Effects of acid neutralization on the morphology and properties of organoclay nanocomposites formed from K+ and Na+ poly(ethylene-co-methacrylic acid) ionomers

Nanocomposites were prepared by melt blending various sodium (Na⁺) and potassium (K⁺) ionomers formed from poly(ethylene-co-methacrylic acid) and the M₂(HT)₂ organoclay formed from montmorillonite (MMT). The effects of the neutralization level of the acid groups and the precursor melt index on the morphology and properties of the nanocomposites were evaluated using stress-strain analysis, wide angle X-ray scattering (WAXS), and transmission electron microscopy (TEM) coupled with particle analysis. The aspect ratio generally increases as the neutralization level increases, except for Na⁺ ionomer nanocomposites with neutralization levels >50%. It appears from both WAXS and TEM analyses that Na⁺ ionomer nanocomposites have higher levels of MMT exfoliation and particle orientation in the flow direction than K⁺ ionomer nanocomposites. DSC results indicate that the level of crystallinity in the Na⁺ ionomers generally increases slightly with MMT addition, while the crystallinity in the K⁺ ionomers decreases slightly with MMT addition. The relative modulus of K⁺ ionomer nanocomposites increases as the degree of neutralization increases. The relative moduli of Na⁺ ionomer nanocomposites are higher than the relative modulus of K⁺ ionomer nanocomposites, likely due to the increased crystallinity of the Na⁺ ionomers and the decreased crystallinity of the K⁺ ionomers upon addition of MMT, the higher exfoliation levels measured by the aspect ratios and the particle densities, and the higher particle orientation indicated by TEM and WAXS. The relative modulus generally increases as the aspect ratio increases. The elongation at break generally decreases as the MMT content increases and as the neutralization level increases for both ionomer types. The fracture energy of most of the ionomers increases with the addition of MMT, reaches a maximum between 2.5 and 5 wt% MMT, and then decreases upon further MMT addition.     

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     

Effect of degree of neutralization of sodium-based ionomers on hot-tack properties

The hot-tack properties of ethylene-methacrylic acid copolymers neutralized with sodium (Na) cations to produce ionomers were investigated. Specimens with neutralization degrees of 20%, 54%, and 70% were examined. After testing at low sealing temperatures (<130°C), the highest hot-tack strength was obtained from a specimen with a neutralization degree of 20%. In contrast, at high sealing temperatures (>140°C), the hot-tack strength increased with an increasing degree of neutralization. Observations of the surfaces of samples tested at low sealing temperatures after hot-tack tests showed that specimens having a neutralization degree of 20% exhibited cohesive breakdown while the 54% and 70% specimens underwent interfacial delamination. The effect of sealing temperature on hot-tack strength was determined by assessing the rheological properties of molten ionomers. The results suggested that, when testing at low sealing temperatures, a low melt viscosity provided high hot-tack strength by allowing flow diffusivity of the resin at the sealed interface. At high sealing temperatures, uniaxial elongational viscosity related to strain hardening contributed to the high hot-tack strength of these Na-based ionomers. The present study highlights the important effect of ionic aggregates on hot-tack properties.     

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.     

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。     

The effect of polypropylene/polyamide 66 blending modification on melt strength and rheologic behaviors of polypropylene

Common linear polypropylene (PP) was modified by blending with polyamide 66 (PA66) under the act of compatibilizer in a twin-screw extruder in an attempt to improve the melt strength (MS) of PP. The MS of pure PP and modified PPs were measured by MS testing unit at three temperature of 190, 210, and 230 °C, and the MS improvement of PP was verified. The MS of the modified PPs increased with increasing the content of PA66. The steady- and dynamic-shear rheological behaviors of pure PP and modified PPs were investigated using a capillary rheometer and a parallel-plate rotating rheometer. The steady-shear rheological analysis results revealed that modified PPs had higher melt shear viscosity, stronger non-Newtonian behaviors, and higher zero shear-rate viscosity. The dynamic-shear rheological analysis showed modified PPs had higher melt complex modulus and smaller phase angle, which indicated that the melt viscosity and melt elasticity of PP were also enhanced. The modified PPs was characterized by DSC. DSC results revealed that the PA66 phase and PP phase of the modified PPs were in state of crystallization. The enhancement of MS, melt viscosity, and melt elasticity of modified PPs could be due to undisaggregated PA66 crystallization phase within the melt of PP blends.     

Synthesis and thermal properties of telechelic poly(lactic acid) ionomers

Telechelic poly(lactic acid) (PLA) ionomers were synthesized using a chemical recycling process. A transesterification reaction between a commercial PLA and 2-hydroxyethyl methacrylate or ethylene glycol was used to produce a hydroxy-terminated PLA. The hydroxy-terminated PLA was then reacted with itaconic anhydride to produce terminal carboxylic acid groups, which were neutralized with appropriate metal acetates to produce Na-, Li-, K-, Zn-, Ca- and Y-ω- and α,ω-telechelic PLA ionomers. ¹H NMR spectroscopy was used to confirm the presence of the itaconic acid end-groups and FTIR spectroscopy was used to quantify the extent of neutralization. The addition of the ionic groups increased the glass transition (T_g), and T_g increased as the strength of the ion-pair increased. The ionic groups suppressed crystallinity, especially when multivalent cations were used.     

Mechanical and thermal properties of potassium salts of poly(ethylene‐co‐ethylacrylate): Polyolefin ionomers in the absence of acid groups

The thermal and mechanical properties of ionomers prepared by partial saponification of poly(ethylene‐co‐ethylacrylate) (EEA) with potassium were investigated by using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The Vicat softening temperature (VST) and bending modulus were also evaluated. Molecular design of the present EEA‐based ionomers eliminates acid groups, which affect ionic aggregates for conventional ionomers. The DSC results showed that the melting enthalpy and main crystallization temperature decreased as the ion content increased, whereas on the other hand, the crystal melting temperature at about 360 K did not depend on the ion content, and a secondary exothermal peak was observed in the cooling process. The variance of the VST increased as the crystallinity decreased. The temperature‐dependent curves of DMA data of the EEA‐based potassium ionomers with a higher ion content showed elastic plateau even at temperatures above their crystal melting points. Our results indicate the existence of strong cross‐linking mediated by ion aggregates. The quadratic increase of stiffness as a function of ion content, increasing VST with decreasing crystallinity, and elastic plateau of temperature‐dependent moduli above crystal melting temperature are significant characteristics of the EEA‐based potassium ionomers, which contain ionic aggregations without acid group presence. POLYM. ENG. SCI., 55:1843–1848, 2015. © 2014 Society of Plastics Engineers     

Effect of organic amine type on the structure and properties of the complex Zn(II) salts of ethylene–methacrylic acid copolymer with organic amines

The complex Zn(II) salts of ethylene–methacrylic acid copolymer (EMAA) were synthesized by using various organic amines from monoamines to polyamines, from primary amines to tertiary amines, and from molecular amines to polymer amines. Thermal analyses by differential scanning calorimetry (DSC), and the measurement of stiffness, melt flow rate (MFR), and dielectric properties were employed for the complex salts. It was found that the valence, strength of base, rigidity and flexibility, and bulkiness of the organic amines affect the degree of crystalline order of the ionic crystallites, which governs the stiffness of the complex ion ionomers. The stiffness is higher for the complex salts which form the higher orderliness in the ionic aggregates. The organic amines with two or more primary aliphatic amino groups and higher boiling temperatures from more rigid ionic crystallites in the complex ion ionomers leading to the enhanced modulus. Monoamines or polyamines with amino groups attached to flexible chains such as polyether and polysiloxane scarcely develop ionic crystallites and preferentially solvate the amorphous region including ionic groups leading to the decreased modulus. These results provide us with the fundamental information to control the modulus of ionomers.     

SBS热塑性弹性体改性回收聚丙烯的研究

采用差示扫描量热法(DSC)和高级流变扩展系统仪(ARES)研究了不同用量的苯乙烯-丁二烯-苯乙烯共聚物(SBS)改性回收聚丙烯(r-PP)的结晶性能和流变性能,同时还研究了r-PP/SBS共混物的力学性能和微观形貌。结果表明,SBS的加入对r-PP有明显的增韧效果,提高了共混物的结晶温度。随着SBS含量的增加,SBS/r-PP共混体系的熔体黏度增大,储能模量增加,而介质损耗角正切减小,这表明熔体流变行为由黏性行为向弹性行为转变。     

煤矸石填充聚酰胺6复合材料的结构与性能研究

采用熔融共混法制备了聚酰胺6／煤矸石复合材料，研究了复合材料的力学性能、微观结构、结晶行为和流变性能。结果表明：煤矸石的加入使聚酰胺6的的拉伸强度、弹性模量、弯曲强度和弯曲模量分别增加了约53．8％、66．1％、37．1％和63．4％，而冲击韧性基本保持，煤矸石最佳填充量为25％；煤矸石在聚酰胺6基体中分散均匀，复合材料具有韧性断裂特征；煤矸石使聚酰胺6的结晶温度由187．0℃升高到191．3℃，过冷度由33．6℃降至18．9℃，结晶温度范围变窄，即煤矸石提高了聚酰胺6的结晶速率，对聚酰胺6具有异相成核作用；在所研究的剪切速率范围内，聚酰胺6及其复合材料的流变行为表现为假塑性，煤矸石的加入使非牛顿指数减小，聚酰胺6对剪切敏感性下降。     

从聚苯乙烯大单体—丙烯酸丁酯—丙烯酸三元共聚物中和制得的热塑性弹性体的力学性能

研究了经离子中和的聚苯乙烯大单体与丙烯酸及丙烯酸丁酯共聚物的力学性能,包括中和方法、羧酸含量、中和度、金属离子种类及聚苯乙烯支链的含量及分子量等对力学性能的影响。这种双重物理交联产物的强度为未中和的三元共聚物或经离子中和的丙烯酸—丙烯酸丁醋共聚物的二倍。动态力学谱表明有二个玻璃化温度,呈现微观相分离。     

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.     

Mechanical behavior,structure, and reinforcement processes of TEMPO‐oxidized cellulose reinforced poly(lactic) acid

Poly(lactic) acid (PLA) was reinforced with acetylated TEMPO‐oxidized fibrillated cellulose (TOFC) prepared from birch pulp. Composite films were studied using dynamic mechanical thermal analysis, differential scanning calorimetry (DSC), as well as static mechanical testing. The storage modulus as well as tensile strength of PLA was improved on the addition of 30 wt% of TOFC by approximately 50% and 40%, respectively. Thermal stability as well as strength properties in moist environments (up to 90% relative humidity) was significantly improved at 15, 20, 25, and 30 wt% of TOFC. DSC showed that crystallization from solution took place during preparation of the composite films and was much greater than melt crystallization. POLYM. COMPOS., 2012. © 2013 Society of Plastics Engineers     

Crystallization and the mechanical and rheological properties of decrosslinked–crosslinked‐high‐density polyethylenes using a supercritical fluid

The crystallization, and mechanical and rheological properties of decrosslinked–crosslinked‐high‐density polyethylenes using supercritical methanol were investigated by DSC, WAXS, DMTA, and UDS. Crosslinked high‐density polyethylenes were successfully decrosslinked in a supercritical methanol condition. The residual gel content of the decrosslinked samples decreased with the reaction temperature. The crystallization behavior, mechanical, and rheological properties of the decrosslinked samples were influenced considerably by the gel content. As the gel content increased, the network gel structure restricted the chain mobility of polymer molecules in the melt state and hindered their crystallization. Thus, the nonterminal yield behavior in the melt state was enhanced and the crystallinity decreased. The dynamic elastic modulus of the decrosslinked sample in solid state increased with the increase in the crystallinity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enhancement of physical properties of thermoplastic polyether-ester elastomer by reactive extrusion with chain extender

The branched thermoplastic polyether-ester elastomer (TPEE) and diisocyanate compound was melt extruded in an effort to enhance melt viscosity for the blow moulding process. The chain-extended TPEE was prepared with melt condensation of a branched TPEE and 4,4′-diphenylmethane diisocyanate (MDI) for enhancement of the molecular weight of TPEE. The effects of MDI contents as a chain extender on melt, thermal, mechanical and rheological properties of the chain-extended TPEE were investigated. By using a solution and melt viscosity analysis, the chain-extended TPEE was found to be an enhancement of molecular weight and a lightly cross-linked structure. The intrinsic viscosity (IV) increased and melt flow index (MI) decreased with an increasing amount of MDI due to the reaction between the hydroxyl end groups of TPEE and isocyanate groups of MDI. The chain-extended TPEE does not lead to an important drop in elongation at break. The tensile strength and the tear strength are characterized by a significant increase, compared with a branched TPEE. The storage modulus, loss modulus and the complex viscosity of the chain-extended TPEE were also higher. The modified Cole–Cole plots revealed that the chain-extended TPEE shows a higher elasticity than the branched TPEE. The chain-extended TPEE has more suitable melt and rheological properties for the blow moulding processes.     

用于FDM的PLA共混改性

采用酰胺成核剂(NT–C)和聚乙二醇(PEG2000)对聚乳酸(PLA)进行熔融共混改性,制备了用于3D打印的PLA/NT–C/PEG2000共混物,并在200℃的温度下通过熔融沉积成型(FDM)工艺制备了共混物FDM打印件。研究了NT–C的用量对PLA/NT–C打印件结晶性能的影响,并在此基础上研究了PEG2000用量对共混物流变性能、共混物打印件的结晶性能和力学性能的影响。差示扫描量热分析表明NT–C可在一定程度上提高PLA/NT–C打印件的结晶度,一定用量的PEG2000的添加进一步提高了共混物打印件的结晶性能,当NT–C和PEG2000的质量分数分别为2%和5%时,打印件的结晶度达到17.1%,相比PLA提高了12倍;流变性能测试表明PEG2000提高了共混物的熔体流动速率,降低了共混物储能模量和损耗模量对温度的依赖性,扩宽了PLA在FDM工艺中的成型温度;力学性能测试表明PEG2000显著提高了PLA/NT–C/PEG2000共混物的缺口冲击强度,降低了打印中断丝的几率,FDM打印件弯曲和拉伸强度相比于PLA也有显著提高,当NT–C和PEG2000的质量分数分别为2%和5%时,打印件的弯曲和拉伸强度分别达到了注塑件的80%和70%以上,扩宽了PLA在FDM中应用。     

Influence of pearlescent pigments on mechanical properties and crystallization behavior of polylactic acid

Polylactic acid (PLA)/pearlescent pigments (PEPs) composites were fabricated by melt blending method and their properties were studied using a rotational rheometry, field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). Because PEP could disperse uniformly in PLA matrix and would form PEP networks, there were improvements made in the flexural strength, tensile strength and impact strength of PLA composites. Interestingly, the viscosity of PLA composites reduced significantly as compared with neat PLA, indicating an improvement in processing properties. The rheological tests confirmed that the storage modulus of PLA composites decreased as PEP content increased at a given frequency. Also, there was a plateau at low frequency range, which was a sign of PEP networks formation. The DMA tests showed that the storage modulus of PLA composite increased with PEP content, suggesting the enhancement of rigidity. According to the XRD results, no change was observed in the crystal structure of PLA in the presence of PEP. The addition of PEP did not change melting temperature, but the glass transition temperature increased a little, and the cold crystallization temperature of PLA decreased largely. The DSC results also showed that nucleation ability of PLA was enhanced by addition of PEP at low cooling rates, but the whole crystallization process of PLA in composite was inhibited at higher cooling rates. This conclusion was also confirmed by the results of crystallization kinetics.     

Melt synthesis of sulfonated EPDM ionomers in batch and continuous processes

Zinc-neutralized sulfonated EPDM ionomers (Zn-SEPDM) were prepared by batch and continuous melt sulfonation processes, and the ionomer products were compared with ionomers synthesized by sulfonation of EPDM in homogeneous solution. The efficiency of a batch melt sulfonation using an intensive mixer as a reactor was comparable to that of the solution sulfonation process, but the efficiency of the melt sulfonation in a twin-screw extruder was considerably lower, which was thought to be a consequence of a relatively short reaction residence time due to limitations of the equipment. Melt neutralization was not complete, which produced a dark colored product. However, the incomplete neutralization and the color of the product did not affect the mechanical properties of the melt sulfonated ionomers, which were comparable to those of ionomers made by conventional solution sulfonation. The metal sulfonate concentration alone determined the mechanical properties of the ionomer. Melt sulfonation of Zn-SEPDM ionomers by batch or continuous melt processes appears to be a practical alternative to solution sulfonation, but further optimization of the melt sulfonation processes is needed to ensure uniform sulfonation and complete neutralization.