星形磺化遥爪离子交联聚合物的力学性质

综述了分子结构、分子量、平衡离子的类型，过量中和剂，水分、离子增塑剂等诸因素对星形磺化遥爪离子交联聚合物的力学性质的影响，阐明三臂星形三官能度结构的遥爪离聚休整体母体，与适当的平衡离子、过量中和剂、离子增塑剂组成的遥爪离聚体体系可望可为一种热塑性弹性体材料。     

Sulphonated polyisobutylene telechelic ionomers: 12. Solid-state mechanical properties

The solid-state mechanical properties of well defined sulphonated polyisobutylene telechelic ionomers are presented. Specifically, the effect of (1) molecular architecture, (2) molecular weight, (3) type of cation used for neutralization and (4) excess neutralizing agent has been investigated. In addition, the effect of moisture and ionic plasticizer on the stress-strain behaviour has also been studied.

These ionomers do not display the characteristic small-angle X-ray scattering (SAXS) peak, which is indicative of the presence of clusters, above a number-average molecular weight of about 10 000. However, below this molecular weight a weak shoulder is sometimes observed on the SAXS curve. The tri-arm species form a network structure at ambient temperatures which results in materials with good mechanical properties. The mechanical properties of the linear difunctional species are inferior to those of the three-arm star trifunctional species due to a less well developed network structure. The monofunctional species are very tacky at ambient temperatures and cannot be handled as solid materials. However, by their incorporation into the trifunctional systems they do serve as a model for ‘dangling ends’. As expected, these blends display significantly different properties than those possessed with the pure trifunctional species.

Addition of excess neutralizing agent significantly increases the high deformation properties with little effect on Young's modulus. A simple morphological model has been postulated in which it is suggested that the excess neutralizing agent resides at the ionic sites rather than being uniformly distributed throughout the matrix. Zinc-neutralized ionomers show stress-strain behaviour which is comparable to the potassium- and calcium-neutralized materials at ambient conditions, but the softening temperature is lower for the zinc neutralized material. Water absorption in these materials is relatively low. Addition of zinc stearate, an ionic plasticizer, facilitates melt processing by lowering the viscosity at high temperatures yet at ambient temperatures it crystallizes and acts as a reinforcing filler thus increasing Young's modulus.     

New polyisobutylene-based model ionomers

Strain induced crystallization has been observed at 25°C in low molecular weight three-arm star polyisobutylene ionomers at elongations exceeding about 550%. The sulfonated form of the polymer was neutralized with calcium hydroxide. The number average molecular weight of the polymer was only 9,000 with a dispersity ratio of about 1.7. This molecular weight is at the edge of the critical molecular weight for entanglements. Strain induced crystallization has been reported in the literature for very high molecular weight linear polyisobutylene. However, no such effects have been observed for linear, low molecular weight polyisobutylene and it has been stated it could not be induced. The cause for this strain induced crystallization in our materials is due to the presence of three ionic terminal groups per molecule which results in sufficient coulombic forces for maintenance of molecular orientation with strain without significant relaxation.     

Linear viscoelastic properties of mixtures of 3- and 4-arm polybutadiene stars

The viscoelastic properties of a three-arm and a four-arm star polybutadiene with the same arm molecular weight (M_a) were studied. The zero-shear recoverable compliance (J⁰_e) and plateau modulus (G⁰_N) for these stars are the same. The zero-shear viscosity (η₀) of the three-arm star is 20% lower than that of the four-arm star. Mixtures of the stars had J⁰_e and G⁰_N unchanged. A $\text{50}\text{50}$ mixture of the three- and four-arm star was diluted with a low molecular weight linear polybutadiene. G⁰_N∝ø²; J⁰_e∝ø^?1 and M_e∝ø^?1, as expected for dilution with a θ-solvent.     

Preparation of star copolymers with three arms of poly(ethylene oxide-co-glycidol)-graft-polystyrene and investigation of their aggregation in water

The star graft copolymers with three arms composed of poly(ethylene oxide) (PEO) as main chain and polystyrene (PS) as side chains were prepared by sequential anionic ring-opening copolymerization of ethylene oxide and ethoxyethyl glycidyl ether (EEGE), and then atom transfer radical polymerization (ATRP) of styrene. The anionic ring-opening copolymerization of EO and EEGE was carried out using 2-ethyl-2-hydroxymethyl-1,3-propanediol as trifunctional initiator and diphenylmethyl potassium (DPMK) as deprotonating agent. The resulting three-arm star copolymer [poly(EO-co-EEGE)]₃ could be easily hydrolyzed to unmask the pendant hydroxyl groups without affecting the PEO chains. The switch from the first to the second mechanism was completed by the reaction of the multi-pendant hydroxyl groups of three-arm PEO chain with 2-bromoisobutyryl bromide. The obtained poly(ethylene oxide-co-2-bromoisobutyryloxyglycidyl ether), [poly(EO-co-BiBGE)]₃, was used as macroinitiators to initiate the polymerization of styrene in bulk at 90 °C by ATRP. The final products and intermediates were characterized by NMR, SEC and IR in detail. The amphiphilic star graft copolymers synthesized can form micelles in water. The critical micelle concentration (cmc) determined by fluorescence spectra was about 5 × 10⁻⁷ g/mL. Sphere micelles were observed by transmission electron microscopy (TEM) at low copolymer concentration (6 × 10⁻⁵ g/mL), but the micelle shape became irregular when the copolymer concentration increased to 6 × 10⁻⁴ g/mL.     

Polyisobutylene model elastomers prepared using demonstrably complete end-linking reactions

Summary Cationic polymerizations with a trifunctional initiator-chain transfer agent were used to prepare three-arm polyisobutylene [C(CH₃)₂CH₂] (PIB) molecules with hydroxyl groups at all three chain ends. Extensive spectroscopic analyses confirmed the essentially perfect trifunctionality of the polymers, which were then end-linked using an aromatic diisocyanate to give trifunctional model networks. The PIB elastomers were found to have negligible sol fractions, which demonstrates that the end-linking reactions used to prepare them were essentially complete. They were studied, swollen, with regard to their equilibrium stressstrain isotherms in uniaxial extension at 25°C. As was found to be the case for trifunctional and tetrafunctional PIB networks prepared from the linear chains, the results were in satisfactory agreement with theory and yielded no evidence that inter-chain entanglements contribute to the modulus at elastic equilibriums.     

Polybenzimidazole gel membrane for the use in fuel cell

Thermoreversible gelation of polybenzimidazole (PBI) in phosphoric acid (PA) is investigated by studying the gel morphology, thermodynamics of the gelation, and gelation kinetics utilizing test tube tilting and UV-Vis spectroscopy techniques. Gelation kinetics studies reveal that both the gelation rate and critical gelation concentration (C^∗_t=∞) are function of gelation temperature (T_gel) and the molecular weight of PBI. Highly dense fibrillar network morphology with large number of longer and thinner fibrils is obtained for higher gel concentration and higher molecular weight PBI. Both the gel melting (T_gm) and gelation (T_gel) temperature depend upon the gelation concentration and molecular weight of PBI. The presence of self-assembled chains of PA molecules, which help to produce the PBI crystallites, is observed from the thermodynamical study. I.R. and Raman studies prove the presence of strong hydrogen bonding interaction between the PBI and the PA molecules, and the free PA molecules in the gel network. The gelation occurs in two-step processes which include a slow rate determining conformational transition from coil to rod and followed by aggregation of rod via crystallization. The PA loading of PBI membrane obtained from the PBI-PA gel is significantly high compared to the conventional imbibing process membrane. The PBI gel membrane displays very high thermal and mechanical stabilities. The high acid loading and superb thermo-mechanical stability are due to the gel network structure of the membrane. The proton conductivity of the membrane at 160 °C and 0% relative humidity (RH) is ∼0.1 S cm⁻¹, which is higher than the reported values in the literature for the PBI. The activation energy of the proton conduction is 14-15 kJ/mol indicating faster proton transfer by hopping process inside the gel network.     

Multi-arm star-branched polyisobutylene ionomers

A series of multi-arm star-branched polyisobutylenes was synthesized via living carbocationic polymerization. Arms with molecular weights ranging from 10,000 to 30,000 g/mol were prepared using the cumyl chloride/TiCl₄/pyridine initiation system in 60/40 (v/v) hexane/methyl chloride at − 80 °C and linked by sequential addition of divinylbenzene. The weight average number of arms per star polymer, N _w, scaled inversely with arm molecular weight and ranged from 32 to 5. Star-telechelic ionomers were produced by sulfonation of the aromatic initiator residue at the end of each arm, followed by neutralization. Sulfonation was quantitative as indicated by acid-base titration. Potassium ionomers were elastic solids which were marginally soluble in THF; the precursors were tacky and freely soluble in THF. Ionic modification did not alter the glass transition temperature (− 66 °C), but the thermal decomposition temperature in N₂ was increased from 375 to 400 °C. Received: 25 July 1997/Accepted: 27 August 1997     

Synthesis and mechanical properties of poly(styrene-b-lsobutylene-b-styrene) block copolymer lonomers

Linear and three-arm star poly(styrene-b-isobutylene-b-styrene) (PS-PIB-PS) block copolymer ionomers possessing various counterions and levels of sulfonation were synthesized by sulfonating the polystyrene blocks of PS-PIB-PS block copolymers. Analysis of compression-molded films of the ionomers showed that the incorporation of sulfonate groups into the polystyrene blocks of these materials resulted in an increase in tensile strength, a decrease in elongation at break, and a persistence of elastic properties to much higher temperatures as compared with unsulfonated precursors. Among all counterions studied, zinc resulted in the strongest ionomers and potassium yielded the most easily processed ionomers. Dynamic mechanical analysis showed that the block copolymer ionomers possessed a phase-separated morphology; however, anomalous relaxations observed during the first heating cycle, but that were substantially reduced or completely absent in subsequent cycles, implied that strong ionic interactions were causing reduced processability and the formation of nonequilibrium morphologies. The observed relaxations were interpreted to be domain rearrangements brought about by the thermal energy supplied by the dynamic experiment. Annealing of films of relatively low ionic contents yielded viscoelastic behavior that was consistent with an equilibrium morphology characterized by phase-separated, partially sulfonated polystyrene domains of the same density and size as the polystyrene domains of the unsulfonated precursor. Compression molded films of high ionic content yielded a higher rubbery plateau modulus than the unsulfonated precursor, suggesting a different morphology. Solution-cast films of zinc ionomers exhibited two values for the rubbery modulus, a higher values at temperature below the T_g of polystyrene and a lower value at temperature above the T_g of polystyrene. Thermogravimetric analysis revealed the major mass-loss process of the parent, linear block copolymer at 417°C (mid-point) and of the tetramethyl ammonium ionomer at 431°C.     

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     

New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers)

Summary The synthesis and quantitative end group characterization of anisole-terminated polyisobutylenes are described. These new telechelic prepolymers consist of a linear or a three-arm star polyisobutylene (PIB) carrying exactly two or three anisole termini, respectively. The synthesis was accomplished by quantitative Friedel-Crafts alkylation of anisole by olefin-and/ortert.-chloro-telechelic PIB's, and characterization involved¹H NMR and UV spectroscopy, GPC and osmometry. According to charcterization research the linear and three-arm star anisole-terminated polyisobutylenes have the following structures:     

Sulfonated polyisobutylene telechelic ionomers. XIV. Viscoelastic behavior of concentrated solutions in nonpolar solvents

The effect of molecular variables upon the dynamic viscoelastic behavior of solutions of sulfonated polyisobutylene telechelic ionomers in nonpolar solvents has been investigated. Intermolecular association of the ionic end groups in nonpolar media results in the formation of a transient ionic network which displays a viscous response at low frequencies and an elastic response at high frequencies. The frequency of the transition from viscous behavior to elastic behavior, as well as the plateau storage modulus, is dependent upon molecular variables such as architecture, molecular weight, neutralizing cation, and extent of neutralization. Variables which affect the strength of the ionic interactions, such as temperature and the type of solvent, also influence the viscoelastic response. Solutions of ionomers neutralized with cations of Groups IA and IIA, such as potassium and calcium, behave elastically over most of the experimentally accessible frequency range, while those neutralized with transition metals, such as zinc, display viscous flow over a rather wide range at low frequencies. As in previous studies of dilute solution viscosity behavior, the threearm star trifunctional species was found to form a more extensive network in nonpolar solvents than the linear difunctional species at equivalent concentrations. The failure of time–temperature superposition indicates that these solutions are thermoheologically complex.     

Oligomeric A2 + B3 synthesis of highly branched polysulfone ionomers: novel candidates for ionic polymer transducers

Highly branched poly(arylene ether sulfone)s with systematically varied degrees of branching and sulfonation were synthesized through oligomeric A₂ + B₃ methods for application as ionic polymer transducer (IPT) membranes. IPTs are a class of electroactive polymer devices that leverage ionomeric membranes to perform electromechanical transduction as actuators and/or sensors. Synthesis of controlled molecular weight A₂ oligomeric polysulfones targeted the global degree of branching (DB_global) to approximately 1–3% in the absence of gelation. Size exclusion chromatography confirmed molecular weights greater than 20 000 g mol^?1 were achieved for linear and branched polysulfones. Increased degree of sulfonation of the A₂ oligomers reduced the development of molecular weight in the oligomeric A₂ + B₃ branching reaction; the formation of tough, flexible, ion‐conducting membranes is required for emerging transducer applications. Variation in the DB_global attained did not affect the thermal transitions or elastic modulus as significantly as changes in the degree of sulfonation. However, an ionic dissociation temperature was detected below the glass transition temperature of the polysulfone matrix and was relatively independent of the degree of sulfonation. Successful synthesis and characterization of these well‐defined branched polysulfone ionomers provide a basis for future investigation of polymer topology effects on IPT performance. Copyright © 2009 Society of Chemical Industry     

Synthesis, characterization and evaluation of amphiphilic star copolymeric emulsifiers based on methoxy hexa(ethylene glycol) methacrylate and benzyl methacrylate

Amphiphilic star copolymers were synthesized by sequential monomer and cross-linker additions using group transfer polymerization (GTP). Benzyl methacrylate (BzMA) and methoxy hexa(ethylene glycol) methacrylate (HEGMA) served as the hydrophobic and hydrophilic monomers, respectively, whereas the also hydrophobic ethylene glycol dimethacrylate (EGDMA) was used as the cross-linker. In total, twelve star copolymers were prepared, covering three different overall hydrophobic compositions, 39, 53 and 70% w/w, and four different architectures, AB star-block, BA star-block, heteroarm star and random star. The theoretical molecular weight of each arm was kept constant at 5000 g mol⁻¹. The molecular weights and molecular weight distributions of the linear precursors and of all the star copolymers were characterized by gel permeation chromatography (GPC) in tetrahydrofuran (THF), while their compositions were confirmed by proton nuclear magnetic resonance (¹H NMR) spectroscopy. Moreover, all the star copolymers were characterized by static light scattering (SLS) in THF to determine the absolute weight-average molecular weight, M_w, and the weight-average number of arms. After polymer characterization, xylene-water and diazinon (pesticide)-water emulsions were prepared using these star copolymers as stabilizers at 1% w/w copolymer concentration and at different overall organic phase/water ratios. The most important factor in determining the emulsion type was the star copolymer composition in hydrophobic units. The four most hydrophilic star copolymers (39% w/w hydrophobic composition) always formed o/w emulsions, while the four most hydrophobic star copolymers (70% w/w hydrophobic composition) always formed w/o emulsions. The type of the emulsion in the case of the star copolymers with the more balanced composition, 53% w/w hydrophobic units, also depended on the emulsion content in the organic solvent, similar to particulate-stabilized emulsions. Considering that the best o/w emulsifier is that star copolymer which can emulsify the largest quantity of organic phase in water resulting in low viscosity, o/w emulsions without excess oil or water phase, it appeared that the most hydrophilic random copolymer star is the optimal emulsifier. Moreover, this star copolymer presented the smallest droplet size in its emulsions. It is also noteworthy that the resulting emulsions almost never had high viscosity, a feature attributable to the compact nature of star polymers.     

Synthesis and characterization of quaternary ammonium ionomers

The cationic monomers, MPDMAC₁₆ and MPDMAC₁₈, were obtained by quaternization of methacrylamidopropyl–N,N′‐dimethylamine with n‐alkyl iodides (1‐iodohexadecane and 1‐iodooctadecane) in ethyl acetate. Hydrophobic ionomers of MPDMAC₁₆ and MPDMAC₁₈ with N‐substituted acrylamides were prepared at 60 ± 0.1°C in DMF using AIBN initiator. The cationic monomers and ionomers were characterized by ¹H‐ and ¹³C‐NMR spectroscopy. The copolymer composition was evaluated from elemental analysis data using carbon/nitrogen (C/N) ratio. The molecular weight distributions of ionomers were obtained from GPC analysis. Both the dilute solution and concentrated solution properties of ionomers were studied by viscometry at 30°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1100–1105, 2005     

Effect of molecular architecture on the self-diffusion of polymers in aqueous systems: A comparison of linear, star, and dendritic poly(ethylene glycol)s

Star polymers with a hydrophobic cholane core and four poly(ethylene glycol) (PEG) arms, CA(EG_n)₄, have been synthesized by anionic polymerization. Pulsed-gradient spin-echo NMR spectroscopy was used to study the diffusion behavior of the star polymers, ranging from 1000 to 10,000 g/mol, in aqueous solutions and gels of poly(vinyl alcohol) (PVA) at 23 °C. The star polymers have a lower self-diffusion coefficient than linear PEGs at equivalent hydrodynamic radius. In water alone, the star polymers and their linear homologues have a similar diffusion behavior in the dilute regime, as demonstrated by the similar concentration dependence of the self-diffusion coefficients. In the semidilute regime, the star polymers tend to aggregate due to their amphiphilic properties, resulting in lower self-diffusion coefficients than those of linear PEGs. ¹H NMR T₁ measurements at 10-70 °C revealed that the PEG arms of the star polymers are more mobile than the core, suggesting the star polymers in solution have a conformation similar to that of poly(propylene imine) dendrimers.     

Fabrication of thermo-responsive hydrogels from star-shaped copolymer with a biocompatible β-cyclodextrin core

A thermally reversible hydrogel composed of a three-arm star copolymer with a specific host β-cyclodextrin (β-CD) center has been developed. The synthesis of this star copolymer initiates with β-CD core, from which sequential polymerization of a temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) block and a hydrophilic poly(N,N-dimethylacrylamide) (PDMA) block as asymmetric arms (named β-CD-g-(PNIPAM-b-PDMA)₃) is performed via RAFT protocol. Below the lower critical solution temperature (LCST) of PNIPAM segment, the polymer is of good water-solubility and exhibits a sol state. Upon thermal stimulus, free-standing hydrogels can be formed rapidly at sufficiently high concentrations. By comparing the sol–gel transition of the star polymer with that of its linear counterpart without this feature, we concluded that the special star-shape topology and the thermal-collapsed PNIPAM chains were responsible for this gelation behavior. The rheology measurements indicate the mechanical properties of the polymer hydrogels and the thermal reversibility of the sol–gel transition. Using Rhodamine B as a molecule to model a typical drug, we realize the favorable encapsulation and releasing process from the hydrogel, demonstrating that this star polymer has the potential to function as an injectable hydrogel for drug delivery and gene transport.     

New polyisobutylene-based model elastomeric ionomers. VIII. Thermal-mechanical analysis

A series of well-characterized telechelic polyisobutylene-based sulfonated metal-neutralized ionomers have been studied using thermal-mechanical analysis (TMA). These ionomers serve as models in the sense that the ionic groups are located exclusively at the chain ends and hence the ionomeric character is well defined. The chemical parameters varied are (i) molecular weight, (ii) molecular architecture (linear or triarm products), (iii) addition of excess neutralizing agent, and (iv) type of cation. The effect of the above parameters on the glass transition temperature and the softening temperature (after the rubbery plateau region) is presented. It is observed that the glass transition temperature is only slightly affected by the above parameters due to the very low ionic content in these ionomers (< 2 mol %). In the case of the triarm ionomer with excess neutralizing agent, the softening temperature following the rubbery plateau is much higher than that of the linear difunctional species. Linear monofunctional species do not show a rubbery plateau behavior and readily flow above their T_g in the absence or presence of excess neutralizing agent. The excess salt is most likely located at the ionic sites rather than being uniformly distributed throughout the matrix. Zinc-neutralized ionomers were found to have the lowest softening temperatures as compared to the corresponding calcium and potassium-neutralized ionomers. The covalent character of zinc is believed to be primarily responsible for this behavior. Thermal stability of these metalneutralized ionomers is not significantly different from the sulfonated hydrocarbon precursor polymer. However, the unneutralized acid precursor polymers start to discolor at relatively lower temperatures, thereby suggesting poorer thermal stability.     

Synthesis of star polymer by means of the living polymerization of [(o-trifluoromethyl)phenyl]acetylene using a MoOCl4-based catalyst and the linking method

A star polymer was synthesized by addition of 1,4-diethynyl-2,5-dimethylbenzene as linking agent (30 °C, 24 h) after living polymerization of [(o-trifluoromethyl)phenyl]acetylene (o-CF₃PA) with MoOCl₄-n-Bu₄Sn-EtOH catalyst (in anisole, 30 °C, 20 min; [Mo]=10 mM, [P^∗]/[Mo]=40%, [o-CF₃PA]₀=200 mM). The M_n values of the living and star polymers were 8.1×10³ and 5.3×10⁴, respectively, according to gel permeation chromatography, while these values determined by multi-angle laser light scattering (MALLS) were 7.8×10³ and 2.5×10⁵. The M_w/M_n and arm number of the star polymer were 1.04 and 29, respectively, according to MALLS. The molecular weight and arm number of star polymer increased with increasing linking agent concentration and polymerization temperature.     

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.