CHAPTER 13

Modifying Processing Characteristics: Couplings Compatibilizing Agents

Coupling agents may have a significant influence on mechanical properties,

including impact strength, by acting as molecular 'bridges' chemically formed at
the interface between two substrates, such as an inorganic fibre or filler and an
organic polymer matrix, to improve the bond between the two. The Coupling
Agent Index (Intertech) identifies six main types:

• Organosilanes
• Organozircoaluminates
• Chartwell adhesion promoters
• Functionalized organic polymers
• Organotitanates
• Organozirconates

Organosilanes have long been used to improve the chemical bond between a
variety of thermosetting resins and glass fibre and other silaceous surfaces, but
they are essentially non-functional with organic-based fibres, such as graphite
or aramid.
Organometallic coupling agents, based on titanium or zirconium, offer a wider
compatibility, in glass fibre-reinforced composites with epoxy and polyester and
in aramid- and carbon-reinforced composites with epoxy, polyurethane, and
vinyl ester. Significant improvements in wetting out and bonding and in the
chemical resistance of thermosetting systems have been gained by, respectively,
use of 0.2% aromatic aminozirconate with epoxy resin and an aromatic
aminotitanate with a vinyl ester, using silane-sized glass in both cases. Improved
process rheology has also been shown in thermoplastic matrices such as
reinforced polyphenylene sulphide and polycarbonate.
In thermoplastics, the organometallics appear mainly to provide a catalytic
support bed for in situ re-polymerization of the polymer matrix, which reflects
itself in improved processing. A test on a 40% polycarbonate/glass compound
showed improvements in mechanical properties, together with significant
improvements in productivity.
Titanium-derived coupling agents are unique in that, by reacting with free
protons at the inorganic interface, organic monomolecular layers are formed on
168 Additives for Plastics Handbook

the inorganic surface. Titanate-treated inorganics tend to be hydrophobic,

organophilic, and organo-functional. When incorporated into polymer systems
they can improve impact strength, promote adhesion, catalyse, and improve
dispersion and rheology. They do not create embrittlement but can improve
mechanical properties and make inorganic loadings of about 50% desirable,
preventing phase separation and inhibiting corrosion.
The use of organotitanate and/or organozirconate coupling agents, either
independently or optionally together with other surface-reactive materials, such
as organosilanes, also significantly improves the properties and processability of
fibre-reinforced polymers, and their resistance to chemical attack and corrosion.
Zirconate coupling agents provide a functional equivalent alternative to the
silanes and titanates, correcting some of their disadvantages. They do not
interact with hindered amines (HALS, used as light stabilizers and/or anti-
oxidants) and, in unfilled plastics, they often improve ultraviolet stability,
compared with titanates. Recent manufacturing improvement has reduced the
original high cost.

Table 13.1 At a glance: coupling, compatibilizing agents

Function To form chemical linkages between molecules that are normally

Properties affected
Materials/characteristics
Disadvantages
New developments
incompatible
Mechanical strength, processability
Organosilanes, adhesion promoters, functionalized organic polymers,
organotitanates, zirconates
Complex chemistry, only partly understood
Could be significant in creating new polymer systems and making useful
polymers from recovered waste

13.1 New Developments

Two additions to its range of polymer modifiers have been introduced by

Uniroyal Chemical, in its Polybond chemically modified polyolefins and Royaltuf
modified ethylene/propylene terpolymer (EPDM) elastomers. Polybond 3109 is
for polyolefins to improve the bonding between the non-polar resins and fillers
and reinforcements such as glass, wood flour, and non-halogenated flame
retardants. Produced from linear low-density polyethylene, functionalized with
1% grafted maleic anhydride, it has a melt flow index of 30 (six times higher than
Polybond 3009), giving easier mixing and better performance.
Royaltuf 498 is designed for nylon 6 resins, giving better impact resistance at
low temperature. It is produced from EPDM, functionalized with 1% maleic, and
has a Mooney viscosity of 30. Applications include housings for hand-held
power tools and sporting goods.