DESIGN PROPERTIES OF HIGH PERFORMANCE

THERMOPLASTIC ELASTOMER COMPOUNDS

BY LAWRENCE A. ACQUARULO, JR. AND CHARLES J. O’NEIL

INTRODUCTION :

Advances in design and function of medical devices have led to an increased need for
consistent, close-tolerance, high-performance thermoplastic elastomer compounds. This paper
will present an overview of thermoplastic elastomers. We will list advantages and
disadvantages of the different families of thermoplastic elastomers. We will then concentrate on
the two families of thermoplastic elastomers that are currently being used successfully in the
manufacture of a number of medical devices. We will introduce ways that these two families
may be modified to produce even more high performance characteristics that could be of great
benefit to the device manufacturer.

TPE OVERVIEW

Thermoplastic elastomers are unique synthetic compounds that combine some of the properties
of rubber with the processing advantages of thermoplastics. They consist of a number of
families, the majority of which are listed in TABLE I .

TABLE I

TPO'S This family of thermoplastic elastomers consists

of the polyolefin based elastomers. (EPDM) Ethylene
Propylene Diene Modified Rubber, (EPR) Ethylene
Propylene Rubber, (FPO) Flexible Polyolefin, and
(POE) Polyolefin Elastomer

SBC This family of thermoplastic elastomers consist

of styrenic block copolymer elastomers. SBS,
SEBS and SIS

TPV'S This family of thermoplastic elastomers consist

of elastomers where the rubber portion is fully
cured or partially cured.

TPU'S This family of thermoplastic elastomers consist

of polyurethane elastomers, polyester type and
polyether type.

COPE'S This family of thermoplastic elastomers consist

of copolyester type of elastomers.

COPA'S This family of thermoplastic elastomers consist

of copolyamide type of elastomers. PEBA

Like rubbers, the thermoplastic elastomers key properties are hardness and stiffness or
flexibility. The families overlap each other in these characteristics. The TPU'S, COPE'S and the
COPA'S offer the hardest and stiffest grades available, because of this they are sometimes
referred to as the engineering thermoplastic elastomers. This group is also the more expensive
group of thermoplastic elastomers and finds use in high end markets. (see Figure 1)

THE TPO FAMILY

The TPO family or thermoplastic polyolefin elastomers are comprised of various mechanical
blends of polyolefin resins. The components for these blends are readily available and are
relatively inexpensive. They have found application in less demanding large volume areas, such
as wire and cable jacketing, paintable automotive exterior trim and some automotive underhood
applications.

More recently a group of flexible polyolefins has been added to this group. They are sometimes
called the FPO'S or POE'S. These flexomers are made in-situ and unlike the physical blends
these materials come directly from the reactor ready to be extruded or molded, a number of
these the POE'S are based on metallocene catalyst technology. They have been finding
application in flexible packaging, resin modification, automotive trim, medical tubing and blood
bags.

THE SBC FAMILY

The SBC family or styrenic thermoplastic elastomers represent a class of elastomers introduced
in the mid 1960's. The most noted of the SBC elastomers are the SBS and the SEBS.

The SIS elastomers are also a member of this family. Styrenic thermoplastic elastomers obtain
their thermoplastic properties because of their structure. This is due to the multiphase
composition in which the phases are chemically bonded by block polymerization. In all cases at
least one phase is a styrenic polymer that is a hard phase at room temperature. The other
phase is a rubber-like material that is soft at room temperature. The proportion of the styrenic
phase controls the hardness and stiffness properties of this family. The greater the proportion of
the styrenic phase in this block copolymer, the harder and stiffer the product will be. The choice
of soft segment will control the chemical resistance and thermal properties. The polybutadiene
SBS and polyisoprene SIS have un-saturation present in their structures which will lead to
poorer chemical resistance and reduced thermal oxidative resistance. The poly(ethylene-
butylene) SEBS being saturated will exhibit better chemical resistance and be thermally more
stable.

SBC thermoplastic elastomers have found a wide range of use in a number of markets, medical,
footwear, sound deadening, automotive and wire and cable.

THE TPV FAMILY

The TPV family or elastomeric alloys are thermoplastic elastomers composed of mixtures of a
plastic and a rubber in which the rubber phase is cured or crosslinked. The plastic phase is
commonly a polyolefin most notably polypropylene. However it is possible to make TPV's with a
variety of thermoplastics. Some that have been used are nylon, SAN, ABS, acrylates,
polyesters, polycarbonates and styrene. The rubber phase is commonly an EPR or EPDM
rubber. Other rubbers that have been used are nitrile, SBR, polybutadiene, butyl and CPE.
The end product is produced during a dynamic vulcanization mixing process. In this case the
curing of the rubber phase occurs during the mastication with the thermoplastic resin. This
process gives a useful elastomeric alloy with properties of a cured rubber but has the
processing characteristics of a thermoplastic. It is important that the mixing be continuous
throughout the masticating step, or a thermoset material could result.

Markets for TPV's have been found in medical, wire and cable, automotive and mechanical
rubber goods.

THE TPU FAMILY

The TPU family or the thermoplastic polyurethane elastomers are made up of two types. The
polyester type and the polyether type. The polyester based TPU'S are generally characterized
as having better physical properties, oxidative stability and oil resistance. While the polyether
based TPU'S at a similar hardness will exhibit better low temperature properties, hydrolytic
stability and resistance to microbial attack. TPU's as a family are noted for their inherent
toughness providing outstanding abrasion resistance and tear resistance. They have found
application in automotive underhood, shoe sole, wire and cable jackets and more recently in
medical applications.

The applications in medical are one of the fastest growing market segments for TPU'S. Some
new aliphatic specialty grades have been developed for this market as well. The applications
here include cardiovascular catheters and vascular grafts. Other medical applications include
blood bags, I.V. sets and bioclusive dressings.

THE COPE FAMILY

The COPE family or thermoplastic polyester elastomers were first developed by DuPont in the
late 60's. They were marketed in 1972 under the trade name Hytrel. Since then a number of
manufactures have developed products that are part of this family. COPE'S are considered
engineering thermoplastic elastomers because of their unusual combination of strength,
elasticity and dynamic properties. They show a high degree of heat and chemical resistance as
well. The COPE'S have found application in fiber optic coatings, sporting goods, transportation
and industrial applications where the combination of mechanical properties and flexibility are
critical.

THE COPA FAMILY

The COPA family or polyether block amide elastomers are based on a block copolymer of nylon
12 and a polyether. Through the proper combination of polyamide and polyether blocks, a wide
range of grades that offer a variety of performance characteristics is possible. The family is
characterized by durometer and flexibility. The higher the durometer and stiffness the higher the
level of nylon 12 in the block co-polymer. COPA'S have been limited to niche markets do to their
cost. Areas where they have been extensively used are where long flex life is required, such as
air hose coils for the air brake systems on trucks. This is due, in part, to the high resilience and
low hysteresis of the polyether block amide. They are finding use in the medical market for
various types of catheters. Other niche use markets have been in sporting goods, pumps and
wire and cable jackets.
TABLE II

PROPERTY CHARACTERISTICS OF TPE'S

PROPERTY TPO'S SBC'S TPV'S TPU'S COPE'S COPA'S

Spg. 0.89-1.0 0.90-1.2 0.90-1.0 1.1-1.3 1.1-1.3 1.1-1.2

Hardness 60A-75D 30A-75D 40A-50D 70A-75D 40A-82D 75A-72D

COMP. SET P P G-E F-G F F-G

@ 100 C

HIGH-TEMP 120 100 135 135 160 150

Deg C

LOW-TEMP -60 -70 -60 -50 -65 -65

Deg C

FLUID REST. P P F-E F-E G-E G-E

COST ($/lB)

P = POOR F = FAIR G = GOOD E = EXCELLENT

HIGH PERFORMANCE TPES IN MEDICAL APPLICATIONS:

Out of all the available families of TPEs, only the polyurethane (TPU) and polyether block amide
(COPA) have the property balance to be successfully utilized in demanding medical applications
such as catheter tubing, balloons for catheters, films for wound dressings, surgical drapes,
storage bags, strain reliefs, etc. These materials offer a good balance of tensile strength,
toughness, elongation, kink-resistance, hydrolysis-resistance, and thermoplastic processability.
TPUs and COPAs are commonly used for short-term implants.

Medical Design engineers are constantly pushing the limits of these TPEs and are always
looking for ways to achieve even higher performance than what is currently available.
Engineers also want to narrow the specification tolerances, enabling their use in micro-precision
molding and thin wall extrusion processes. Basically, it doesn’t matter how good the material is,
if it can’t be processed with the required accuracy, it is still no good.

MODIFICATION OF TPES VIA FORMULATION AND SPECIALTY COMPOUNDING

Many of the high performance TPEs require some form of compounding or modification prior to
use in a medical device application. The addition of colors, radiopaque fillers, reinforcements,
lubricants, and process aids is common. Melt filtering to reduce gels and visual impurities as
well as melt homogenization and repelletizing to uniform small pellets is also quite popular.
Alloying TPEs to achieve enhanced performance is also catching on.
By melt compounding one or more additional polymers into a COPA elastomer, you can
effectively extend its performance range as shown in Figures 1 and 2.

COPAs and TPUs can be alloyed with a number of different resins; however, achieving the
exact property profile you need can be tricky business. The development of new blends is still
mostly a painstaking process of trial and error, even if using advanced statistical methods such
as Design of Experiments (DOE) and the like. Unless your budget and time permits, it is best to
evaluate proven blends first.

Another and more exciting way in which COPA elastomers have been modified to enhance
design properties is through crosslinking by either gamma or E-Beam irradiation.

Crosslinking of COPA addresses one of the main disadvantages of TPEs versus Vulcanized
(thermoset) rubber; temperature resistance. Figure 3 shows the hot creep temperature
performance of uncrosslinked COPA versus crosslinked versions. Crosslinking the COPA is
shown to have a significant effect upon elevated temperature performance, allowing the design
engineer to utilize a TPE in demanding high heat applications for the first time.

Crosslinking also increases stiffness (Figure 4), improves hydrolysis resistance, chemical
resistance, and reduces elongation.

The advantage of irradiation crosslinking a COPA elastomer is that it allows a design engineer
to fabricate the device using conventional thermoplastic processing methods and then adjust
the material properties in a post-processing operation. Many of the crosslinkable COPAs have
been designed to crosslink at radiation doses similar to sterilization doses; therefore,
accomplishing both tasks simultaneously.

SUMMARY:

Of all the thermoplastic elastomers available, only two families, the Polyurethanes (TPUs) and
the polyether block amide (COPA) demonstrate high performance design properties. Flexural
modulus, hardness and tensile strength may be enhanced by alloying COPA or TPU with one
or more polymers. Crosslinking COPA by gamma or E-Beam irradiation after processing is
shown to have a significant effect upon elevated temperature performance. Crosslinking also
imparts other characteristics of thermoset rubbers as well as increased stiffness with good kink
resistance.

REFERENCES:

1. Specialty Compounds for Medical Applications: An Introduction, L.A. Acquarulo, Medical

Plastics and Biomaterials, Sept. 1996.
2. High Performance Crosslinkable Thermoplastic Elastomers for Medical and Electronic
Applications, L.A. Acquarulo, C.J. O’Neil, Society of Plastics Engineers, Antec 1999, NY,
NY.
3. Plastics Failure Guide, Cause, & Prevention, Myer Ezrin, Hanser/Gardner Publications, Inc.,
Cincinnati, OH, 1996.
 COPA Alloys, Durometer Shore D

85

80

75

70

65
COPA 72D 5200 Fostalon 5400 Fostalon 5600 Fostalon 5800 Fostalon 5900 Fostalon Nylon 11 Nylon 12

Figure 1

COPA Alloys
Flexural Modulus
250000

200000

P 150000
S
I 100000

50000

0
COPA 72D 5200 Fostalon 5400 Fostalon 5600 Fostalon 5800 Fostalon 5900 Fostalon Nylon 11 Nylon 12

Figure 2
 Crosslinked COPA, Hot Creep Elongation
@ 200° C, 29 PSI

60
50 M
% of Elongation 40 E
30 L
20 T
10 E
0
D
Unmodified Lightly Moderately
COPA 72D Crosslinked Crosslinked
COPA 72D COPA 72D

Figure 3

Crosslinked COPA, Flexural Modulus

200,000
F
M
l
o 150,000
e
d
x
u
u 100,000
l
r
u
a
s 50,000
l

0
Unmodified Fostalink Nylon 12
COPA 72D FK17200XXA
Figure 4