Thermoplastics thermoplastic rubber

Table 6. Typical Properties of Hard Blends of Thermoplastic Natural Rubber...

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. 

Tbe system may be used for homopolymers and for block copolymers. Some commercial SBS triblock thermoplastic rubbers and the closely related K-resins produced by Phillips are of this type. Anionic polymerisation methods are of current interest in the preparation of certain diene rubbers. 

Butadiene and styrene may be polymerised in any proportion. The Tfs of the copolymers vary in an almost linear manner with the proportion of styrene present. Whereas SBR has a styrene content of about 23.5% and is rubbery, copolymers containing about 50% styrene are leatherlike whilst with 70% styrene the materials are more like rigid thermoplastics but with low softening points. Both of these copolymers are known in the rubber industry as high-styrene resins and are usually used blended with a hydrocarbon rubber such as NR or SBR. Such blends have found use in shoe soles, car wash brushes and other mouldings but in recent times have suffered increasing competition from conventional thermoplastics and to a less extent the thermoplastic rubbers. 

In addition to the somewhat sophisticated triblock thermoplastic elastomers described above, mention should be made of another group of thermoplastic diene rubbers. These are physical blends of polypropylene with a diene rubber such as natural rubber. These may be considered as being an extension to the concept of thermoplastic polyolefin rubbers discussed in Section 11.9.1 and although extensive experimental work has been carried out with these materials they do not yet appear to have established themselves commercially. 

These rubbers are now also being blended on a large scale with polyolefin plastics, particularly polypropylene, to produce a range of materials which at one extreme are tough plastics and at the other the so-called thermoplastic polyolefin rubbers (TPORs) (.see Section 11.9.1). 

Subsequently, much improved thermoplastic polyolefin rubbers were obtained by invoking a technique known as dynamic vulcanisation. This process has been defined (Coran, 1987) as the process of vulcanizing elastomer during its intimate melt-mixing with a non-vulcanizing thermoplastic polymer. Small elastomer droplets are vulcanized to give a particulate... 

A somewhat different approach to the production of thermoplastic polyolefin rubbers has been adopted by Allied Chemical with their ET polymers. With these materials butyl rubber is grafted on to polyethylene chains using a phenolic material such as brominated hydroxymethyl phenol. The initial grades of these polymers, which were introduced commercially towards the end of the 1970s, had polyethylene butyl rubber ratios of 50 50 and 75 25. Both low-density and high-density polyethylene-based varieties were produced. 

In this chapter brief consideration has been given to the major tonnage mbbers. Derivatives of natural mbber such as ebonite are discussed in Chapter 30 and thermoplastic rubbers are reviewed in Chapter 31. Other important speciality mbbers (with their ASTM designations) include ... 

This route has only been developed during the 1980s and has proved of particular interest in the manufacture of thermoplastic polyamide rubbers. 

Although some of the polyamides described in Section 18.10 are somewhat rubbery, they have never achieved importance as rubbers. On the other hand, the past decade and a half has seen interest aroused in thermoplastic elastomers of the polyamide type which may be considered as polyamide analogues of the somewhat older and more fully established thermoplastic polyester rubbers. 

Other companies interested in thermoplastic polyamide rubbers have been Dow (following on work by Upjohn) and Akzo, whose initial development grades have been trade marked Ametal. 

With the expiry of the basic ICI patents on poly(ethylene terephthalate) there was considerable development in terephthalate polymers in the early 1970s. More than a dozen companies introduced poly(butylene terephthalate) as an engineering plastics material whilst a polyether-ester thermoplastic rubber was introduced by Du Pont as Hytrel. Polyfethylene terephthalate) was also the basis of the glass-filled engineering polymer (Rynite) introduced by Du Pont in the late 1970s. Towards the end of the 1970s poly(ethylene terephthalate) was used for the manufacture of biaxially oriented bottles for beer, colas and other carbonated drinks, and this application has since become of major importance. Similar processes are now used for making wide-neck Jars. 

In the case of the polycrystalline polyester thermoplastic rubbers the simple domain theory does not seem to apply. With these rubbers it would appear that they contain spherulitic structures consisting of 4GT radial lamellae with inter-radial amorphous regions that are mixtures of PTMEG soft segments and noncrystalline hard segments. 

The market is dominated by flexible foam applications (43% in the United States) and rigid and semi-rigid foam (29%). Cast elastomers (4%) and RIM elastomers (3%) have only specialised outlets. The remaining sizeable 21% of the market cover such diverse uses as thermoplastic rubbers, surface coatings, adhesives, sealants and synthetic leathers. 

It is generally more convenient to use the thermoplastic polyurethane rubbers discussed in Section 27.4.4 for those applications where a cast process is not appropriate. 

The thermoplastic rubbers have properties similar to those of the cast polyurethane rubbers but, because of the absence of covalent cross-links, have rather higher values for compression set, a common problem with thermoplastic rubbers. Their main uses are for seals, bushes, convoluted bellows and bearings. 

One partieular form of thermoplastic polyurethane elastomers is the elastic fibre known as spandex fibre. Like the usual thermoplastic rubbers these materials consist of hard and soft segments but to qualify for the term spandex by the US Federal Trade Commission the polymer used should contain at least 85% of segmented polyurethane. The first commercial material of this type was introduced by Du Pont in 1958 (Lycra). Several other similar materials have since been introduced including Dorlastan (Bayer), Spanzelle (Courtaulds) and Vyrene (US Rubber). 

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. 

A manufacturer considering using a thermoplastic elastomer would probably first consider one of the thermoplastic polyolefin rubbers or TPOs, since these tend to have the lowest raw polymer price. These are mainly based on blends of polypropylene and an ethylene-propylene rubber (either EPM or EPDM) although some of the polypropylene may be replaeed by polyethylene. A wide range of blends are possible which may also contain some filler, oil and flame retardant in addition to the polymers. The blends are usually subject to dynamic vulcanisation as described in Section 11.9.1. 

PEBA thermoplastic polyamide rubber, polyether block amide... 

The applications of rubber as an engineering material almost invariably involve bonding to a rigid substrate or reinforcement. In some instances these bonds need to be established to a fully cured thermoset rubber or a molded thermoplastic rubber, and a wide variety of adhesives suitable for this purpose are available. In... 

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