Thermoplastic elastomers processing

C.P. Rader, J. R. Richwine, E. P. Tam, G. E. O Connor, Santoprene thermoplastic elastomer processability and product applications. International rubber and plastic exhibition and conference for Asia, Singapore, 1986 A. Seeffied, M. Fuchs, D. Drummer, Plast. Eng. 68(10), 14 (2012)... 

Considerable work has also been conducted to try to find thermoplastic elastomers that can be used to simplify processing by enabling dry blending and melt casting instead of the conventional mixing and curing process (see Elastomers, synthetic). 

EPDM-Derived Ionomers. Another type of ionomer containing sulfonate, as opposed to carboxyl anions, has been obtained by sulfonating ethylene—propjlene—diene (EPDM) mbbers (59,60). Due to the strength of the cross-link, these polymers are not inherently melt-processible, but the addition of other metal salts such as zinc stearate introduces thermoplastic behavior (61,62). These interesting polymers are classified as thermoplastic elastomers (see ELASTOLffiRS,SYNTHETIC-THERMOPLASTICELASTOLffiRS). 

As with all thermoplastic elastomers, the copolyesterethers can be processed as thermoplastics. They are linear polymers and contain no chemical cross-links, thus the vulcanisation step needed for thermosetting elastomers is eliminated and scrap elastomer can be re-used in the same process as virgin material (176—180). 

Urethanes are processed as mbber-like elastomers, cast systems, or thermoplastic elastomers. The elastomer form is mixed and processed on conventional mbber mills and internal mixers, and can be compression, transfer, or injection molded. The Hquid prepolymers are cast using automatic metered casting machines, and the thermoplastic peUets are processed like aU thermoplastic materials on traditional plastic equipment. The unique property of the urethanes is ultrahigh abrasion resistance in moderately high Shore A (75—95) durometers. In addition, tear, tensUe, and resistance to many oUs is very high. The main deficiencies of the urethanes are their resistance to heat over 100°C and that shear and sliding abrasion tend to make the polymers soft and gummy. 

The more important grades of thermoplastic natural mbber, which fall into the olefinic class of thermoplastic elastomers, are prepared with the natural mbber phase partially cross-linked during blending, a process known as dynamic vulcanization. The hardness of the soft blends is controlled by the natural mbber content, and typical properties of those of 50—90 hardness (Shore A) are shown in Table 7. 

Blends of isobutylene polymers with thermoplastic resins are used for toughening these compounds. High density polyethylene and isotactic polypropylene are often modified with 5 to 30 wt % polyisobutylene. At higher elastomer concentration the blends of butyl-type polymers with polyolefins become more mbbery in nature, and these compositions are used as thermoplastic elastomers (98). In some cases, a halobutyl phase is cross-linked as it is dispersed in the polyolefin to produce a highly elastic compound that is processible in thermoplastic mol ding equipment (99) (see Elastomers, synthetic-thermoplastic). ... 

The classification given in Table 1 is based on the process, ie, thermosetting or thermoplastic, by which polymers in general are formed into usehil articles and on the mechanical properties, ie, rigid, flexible, or mbbery, of the final product. AH commercial polymers used for molding, extmsion, etc, fit into one of these six classifications the thermoplastic elastomers are the newest. 

Thermoplastic elastomers based on blends of a siUcone mbber (cross-linked during processing) with block copolymer thermoplastic elastomers have also been described (37,38). 

Most thermoplastic elastomers are stable materials and decompose only slowly under normal processing conditions. If decomposition does occur, the products are usuaHy not particularly ha2ardous and should not present a problem if good ventilation is provided. Extra caution should be exercised when processing polyurethanes, especiaHy those containing polycaprolactone segments. In these cases the decomposition products may include isocyanates and caprolactam, both of which are potential carcinogens. 

In the absence of impurities there is frequently no termination step in anionic polymerisations. Hence the monomer will continue to grow until all the monomer is consumed. Under certain conditions addition of further monomer, even after an interval of several weeks, will eause the dormant polymerisation process to proceed. The process is known as living polymerisation and the products as living polymers. Of particular interest is the fact that the follow-up monomer may be of a different species and this enables block copolymers to be produced. This technique is important with certain types of thermoplastic elastomer and some rather specialised styrene-based plastics. 

All three types of material have now been available for some years and it is probably also true that none have yet realised their early promise. In the case of the thermoplastic elastomers most of the commercial materials have received brief mention in earlier chapters, and when preparing earlier editions of this book the author was of the opinion that such materials were more correctly the subject of a book on rubbery materials. However, not only are these materials processed on more or less standard thermoplastics processing equipment, but they have also become established in applications more in competition with conventional thermoplastics rather than with rubbers. 

Thermoplastic elastomers have now been available for over 30 years and the writer recalls organising a conference on these materials in 1969. In spite of considerable publicity since that time these materials still only comprise about 5-10% of the rubber market (equivalent to about 1-2% of total plastics consumption). It is important to appreciate that simply being a thermoplastic material (and hence being processed and reprocessed like a thermoplastic plastics material) is not enough to ensure widespread application. Crucially the material must have acceptable properties for a potential end-use and at a finished product price advantageous over other materials. 

Thermoplastic polyurethane (TPU) is a type of synthetic polymer that has properties between the characteristics of plastics and rubber. It belongs to the thermoplastic elastomer group. The typical procedure of vulcanization in rubber processing generally is not needed for TPU instead, the processing procedure for normal plastics is used. With a similar hardness to other elastomers, TPU has better elasticity, resistance to oil, and resistance to impact at low temperatures. TPU is a rapidly developing polymeric material. 

The processing technologies for elastomeric blends, thermoplastic elastomer-based on mechanical mixing, and elastomer-plastic vulcanizates are distinctly different. Depending on the type and nature of blend, size, and their final application, a wide range of processing equipment is now in use both industrially as well as in laboratory scale preparation. 

Thermoplastic elastomers are materials that have the properties of vulcanized rubbers but can be processed by techniques associated with thermoplastics. The commercial importance of TPEs is due to their superior processing properties and economic advantages over conventional rubbers and plastics. TPEs from rubber-plastic blends became important because they combine the superior processability of thermoplastics and the... 

Thermoplastic elastomers (TPES), as the name indicates, are plastic polymers with the physical properties of rubbers. They are soft, flexible, and possess the resilience needed of rubbers. However, they are processed like thermoplastics by extrusion and injection molding. 

Handbook of elastomers , A.K. Bhowmick and H.L. Stephens Marcel Dekker (1988) Series Plastics Engineering, Volume 19 ISBN 0824778006. This handbook systematically addresses the manufacturing techniques, properties, processing, and applications of rubbers and rubber-like materials. The Handbook of Elastomers provides authoritative information on natural rubbers, synthetic rubbers, liquid rubbers, powdered rubbers, rubber blends, thermoplastic elastomers, and rubber-based composites— offering solutions to many practical problems encountered with rubber materials. 

Table 17 provides a list of various polysiloxane-poly(aryl ether) copolymers investigated. Depending on the type, nature and the level of the hard blocks incorporated, physical, thermal and mechanical properties of these materials can be varied over a very wide range from that of thermoplastic elastomers to rubber modified engineering thermoplastics. Resultant copolymers are processable by solution techniques and in some cases by melt processing 22,244). 

Advantages of Thermoplastic Elastomer over Thermoset Rubber Processing... 

Umpleby J.D., Process of preparation of thermoplastic elastomers, US Patent 4803224, 1989. 

Wallace J.G., Single phase melt processible rubber. Handbook of Thermoplastic Elastomer (Walker B.M. and Rader C.P., eds.). Van Nostrand Reinhold, New York, 1988, 141. 

TPE Processing Guide, Thermoplastic Elastomer Division, GLS Corporation, McHenry, IL. 

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