Thermoplastic Elastomers

Geoffrey Holden, in Applied Plastics Engineering Handbook, 2011

Thermoplastic elastomers are a significant part of the elastomers

industry. Polymers can be characterized by how they are processed (as
thermosets or thermoplastics) and the physical properties (rigid,
flexible, or rubbery) of the final product. Thermoplastic elastomers
have many physical properties of rubbers, e.g., softness, flexibility,
and resilience, which they achieve by a physical process, compared to
the chemical process in vulcanized rubbers. Vulcanization is a
thermosetting process and is slow and irreversible. With thermoplastic
elastomers, the transition from a processable melt to a solid, rubber-
like object is rapid and reversible. Thermoplastic elastomers can be
processed using conventional techniques, such as injection molding
and extrusion; scrap can be recycled. Since the properties of
thermoplastic elastomers are usually not as good as those of
vulcanized rubbers at higher temperatures, they are used in areas
where these properties are less important (footwear, wire insulation,
adhesives), but not in areas such as automobile tires.
Laurence W. McKeen, in The Effect of Creep and Other Time Related
Factors on Plastics and Elastomers (Second Edition), 2009

8.1 Background

Thermoplastic elastomers (TPEs) have two big advantages over the

conventional thermoset (vulcanized) elastomers, namely ease and
speed of processing. Other advantages of TPEs are recyclability of
scrap, lower energy costs for processing, and the availability of
standard, uniform grades (not generally available in thermosets).

Physical and chemical properties can be controlled by varying the ratio

of the monomers and the length of the hard and soft segments. Block
techniques create long-chain molecules that have various or
alternating hard and soft segments. Graft polymerization methods
involve attaching one polymer chain to another as a branch. The
properties that are affected by each phase can be generalized as
follows.

“Hard phase”—plastic properties:

(1)Processing temperatures

(2)Continuous use temperature

(3)Tensile strength

(4)Tear strength

(5)‫ر‬Chemical and fluid resistance

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“Soft phase”—elastomeric properties:

(1)Lower service temperature limits

(2)Hardness

(3)Flexibility

(4)Compression set and tensile set

Three high performance types of TPEs make up this chapter.

8.1.1 Thermoplastic Polyurethane Elastomers (TPUs)

Urethanes are the reaction product of a long- or short-chain
polyether, polyester, or caprolactam glycol. The polyps and the short-
chain diols react with the to form linear polyurethane molecules. This
combination of and short-chain diol produces the rigid or hard
segment. The polyps form the flexible or soft segment of the final
molecule. Figure 8.1 shows the molecular structure in schematic form.

Figure 8.1. Molecular structure of a thermoplastic polyurethane elastomer.

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13.8 Applications

The processing advantages of thermoplastic elastomers in comparison to

thermoset rubbers were described earlier. Figure 13.20 highlights these
differences. Due to the ability to melt TPEs at high temperatures, these materials
can be simply shaped into desired products using traditional thermoplastic
processing equipment. This benefit is also a detriment; the fact that a TPE can
flow at elevated temperatures due to lack of crosslinks in the continuous phase
also means that it has a limited temperature range over which it can be used as
an elastomeric material. Therefore, the intended use temperature range must be
considered in selecting which TPE to use for an application. An illustration of the
temperature use window as defined by the temperature dependence of modulus
is shown in Figure.

Figure 13.20. General contrast between the processing of thermoset rubbers and thermoplastic
elastomers.

4 Taha Mushtaq