14 Coupling and Compatibilizing
The modification of polyolefin resins with addi-
tives is not straightforward; the polyolefin matrix
itself is typically resistant to interacting with additives
in the ways desired by the formulator or end user.
After all, polyethylene (PE) and polypropylene (PP)
molecules are relatively nonpolar and chemically
inert and tend not to bond or interact with many addi-
tives or fiber or fillers, or with many other polymers.
Thus this chapter covers coupling and compa-
tibilization: the uses of various modifiers are make
polyolefins interact better with additives or other
materials for better properties. This chapter is orga-
nized by making distinctions between coupling
agents and compatibilizing chemistries and their
functions. The first section covers coupling agents
that promote the adhesion of fillers or fibers with
the polyolefin matrix; the second section covers
compatibilizing agents that help commingled and/or
degraded recycled polymers to be reappropriated
for reuse. The following questions are addressed:
• What additives are effective for coupling
polyolefins with fillers or reinforcements?
(Section 14.1)
• How can compatibilizing additives allow the
more efficient use of regrind and recycled
polyolefin content? (Section 14.2)
14.1 Coupling Fillers and Fibers
with the Polyolefin Matrix
Since most common fillers have no inherent
reactivity with inert, nonpolar polyolefins, reactive
dispersion aids and coupling agents are essential.
Without proper dispersion and bonding to the matrix,
fillers and fibers added to polyolefins are greatly
limited in improving a compound’s properties—or
they may even degrade essential properties, acting
simply as contaminants in the polymer. Many of
these dispersants and coupling agents have been
mentioned in previous chapters on fillers, fibers,
colorants, and processing aids.
Additives for Polyolefins. DOI: http://dx.doi.org/10.1016/B978-0-323-35884-2.00014-4
© 2015 Michael Tolinski, Published by Elsevier Inc.
To be effective, coupling agents must essen-
tially surround each filler particle and link the
particle to the polymer. Typically, filler and fiber
suppliers precoat their products with coupling
agents, somewhat making the coupling agent’s
important role less obvious to the end user. Agents
may also be added when mixing or extruding the
filled polymer compound. Here, they may help
increase throughput (like processing aid lubricants)
while also improving the dispersion/properties of
high pigment or filler loads (like high loadings of
mineral flame retardants or cheap CaCO3 or other
fillers). The selection of a coupling agent can have
an important effect on how well the filler is dis-
persed and bonded to the matrix, how much can be
incorporated, and on how easily the compounding/
converting process runs [14-1, 14-30].
14.1.1 Traditional Coupling
Agents
One traditional approach for coupling glass fiber
or wood cellulose fibers to polyolefins uses maleic
anhydride (MA) grafted to a polymer or copolymer
(g-MA) and mixed with the resin. This coupling
agent is made with a two-step process: a base
polymer (such as a polyolefin) is created in a reac-
tor, and then MA monomers are grafted onto its
polymer backbone. When the g-MA polymer is
added to the compound at just a few percent load-
ing, the polar functional groups of the MA bond
with hydroxyl groups on the fiber or filler surface,
while the polymeric part of the g-MA stays compat-
ible with the bulk polyolefin matrix. Grafted MA
coupling agents increase the physical properties of
fiber-filled compounds such as the bending elastic-
ity and density of HDPE wood-plastic composites
(WPCs). The improvement in properties is usually
proportional to the concentration of MA that is
grafted onto its polymer carrier [7-49, 14-3].
Grafted MA coupling agents have also been
effectively used for bonding long glass fiber to PP
in LF-PP composites loaded with 30 50% glass.
153
154 ADDITIVES FOR POLYOLEFINS

Here, the coupling agent concentration, glass
grade, melt flow of the PP, and processing fac-
tors create complicated relationships with the
resulting mechanical properties, as discussed in
Case 14.1 [14-7].
Organosilane coupling agents have also been
heavily used, especially for bonding nonorganic
siliceous fillers and fibers (such as talc, clay, and
glass), metals, and metal oxides to the polyolefin
matrix. Along with chemically coupling the outer
surface of the filler particles with the polyolefin,
silane agents, like MA, act as filler dispersants, pre-
venting filler agglomeration and allowing higher
filler loadings and properties. The silicon atoms in
silanes are bonded to “head” functional (alkoxy)
groups that bond (or adsorb) onto the filler parti-
cle’s surface chemistry. The silane’s silicon is also
bonded to a “tail” organic (alkyl) group that is
compatible with the polymer. Linking filler and
polymer, this structure lowers the filler’s surface
energy, improving its compatibility and wetting
with the low energy polyolefin. It also creates a
barrier that prevents a filler particle from bonding
with other filler particles. These mechanisms help
the silane serve as a coupling agent with high sur-
face energy fillers such as (from the most effective
coupling to least effective) silica, glass fiber, mica,
kaolin, wollastonite, aluminum trihydrate (ATH),
talc, titanium dioxide, calcium carbonate, and car-
bon black [8-14, 14-1, 14-31].

Case 14.1 Coupling Agents in Long Glass Fiber Polypropylene [14-7]

Problem: Some new LF-PP formulations are not yet optimized for costs and properties.
Objective: Determine how to minimize the costs of the expensive components in LF-PP, such as the
grafted MA coupling agent.
Solution: Better grades of glass fiber allow reduced coupling agent use.
Given the rapid growth of long glass fiber PP composites for structural applications in automotive and
other areas, there is interest in maximizing the influence of glass fiber on the mechanical properties of
the composite. Since the g-MA coupling agent is one of the most expensive components of LF-PP, one
goal is to maximize the effects of the glass with while minimizing the amount of coupling agent required.
Thus researchers from glass supplier PPG Industries studied various factors based on the coupling agent
and glass fiber in LF-PP, including key systems characteristics, such as melt flow of the PP resin and
processing method.
The PPG researchers compared various compositions of LF-PP. They studied homopolymer PP resins
with melt flow index (MFI) values from 5 to 100 and glass percentages of 30 50% (added as 17-micron
glass rovings pultruded with the PP and cut into pellets 12-mm long). They compared different grades of
glass fiber and also varied the coupling agent concentration from 0.5% to 3% in the study. The resulting
injection molded samples were then evaluated with a variety of mechanical tests.
The study revealed expected (and unexpected) trends:

• At high glass loadings, an increased concentration of coupling agent increases tensile strength, as
expected, but the properties are not increased above a plateau “saturation” concentration of g-MA
(at which point the glass fiber surfaces are completely covered with coupling agent).
• Heat deflection temperature increases with increased MFI. This perhaps “counterintuitive” trend may
be explained by the greater impregnation and wet out of the glass by the high-flow PP. (This wetting
out is said to reduce voids, allowing better load transfer between resin and fiber, as well as greater
retention of the original fiber length, which is typically reduced by fiber breakage during molding.)
• Modulus is not significantly affected by the coupling agent, but rather is controlled by fiber content
(and is ideally predicted by the traditional “rule of mixtures” law, in which the composite modulus is
simply a weighted volume average of the moduli of the composite’s matrix and reinforcement).
• Higher MA content in the coupling agent can increase composite properties, enabling perhaps less
overall use of coupling agent and thus less cost.
• Glass fiber grades with modified chemistries (such as PPG’s TufRov 4576) allow higher composite
properties—and thus potentially require lower amounts of coupling agent.
14: COUPLING AND COMPATIBILIZING
14.1.2 Alternative Coupling
Agents
Since silane agents are less effective with coupling
lower energy carbon black and CaCO3, other agents
may be tried. For coupling these fillers, organome-
tallic complexes based on “neoalkoxy” titanates
and zirconates have been used as coupling agents.
These complexes contain oxygen groups that are
reactive with surface protons (H1) found on most
common fillers, unlike silanes which require
hydroxyl (OH2) groups on a filler’s surface and the
presence of water (under 100°C) to be most effec-
tive. These agents are molecular complexes whose
Ti O or Zr O bonds and other catalytic functional
groups are said to have a strengthening, “repoly-
merizing” effect on the polymer (to be discussed
more in the following section) The agent improves
properties in compounds such as talc-filled PP,
where a titanate coupling agent was found to
decrease melt viscosity, improve dispersion, and
improve mechanical properties. Or, in a highly
filled 60% ATH flame-retardant compound, a tita-
nate reportedly was found to increase flow and
impact strength. The Ti/Zr coupling agents can be
coated on filler particles or are available in master-
batch or other forms that match the resin’s form for
proper mixing with the polymer [14-2].
14.1.3 Coupling Agents: Special
Situations
For WPC processing, improved coupling agent
technologies focus on strengthening the connection
between the polyolefin and wood or natural cellu-
lose fiber, providing stronger products for the
construction industry. For example, Clariant offers
a coupling agent (Licocene PP MA 6452 TP) com-
posed of a metallocene-catalyzed polypropylene
wax grafted with MA, which reportedly is a more
precisely controlled product offering better perfor-
mance. Other alternatives to traditional g-MA
agents are said to improve dispersion, resulting in
higher strength properties and lower absorption.
DuPont offers a reactor produced ethylene/MA
copolymer, which contains higher levels of anhy-
dride than in grafted MA. The product, designated
Fusabond W PC-576D, is said to increase bending
modulus of elasticity and density more than an
LLDPE-g-MA, when added in HDPE board with
60% pine fiber and 5% untreated talc. Water
155
absorption with the product is also noticeably less
than with g-MA (at 2% loadings and higher),
reducing the potential of rot or mold growth [7-49,
14-3, 14-4, 14-5].
Even more complex recipes for coupling fibers in
WPCs have been studied. For example, in one study,
MA grafted onto a styrene ethylene butylene
styrene block copolymer (SEBS-g-MA) was added at
1%, along with 2% PP-g-MA, in a WPC system. This
reportedly doubled the impact strength over PP-g-MA
alone, though it reduced the modulus. However,
when researchers used a WPC that was also loaded
with nanoclay (1 5%), the SEBS-g-MA likewise
increased impact strength, but the nanoclay helped
support the modulus value [14-6].
Silane coupling/crosslinking agents have also
shown some effectiveness with wood- and/or natu-
ral fiber composites. One study has suggested that a
silane-treated composite had higher tensile strength
and lower water absorption and better other pro-
perties than a corresponding g-MA/PP wood-
fiber composite. Silane-based agents have come
available from Dow Corning for bonding PP with
natural fibers as well as glass fibers. In compound-
ing, the liquid products are injected right before the
addition of the fibers [14-28, 14-31].
With nanocomposites, there is likewise a drive
to determine the best coupling agents. With a PP
nanocomposite made with cellulose nanofibrils, the
situation is analogous to WPCs: adding PP-g-MA
can improve tensile, flexural, and impact properties
of the nanocomposite [14-29].
With nanoclay nanocomposites, agents are needed
that best help exfoliate and disperse nanoclay parti-
cles, thus increasing the composite’s properties and
expanding these materials into new applications. PP-
g-MA has been used, and, in one study, has shown
some effectiveness especially when combined with a
“hyperbranched” polyester terminated with hydroxyl
groups that aid dispersion [14-32].
But nanoclay exfoliation has been achieved
mainly with surfactants like charged quaternary
ammonium compounds (quats). Nanoclay is typi-
cally exfoliated in a water slurry with a high per-
centage of an ammonium quat before incorporation
with the polymer. However, the high percentage of
ammonium quat required for exfoliation reportedly
creates compatibility problems with polyolefins.
Alternatively, research from Kenrich Petrochemicals
argues that instead of ammonium quats, a much
lower percentage of a titanate quat coupling agent
156
should be used in the wet slurry or in the polymer
system. This effectively exfoliates nanoclay by cre-
ating a monolayer on each clay nanoparticle. It does
not create polyolefin compatibility problems, but
instead is said to enhance many polymer properties
through its catalytic effects on the polymer [14-8].
14.2 Compatibilizers
for Integrating Regrind
and Recycled Materials
For most operations that handle polyolefins, the
reprocessing of in-house scrap material is a “no-
brainer,” when it is permitted by the application.
Recycling regrind keeps costs as low as possible, as
well as allowing a company to consider itself more
environmentally sustainable. Purchasing and reus-
ing postindustrial or postconsumer polyolefins can
be a more difficult matter. And in recent years,
more mixed polymer streams of recycled materials
have come online, creating a need for better
approaches for compatibilizing these materials to
reuse them [14-31].
There is usually no shortage of recycled mate-
rial. Among all the resins that recyclers buy and
sell, polyolefins, including HDPE, PP, LLDPE,
and LDPE, have the largest shares. And postcon-
sumer polyolefins, particularly HDPE, are flooding
the marketplace (with over 40% of all bottles
that are recycled being made from HDPE, even
though ,40% of all bottles produced are HDPE).
Also, the highest rate of postconsumer plastic
bottles collected for recycling is for bottles made
from HDPE, ahead of PET. But the costs to collect
and reprocess postconsumer materials are high, and
the overall prices and quality of these external
recycled materials are unstable, sometimes making
their reuse hard to justify [14-9, 14-10, 14-26].
Whether using scrap produced internally or
recycled material from outside the operation, inte-
grating recycled material with virgin material and
creating quality output is not easy, for several
reasons:
• Though all grouped under the generic term
“commodity polyolefins,” polyethylene, LDPE,
and other polyolefins typically are relatively
immiscible with each other and do not always
process efficiently as blends.
ADDITIVES FOR POLYOLEFINS
• Even when the polyolefin families and colors
match, and the recyclate is free of contami-
nation, the average molecular weight distribu-
tion and MFI of different lots can vary wildly
(and be generally reduced by degradation
during service). Additives such as peroxides
in masterbatch form have been proposed
as means for making the melt properties of
mixed polyolefin recyclate streams more
homogenous.
• Different levels of copolymers, modifiers, or
other additives in the recycled material can
frustrate those who try to combine various
sources of scrap and produce a quality product.
• Because the recycled material may have
partially degraded after going through repeated
processing cycles and heat histories, the
allowed recycled content is typically limited to
30% or less in visually sensitive functional
products. Even when different polymers or
grades can be blended or used in different
layers of a multilayer product, maximizing the
recycled content of a product may require
changing the gauge thickness or part design to
accommodate for the reduced mechanical
properties of the blend. (It also should be
noted that recycled polyolefins with degraded
properties can be upgraded to useful purposes
simply by adding the functional fillers and
reinforcements covered in Chapters 7 and 8.)
• Moreover, certain additives that were originally
added to the regrind material may have since
been consumed or lost (especially heat stabili-
zers or migratory agents like antistats or proces-
sing lubricants); thus, high additions of these
additives in the virgin/recyclate blend may be
needed in compensation.
In other words, regrind or recycled material
might often be thought of as an additive that unpre-
dictably degrades the properties of virgin material,
rather than enhancing them. But such obstacles are
being overcome to allow more recycled content use
in more polyolefin applications, including durable
automotive parts (Case 14.2) [3-4, 14-12, 14-27].
For polyethylene in particular, the charac-
teristics of recycled off-spec or wide-spec grade
materials that are available may vary greatly. These
materials are often difficult to fit into the relatively
narrow processing windows of extrusion, blow
14: COUPLING AND COMPATIBILIZING 157

Case 14.2 Recycled TPO in Automotive Moldings [14-16, 14-17]

Problem: More recycled plastic content is desired in automotive components.

Objective: Determine how to cost-effectively increase the recycled content in durable moldings.
Solution: Automotive panels made from TPO recycled from discarded moldings or postconsumer PP.
For cutting costs while improving their “green” image, automakers are seeking new ways of
incorporating recycled plastic content in new vehicles. In one application, General Motors, resin supplier
MRC Polymers Inc., and molder NylonCraft Inc. determined how they could use TPO from recycled
bumper fascia in the new air-intake (cowl) molding for GMT360 sport utility vehicles. (This molding is the
long black part located between the hood and the windshield.)
One of the keys to the application was a process that removes paint from the scrap fascia moldings so
that it does not contaminate the cowl molding. The material supplier used a proprietary water-based
process to remove the paint.
The recycled TPO met color and weatherability requirements, and was molded using the same tooling
as virgin TPO. It also created a minor cost savings, along with saving hundreds of thousands of kilograms
of fascia TPO that would otherwise end up in landfills.
In another development, postconsumer recycled PP was used in the TPO underbody moldings of the
Ford Flex vehicle. Supplier Flex-n-Gate supplied about 9 kg of the material per vehicle for use in splash
shields, spoilers, and radiator air deflectors. The material had to be compounded with additives to improve
its UV stability and impact strength. However, because the cost of recycled material is not tied to
petroleum prices, the supplier said that significant cost savings were possible.

molding, or injection molding. Extrusion and blow
molding processes require PE with melt indices
from 0.05 to 1, typically, while injection and
rotational molding require 5 100 melt index PE.
Recycled materials may be identified by melt index
and density, but unfortunately, the melt index may
be stated inaccurately by the source, and the mate-
rial may contain unknown fillers or colorants that
affect its modulus and processing. All these issues
increase the potential for downtime and increased
scrap, thus reducing the motivation for using scrap
at all [14-11].
But additives that compatibilize different compo-
nents in a blend can make recycling more efficient.
Coupling agents can improve melt flow, processing,
and final properties. These additives offer conver-
ters more flexibility and options for controlling
and reusing material, rather than relying on outside
brokers or recycler/distributors to provide the right
grade of material at the right time. (And as recent
history shows, these businesses themselves are sub-
ject to economic cycles and radical swings in resin
prices, which influence what high-quality scrap
they can provide.)
When used as compatibilizers in polyolefin
regrind blends, MA-grafted polymer coupling agents
and other modifiers chemically unite ingredients in
the blend, producing higher properties and allowing
more recyclate to be included. Compatibilizers
can improve the properties of recycled feedstreams
that contain common ingredients normally found
in PE. These “contaminants” may include zinc stea-
rate lubricants, ethylene vinyl alcohol copolymer
(EVOH) packaging barrier resin, and water. Some
compatibilizing modifiers are effective at low load-
ings for improving properties of these blends and for
reducing die buildup. For example, DuPont’s
Fusabond E EC-603D copolymer modifier is said to
improve notched Izod impact strength at 0.5% load-
ing in PE containing 2% zinc stearate, 9% EVOH,
and moisture [14-14].
PP and PE have been successfully recycled
together into materials with high properties, despite
their incompatibility. Work by Dow Chemical
has shown that olefin block copolymers added as
compatibilizers can “stitch” together PP and PE
polymer phases. The soft block segment of the
copolymer is said to be miscible and compatible
with the PP, and the hard segment is miscible with
HDPE. In one study, a random ethylene octene
copolymer, Dow’s Affinity elastomer, was used as
the compatibilizer at 7% net loading in a 63% PP/
30% HDPE blend. The tensile strength in the com-
patibilized blend reported more than doubled, and
the elongation increased by over six times, com-
pared with the uncompatibilized blend. DuPont has
158
released its own ethylene copolymer compatibilizer
(Entira EP) for compounding PP with PE together,
requiring about 4% loading [14-13, 14-31].
Titanate and zirconate coupling agents have also
been used to compatibilize PP and PE to create
useful products that contain more recyclate. For
example, a titanate reportedly created a useful 80%
LDPE, 20% PP regrind blend, enhanced by the
catalytic “repolymerizing” effect of the additive,
re-building the polymer’s molecular weight. Useful
50/50 PE/PP blends with coupling agents have also
been suggested as possible, with very high
proportions of regrind in a product. In an HDPE
blow-molded toy application, 0.2% loading of a
zirconate agent, added within a color concentrate,
allowed the amount of regrind in the product to
increase from 50% to 80%, while reducing cycle
time, process temperature, and part weight [13-15,
14-2, 14-30].
Other additives supporting recycling allow
mixed polymer scrap material downstream to
be more easily reused. For example, mostly PE
blow-molded containers often contain layers of
polyamide and/or ethylene vinyl alcohol barrier
ADDITIVES FOR POLYOLEFINS
polymers. A grade of g-MA polyolefin copolymer
(Fusabond from DuPont) has been proposed as a
way of linking PE with the normally immiscible
PA/EVOH in scrap bottles to obtain usable recycled
material that can be used as a structural layer in
products [14-30].
One more, much different approach for using
an additive to recycle mixed polymer scrap con-
cerns material sorting. Eriez Magnetics’ PolyMag
additive is said to aid in the sorting of mixed
scrap polymer streams using an additive that
changes the magnetic properties of one of the
streams of material, when it is used in that mate-
rial. This makes the material identifiable by
specialized automated sorting equipment. Such an
approach may be useful for operations that pro-
duce multilayer or overmolded parts with streams
of multiple grades of material, which inevitably
cross-contaminate when they become scrap. For
example, in a pulverized stream of scrap from a
multilayer HDPE blow molding operation, the
system reportedly even separated EVOH barrier
resin containing the magnetic additive from the
HDPE regrind [14-15].