Plastics ionomers

In the preparation and processing of ionomers, plasticizers may be added to reduce viscosity at elevated temperatures and to permit easier processing. These plasticizers have an effect, as well, on the mechanical properties, both in the rubbery state and in the glassy state these effects depend on the composition of the ionomer, the polar or nonpolar nature of the plasticizer and on the concentration. Many studies have been carried out on plasticized ionomers and on the influence of plasticizer on viscoelastic and relaxation behavior and a review of this subject has been given 119]. However, there is still relatively little information on effects of plasticizer type and concentration on specific mechanical properties of ionomers in the glassy state or solid state. 

A stress relaxation study of plasticized ionomers contrasts the effects of DOP and... 

Even less is known about ionomer/plasticizer interactions on a molecular level. A variety of scattering and spectroscopic techniques that can probe this level have been mentioned, but they have been applied primarily to the specific case of water in ionomers, and in particular to hjdrated perfluorinated ionomers. At the least, these studies demonstrate the powerful potential of the techniques to contribute to a more complete understanding of structure-property relationships in plasticizer/ionomer systems. For e.xample, to return to the question of the effect of nonpolar plasticizers on the ionic domains how can the decrease in the ionic transition temperature be reconciled with the apparently minimal effect on the SAXS ionomer peaks and with the ESR studies that indicate (not surprisingly) tiiat these plasticizers have essentially no influence on the local structure of the ions Is it due to their association with the hydrocai bon component of the large aggregates or clusters Or if these entities do not exist, as some researchers postulate, what is the interaction between the nonpolar plasticizer, the hydrocarbon component and the ionic domains These questions are, of course, intimately related to the understanding of ionomer microstructure even in the absence of plasticizer. The interpretation of SAXS data in particular is subject to the choice of model used. 

In conclusion, there is clearly a need for in-depth, systematic studies of a wide variet.v of plasticizer/ionomer syst.ems. Such studies may additionally contribute to a better understanding of the ionomer microstructure in general. 

This analysis suggests that two different kinds of plasticizers may be needed to plasticize ionomers ... 

Fig. 11. Schematic diagrams of a multiplet and restricted mobility region surrounding it for plasticized ionomers (a) polar plasticization, (b) nonpolar plasticization, and (c) amphiphilic plasticization. The thicker curved lines represent plasticizer molecules.

Other Films. Although commercially less important than polyethylenes and polypropylenes, a number of other plastic films are in commercial use or development for special appHcations, including ethylene—vinyl acetate, ionomer, and polyacrylonitrile [25014-41-9]. 

In addition to time-related effects, the soUd-state physical properties are also affected by adsorbed water, which functions as a plasticizer. Water pickup is affected by the nature of the cation, with sodium ionomers absorbing about 10 times the level of the zinc equivalent (6) under the same conditions. Drying must be carried out at temperatures below 100°C and is therefore a slow process. In commercial practice, ionomers are suppUed dry, and techniques have been developed to minimize moisture absorption during processing. 

Many methods for the conversion of acid copolymers to ionomers have been described by Du Pont (27,28). The chemistry involved is simple when cations such as sodium or potassium are involved, but conditions must be controlled to obtain uniform products. Solutions of sodium hydroxide or methoxide can be fed to the acid copolymer melt, using a high shear device such as a two-roU mill to achieve uniformity. AH volatile by-products are easily removed during the conversion, which is mn at about 150°C. A continuous process has been described, using two extmders, the first designed to plasticate the feed polymer and mix it rapidly with the metal compound, eg, zinc oxide, at 160°C (28). Acetic acid is pumped into the melt to function as an activator. Volatiles are removed in an extraction-extmder which follows the reactor-extmder, and the anhydrous melt emerges through a die-plate as strands which are cut into pellets. 

As the author pointed out in the first edition of this book, the likelihood of discovering new important general purpose materials was remote but special purpose materials could be expected to continue to be introduced. To date this prediction has proved correct and the 1960s saw the introduction of the polysulphones, the PPO-type materials, aromatic polyesters and polyamides, the ionomers and so on. In the 1970s the new plastics were even more specialised in their uses. On the other hand in the related fields of rubbers and fibres important new materials appeared, such as the aramid fibres and the various thermoplastic rubbers. Indeed the division between rubbers and plastics became more difficult to draw, with rubbery materials being handled on standard thermoplastics-processing equipment. 

The stable sodium ion has a positive charge because it is short of one electron and the chlorine atom is negatively charged for the converse reason. Ionic bonds are seldom found in polymers of current interest as plastics materials although the ionic bond is important in ion-exchange resins and in the ionomers (see Chapter 11). 

In the late 1970s several developments occurred causing renewed interest in poly(ethylene terephthalate) as a plastics material. These included the development of a new mouldable grade by ICI (Melinar) and the development of a blow moulding technique to produce biaxially oriented PET bottles. In addition there appeared a glass-fibre filled, ionomer nucleated, dibenzoate plasticised material by Du Pont (Rynite) (see Chapter 26). 

Optical Properties. The optical properties of a plastic which are important are refraction, transparency, gloss and light transfer. The reader is referred to BS 4618 1972 for precise details on these terms. Table 1.9 gives data on the optical properties of a selection of plastics. Some plastics may be optically clear (e.g. acrylic, cellulosics and ionomers) whereas others may be made transparent. These include epoxy, polycarbonate, polyethylene, polypropylene, polystyrene, polysulphone and PVC. 

The mechanical properties of ionomers can be appreciably altered by the manner in which the ionomer is prepared and treated prior to testing. Some of the factors that are influential are the degree of conversion (neutralization) from the acid form to the salt form, the nature of the thermal treatment or aging, the type of counterion that is introduced, the solvent that is used for preparation of thin films, and the presence and nature of any plasticizers or additives that may be present. In the scope of this chapter, it is not possible to provide a complete description of the influence of each of these variables on the wide variety of ionomers that are now commercially available or produced in the laboratory. Instead, one or more examples of the changes in properties that may be induced by each of the processing variables is presented and discussed. 

Aside from ion content, a wide range of properties is available in ionomers by control of various processing variables, such as degree of conversion (neutralization), type of counterion, plasticizer content and thermal treatment. Various examples illustrating possible effects of these variables on mechanical relaxation behavior and on such mechanical properties as stiffness, strength, and time- or energy-to-fracture have been given. 

A membrane ionomer, in particular a polyelectrolyte with an inert backbone such as Nation . They require a plasticizer (typically water) to achieve good conductivity levels and are associated primarily, in their protonconducting form, with solid polymer-electrolyte fuel cells. 

Elasticity If the product requires flexibility, examples of the choices includes polyethylene, vinyl, polypropylene, EVA, ionomer, urethane-polyester, fluorocarbon, silicone, polyurethane, plastisols, acetal, nylon, or some of the rigid plastics that have limited flexibility in thin sections. 

A route to compatibility involving ionomers has been described recently by Eisenberg and coworkers [250-252]. The use of ionic interactions between different polymer chains to produce new materials has gained tremendous importance. Choudhury et al. [60] reported compatibilization of NR-polyolefin blends with the use of ionomers (S-EPDM). Blending with thermoplastics and elastomers could enhance the properties of MPR. The compatibility of copolyester TPE, TPU, flexible PVC, with MPR in aU proportions, enables one to blend any combination of these plastics with MPR to cost performance balance. Myrick has reported on the effect of blending MPR with various combinations and proportions of these plastics and provided a general guideline for property enhancement [253]. 

Unlike other aqueous dental cements, the zinc polycarboxylate retains plastic characteristics even when aged and shows significant stress relaxation after four weeks (Paddon Wilson, 1976). It creeps under static load. Wilson Lewis (1980) found that the 24-hour creep value for one cement, under a load of 4-6 MPa, was 0-7 % in 24 hours, which was more than that of a zinc phosphate cement (0-13 %) and a glass-ionomer cement (0-32%), but far less than that of the zinc oxide eugenol cement (2-2%). 

The diametral compressive strength has been used to estimate the tensile strength of certain AB cements (Smith, 1968). In this test, the load is applied diametrically across a cylinder of cement. Theoretical consideration of the test geometry shows that for a perfectly brittle material the failure that occurs is tensile in character. The difficulty in applying this test to AB cements is that they are not sufficiently brittle for this to hold true. In particular, the zinc polycarboxylate and glass-ionomer cements show sufficient plastic character to make the relationship between diametral compressive and tensile strength vary between AB cements of different types like the compressive strength test, this test is valid only as a means of comparison between similar materials (Darvell, 1990). 

Ion nitriding, 16 205 Ionomer blends, 14 476-478 Ionomer food packaging, 13 44 Ionomer peak, 14 464 Ionomer properties, effects of polar plasticizers on, 14 479 Ionomers, 14 460-489... 

Polar plasticizers, effects on ionomer properties, 24 479 Polar solvents, 10 205, 207, 409... 

---