Polyolefins Thermoplastic

In the early stages of development of polypropylene rubbers, particularly butyl rubber, were used to reduce the brittleness of polypropylene. Their use declined for some years with the development of the polypropylene copolymers but interest was greatly renewed in the 1970s. This interest has been centred largely around the ethylene-propylene rubbers which are reasonably compatible in all proportions with polypropylene. At first the main interest was with blends in which the rubber content exceeded 50% of the blend and such materials have been designated as thermoplastic polyolefin elastomers (discussed in Section 11.9.1). There is also increasing interest in compounds with less than 50% rubber, often referred to as elastomer-modified thermoplastics. It is of interest to note... 

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... 

Although the elastomer phase is essentially in particulate form, the tensile strength of the blend can be increased five-fold by increasing the cross-link density from zero to that conventionally used in vulcanisation processes, whilst tension set may be reduced by over two-thirds. Since the thermoplastic polyolefin phase may be completely extracted by boiling decalin or xylene, there is apparently no covalent chemical bonding of elastomer and thermoplastic phases. 

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. 

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. 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

Currently, important TPE s include blends of semicrystalline thermoplastic polyolefins such as propylene copolymers, with ethylene-propylene terepolymer elastomer. Block copolymers of styrene with other monomers such as butadiene, isoprene, and ethylene or ethylene/propy-lene are the most widely used TPE s. Styrene-butadiene-styrene (SBS) accounted for 70% of global styrene block copolymers (SBC). Currently, global capacity of SBC is approximately 1.1 million tons. Polyurethane thermoplastic elastomers are relatively more expensive then other TPE s. However, they are noted for their flexibility, strength, toughness, and abrasion and chemical resistance. Blends of polyvinyl chloride with elastomers such as butyl are widely used in Japan. ... 

Thermoplastic polyolefin rubbers are usually blends based on polypropylene and ethylene-propylene rubbers. They are not resistant to hydrocarbons. 

In addition to the two-phase TPEs, two new technologies have emerged. They are the metallocene-catalyzed polyolefin plastomers (POPs, the name given to Exxon s EXACT product line) and polyolefin elastomers (POEs, DuPont Dow Elastomer s ENGAGE), and reactor-made thermoplastic polyolefin elastomers (R-TPOs). These new types of TPEs are often called metallocene elastomers-TPEs (MEs-TPEs) [87]. The new POPs and POEs are essentially very low-molecular-weight-Unear low-density PEs (VLMW-LLDPE). These new-generation TPEs exhibit mbber-like properties and can be processed on... 

RECYCLING TECHNOLOGY FOR LAMINATES COMPOSED OF THERMOPLASTIC POLYOLEFIN ELASTOMER AND CROSSLINKED POLYPROPYLENE FOAM... 

One would expect that addition filler of similar structure would reinforce the hard segments. It was found that the addition of thermoplastic polyolefins of high melting point did improve the physical properties. 

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