Polyether-based polymers

The minimum service temperature is determined primarily by the Tg of the soft phase component. Thus the SBS materials ctm be used down towards the Tg of the polybutadiene phase, approaching -100°C. Where polyethers have been used as the soft phase in polyurethane, polyamide or polyester, the soft phase Tg is about -60°C, whilst the polyester polyurethanes will typically be limited to a minimum temperature of about 0°C. The thermoplastic polyolefin rubbers, using ethylene-propylene materials for the soft phase, have similar minimum temperatures to the polyether-based polymers. Such minimum temperatures can also be affected by the presence of plasticisers, including mineral oils, and by resins if these become incorporated into the soft phase. It should, perhaps, be added that if the polymer component of the soft phase was crystallisable, then the higher would also affect the minimum service temperature, this depending on the level of crystallinity. 

Besides the polyether-based polymer electrolytes, the nitrogen analogues (polyimines) were also extensively studied. Various other oxygen-containing... 

The chemical structure and molecular weight of the polymer both influence the rate of coagulation and the structure produced. A high molecular weight polymer coagulates more rapidly than one of lower molecular weight. It is found that in a DMF/water system, a polyether-based polymer coagulates more rapidly than a polyester-based polymer of the same urethane content. 

The quasi-prepolymer system of RIM can be operated with polyester or polyether-based polymers. Clarks have concentrated on the use of polyesters, because they have offered consistently and markedly superior physical performance, particularly flex and abrasion resistance. The characteristics of the moulding are determined by the mix, the shot size, the mould design etc., and the polyester-based system developed within the Clarks organization is basically a microcellular product, with a graded density cell structure, see Fig. 13.6. There is a thin (about 0.025 mm) solid surface, rather than a skin, which allows applications of solvent-based finishes without damage. 

TAMBELLi, C.E., DONOSO, J.P., REGIANI, A.M., et flZ., Nnclear magnetic resonance and conductivity study of HEC/polyether-based polymer electrolytes, Electro-chim. Acta, 2001, 46,1665-72. 

Heteroatom Chain Backbone Polymers. This class of polymers includes polyesters, which have been widely studied from the initial period of research on biodegradable polymers, polyamides, polyethers, polyacetals, and other condensation polymers. Their linkages are quite frequendy found in nature and these polymers are more likely to biodegrade than hydrocarbon-based polymers. 

Reactive (unsaturated) epoxy resins (qv) are reaction products of multiple glycidyl ethers of phenoHc base polymer substrates with methacrylic, acryhc, or fumaric acids. Reactive (unsaturated) polyester resins are reaction products of glycols and diacids (aromatic, aUphatic, unsaturated) esterified with acryhc or methacrylic acids (see POLYESTERS,unsaturated). Reactive polyether resins are typically poly(ethylene glycol (600) dimethacrylate) or poly(ethylene glycol (400) diacrylate) (see PoLYETPiERs). 

Thermoplastic polyurethane elastomers have now been available for many years (and were described in the first edition of this book). The adipate polyester-based materials have outstanding abrasion and tear resistance as well as very good resistance to oils and oxidative degradation. The polyether-based materials are more noted for their resistance to hydrolysis and fungal attack. Rather specialised polymers based on polycaprolactone (Section 25.11) may be considered as premium grade materials with good all round properties. 

Whilst approximately twice the raw material cost of TPO- and S-B-S-type polymers, thermoplastic polyurethane elastomers find applications where abrasion resistance and toughness are particular requirements. Uses include gears, timing and drive belts, footwear (including ski boots) and tyre chains. Polyether-based materials have also achieved a number of significant medical applications. There is also some minor use as hot melt adhesives, particularly for the footwear industry. 

The general molecular structure of polyether-based polyurethanes is illustrated in Fig. 25.3 a). Typical polyether sequences include polyethylene glycol and polypropylene glycol. The length of the polyether sequences between urethane links can vary from one or two ether groups up to several hundred. As the length of the polyether sequences between urethane links increases, the polymer exhibits more of the properties normally associated with polyethers. 

The unique surface characteristics of polysiloxanes mean that they are extensively used as surfactants. Silicone surfactants have been thoroughly studied and described in numerous articles. For an extensive, in-depth discussion of this subject, a recent chapter by Hill,476 and his introductory chapter in the monograph he later edited,477 are excellent references. In the latter monograph, many aspects of silicone surfactants are described in 12 chapters. In the introduction, Hill discusses the chemistry of silicone surfactants, surface activity, aggregation behavior of silicone surfactants in various media, and their key applications in polyurethane foam manufacture, in textile and fiber industry, in personal care, and in paint and coating industries. All this information (with 200 cited references) provides a broad background for the discussion of more specific issues covered in other chapters. Thus, surfactants based on silicone polyether co-polymers are surveyed.478 Novel siloxane surfactant structures,479 surface activity and aggregation phenomena,480 silicone surfactants application in the formation of polyurethane foam,481 foam control and... 

Percec et al. have described the possibility of making hyperbranched polymers which exhibit liquid crystalline phases [34, 35]. They made hyperbranched polyethers based on an A B monomer having both a spacer and a... 

Membrane research is a rather diverse field, exploiting perfluorinated iono-mers, hydrocarbon and aromatic polymers, and acid-base polymer complexes. Polyether and polyketo polymers with statistically sulfonated phenylene groups such as sPEK, sPEEK, and sPEEKK or polymers on the basis of benzimidazole have been tested as well. Recent reviews on membrane synthesis and experimental characterization can be found in the literature. ... 

Miyamoto and Shibayama (1973) proposed a model which is essentially an extension to free volume theory, allowing explicitly for the energy requirements of ion motion relative to counter ions and polymer host. This has been elaborated (Cheradame and Le Nest, 1987) to describe ionic conductivity in cross-linked polyether based networks. The conductivity was expressed in the form... 

Despite the initial misinterpretation in the ion conduction mechanism, it was soon realized that the ion conduction in PEG and other similar polyether-based media mainly occurred in the amorphous phases. Increasing evidences were obtained that ionic motion in these polymer ion conductors was closely... 

Polyethers are typically products of base-catalyzed reactions of the oxides of simple alkenes. More often than not, ethylene oxides or propylene oxides and block copolymers of the oxides are used. A polypropylene oxide-based polymer is built and then capped with polyethylene oxides. An interesting aspect of this chemistry is the use of initiators. For instance, if a small amount of a trifunctional alcohol is added to the reactor, the alkylene oxide chains grow from the three alcohol end groups of the initiator. Suitable initiators are trimethylol propane, glycerol or 1,2,6 hexanetriol. The initiator is critical if one is to make a polyether foam for reasons that we will discuss shortly. 

Copolymers of methacrylic add and ethylene termed as ethylene ionomers have been used as the base polymer for binding alkali, alkaline earth and transition metal ions. Organic amines such as n-hexylamine, hexamethylene tetraamine, 2,2,6,6-tetramethyM-hydroxy piperazine, ethylene diamine and polymeric diamines such as silicone diamine, polyether diamine and polymeric diamines such as silicone diamine, polyether diamine and polyamide oligomers considerably enhance the complex formation characteristics of Zn(II) ethylene ionomers thereby enhancing the physico-chemical properties [13]. 

Polymer Type Polyester Based Polyether Based Polyether Based Polyether Based... 

Oligomeric carbodiimides are useful stabilizers for ester based polymers, such as polyesters, polyester based polyurethanes, polyether based polyurethanes, polyether based poly(urethane ureas) and polycarbonates. The scavenging of carboxyl end groups or carboxyl groups, generated in the hydrolysis of polyesters, with carbodiimide prevents hydrolysis of the polymers caused by the catalytic effect of the carboxyl groups. Neumann... 

M. Ravey and E. M. Pearce, Elexible polyurethane foam. 1. Thermal decomposition of a polyether-based, water-blown commercial type of flexible polyurethane foam, J. Appl. Polym. Sci., 63, 47-74 (1997). 

This paper presents some of our results on the synthesis and structure of thermotropic main-chain liquid crystalline polyethers based on bis(4-hydroxy-phenoxy)-p-xylene. It also deals with two areas in the field of liquid crystalline polymers that have received only little attention, namely the dielectric relaxation (5-10 and Gedde, U.W. Liu, F. Hult, A. Gustafsson, A. Jonsson, H. Boyd, R.H. Polymer submitted) and the kinetics of isotropic-mesomorphic state transitions (11-14. 32). They are both very important for the understanding of the nature of the mesomorphic state in polymers and for the understanding of similarities and differences of physical phenomena between liquid crystalline and semi-crystalline polymers. 

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