutralization of the acid groups and, to some extent, the precursor melt index on the thermal, rheological, and mechanical properties of two series of poly(ethylene-co-methacrylic acid) (EMAA) ionomers, one based on sodium (Na⁺) cations and one based on potassium cations (K⁺), were examined. Differential scanning calorimetry (DSC) and modulus results indicate that the secondary crystallization of the ionomers is generally completed 21 days after melt processing. DSC results indicate that the extent of crystallization increases with increasing neutralization level. The mechanical relaxation seen by dynamic mechanical analysis (DMA) in the vicinity of the secondary crystal melting point shifts to higher temperatures as the neutralization level increases. The rheological properties increase with decreasing precursor melt index and with increasing neutralization level to a lesser extent. The ionomer modulus and yield strength increase with increasing neutralization level up to 40% neutralization and then plateau or slightly decrease with further neutralization. The plateaus/maxima may be the result of an optimal spacing of alkaline ions and carboxyl groups within ionic groups at neutralization levels near 33%. The elongation at break and the Izod impact strength decrease with increasing neutralization. The modulus, yield stress, and impact strength are generally lowest for the ionomers with the highest precursor melt index.     

磺化PS及其离聚物的合成及性能研究

用乙酸硫酸作为磺化试剂合成了一系列低磺化度磺化聚苯乙烯(SPS),并将其离子化得到锌、镧离聚物。考察了反应温度、磺化试剂用量对磺化反应的影响。同时通过溶解测试、热分析、红外光谱法研究了系列SPS及其离聚物的溶解性、玻璃化转变温度(t_g)值、热稳定性及吸水性。实验表明:随着反应温度的提高及磺化试剂用量的增加,产物磺化度有不同程度的增加;随磺化度提高,产物在非极性溶剂中溶解性下降,t_g值增大,吸水性提高,离聚物比相应磺化物具有更好的热稳定性。     

Melt rheology of ion-containing polymers. I. Effect of molecular weight and excess neutralizing agent in model elastomeric sulfonated polyisobutylene-based ionomers

Melt rheology of elastomeric triarm sulfonated polyisobutylene model ionomers has been studied. The molecular weights (M _n) of the polymers have been varied from 8300 to 34,000. The sulfonated materials were neutralized with potassium hydroxide either to the exact stoichiometric equivalence point or to twice this amount, i.e., 100% excess neutralizing agent was added. For comparison one nonsulfonated precursor of M _n = 8300 was also studied. It was observed that the introduction of one sulfonate group at each chain end of the triarm poly-isobutylene molecule changes the state of matter at room temperature. Specifically, the unsulfonated materials are viscous liquids while the sulfonated ionomers are solid elastomers at room temperature. The zero-shear melt viscosity of the unsulfonated precursor is 900 poise (90 Pa·s), at room temperature while for those materials neutralized with potassium hydroxide to the exact stoichiometric point it is above 9 × 10³ poise (900 Pa·s) at 180°C. As expected, the zero shear viscosity increases with an increase in the molecular weight. Significant ionic interactions still persist at 180°C as evident by the high viscosity of the ionomers. However, at higher frequencies (～600 rad/s), the melt viscosity decreases to about 5 × 10³ poise for the different molecular weight materials. The melt viscosity of ionomers containing 100% excess neutralizing agent shows a dramatic increase. The excess KOH is speculated to be incorporated into the ionic domains rather than uniformly distributed throughout the matrix. This results in an increased strength of the ionic aggregates, thereby increasing the melt viscosities. Thus, due to the very pronounced effect on rheological properties it is important to know not only the extent of neutralization (up to full neutralization) but also the amount of excess neutralizing agent, if any, which is present in the sample.