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5

Toughening agents for engineering


polymers
H. Keskkula and D. R. Paul

5.1 INTRODUCTION
Most plastics designed for engineering applications are multi phase materials
that contain elastomeric impact modifiers and often other polymers. The
addition of toughening agents usually increases the overall ductility of the
polymer over a wide temperature range but also improves resistance to notch
sensitivity and toughness of thick sections, reduces water absorption, etc. As
more knowledge of miscibility, compatibility and interaction of polymers has
become available in recent years, more varied approaches to improved poly-
mer blends have become apparent. Simultaneous with this, there has been an
explosion of activity in the field of toughened engineering plastics. Many new
tough polymer blends based on polyamides, poly(phenylene oxide) (PPO),
polyesters and polycarbonates (PCs) have been introduced in large volume
applications, particularly in the automotive industry [1].
The manufacture of engineering polymer blends grew tremendously in the
1980s. Before 1980, blend technology leading to engineering polymers was
essentially unknown on a commercial basis [2-5], except, of course, for blends
of PPO with high impact polystyrene that were introduced in the late 1960s by
General Electric Company under the trademark Noryl@. Recently, a number
ofmulticomponent engineering polymers that contain impact modifiers have
been introduced. The world-wide patent activity of compositions useful for
such applications has been explosive. Hundreds of patents on the modification
of polyamides alone have been issued during the 1980s. It is clear that the
growth of rubber toughened engineering plastics will continue at a very high
rate involving many combinations of polymers. Table 5.1 shows the growth of
engineering polymers in the 1980s.
Alloys and blends involving combinations of various engineering polymers
designed for improved heat deformation characteristics, rigidity, solvent
resistance and toughness will be the main area for significant growth. Such

A. A. Collyer (ed.), Rubber Toughened Engineering Plastics


© Chapman & Hall 1994
Background 137
Table 5.1 US sales of engineering polymers*
Sales for the following years
( x 106 tons)t
Percentage
Polymer 1981 1985 1989 increase since 1981
-----_._---
Thermoplastic polyesters 0.56 0.65 0.96 71
ABS 0.44 0.48 0.57 30
Polycarbonate 0.11 0.13 0.28 155
Nylon 0.13 0.18 0.27 108
Epoxy 0.15 0.16 0.22 47
PPO and copolymers 0.06 0.08 0.08 33
Polyacetal 0.04 0.05 0.06 50

* Data from Modern Plastics, January issues.


t Tons are long tons; 1 ton ~ 1000 kg.

blends are expected to account for approximately 160000 tons of engineering


thermoplastic consumption in the US for 1990 [6]. As seen from Table 5.1, this
is a significant percentage of the combined US sales of nylon, PC and PPO
(630000 tons in 1989).
In this chapter, the general synthetic methods and description of impact
modifiers used in engineering polymers will be reviewed, as well as some
specific uses in various polymer blends. However, because of the very large
number of possibilities, the impact modifiers for combinations of engineering
polymers, e.g. nylon- PPO [2,7], PC-polyester [2], will not be covered in
detail, since many impact modifiers described for a specific polymer are often
used for such blends.

5.2 BACKGROUND

5.2.1 Historical
Acrylonitrile, butadiene, styrene or ABS materials, developed in the 1950s,
were the first family of rubber toughened polymers that were useful for
engineering applications. ABS polymers have an excellent balance of strength,
rigidity and toughness, but they are deficient in some critical properties such as
heat deformation temperature and resistance to solvent attack. These defi-
ciencies have limited their use in many applications. Styrene-acrylonitrile
grafted rubbers such as those that give ductility to the SAN matrix in ABS are
widely used as components to enhance toughness in a number of modern
engineering polymer systems.
Blends of poly(phenylene oxide) and high impact polystyrene (HIPS) were
introduced in the late 1960s by the General Electric Company under the
Noryl® trademark. These products were useful in many applications that
required high heat deformation temperature, mechanical strength and tough-

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