Novel Processing Aids in Extrusion

The Use of Thermoplastic The Use of Thermoplastic Elastomers Elastomers as Novel as Novel
Processing Aids in Extrusion of Polyethylene Processing Aids in Extrusion of Polyethylene
M.H. Wagner
1
, M. Mller
1
, O. Kulikow
2
, K. Hornung
2
1
Technische Universitt Berlin, Polymertechnik/-physik
2
Universitt der Bundeswehr der Mnchen, Luft- und Raumfahrttechnik
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Outline
Introduction
Motivation
Background
Additives
Mode of action
Benefits
Outlook
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Motivation
Polyolefins (Polyethylene, Polypropylene and copolymers) are the
world's fastest growing polymer family:
Cost / performance: modern polyolefins cost less to produce and
process than many other plastics. In addition, continuous improvement
in strength and durability enables manufacturers to use less of them.
Extremely low environmental impact: The processes that are used
to produce them are considered to be the cleanest and most efficient in
the industry. At the end of their useful life polyolefins are inert products
that lend themselves to a multitude of safe, efficient waste disposal
processes, including recycling.
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Metallocene Polyethylene
mPE is a new development which is of special interest because of
narrow molar mass distribution:
Polyethylene made from metallocene catalysts is tougher, stronger and
cleaner than resin made from conventional catalysts
The film manufactured with metallocene PE offers downgauging
opportunities to reduce costs and environmental pollution
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Problems with Polyethylene
LLDPE and metallocene PE are
especially subject to various
flow instabilities (so called melt
fracture) during extrusion and
blown film production.
LDPE low density polyethylene
LLDPE linear low density PE
m-LLDPE metallocene PE
Ref.:ExxonMobil
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Appearance of melt-fracture during extrusion
Extrusion at 165 C
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Mechanism of sharkskin
Strain stress near the die rim.
Swelling of the extrudate.
Eruptive detachment of molten
polymer from the die exit.
detachment
point oscillates
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The use of Polymer Processing Aids
Aim
By postponing the onset of these instabilities to higher rate it becomes
possible to enhance both the processing efficiency and the final
product quality
Solution
A solution for a better processability of LLDPE and m-PE is the use of
Polymer Processing Aids (PPA), i.e. additives designed to improve the
processing of polymers
A typical amount of PPA is 500 to 1,000 ppm
Market size for PPA nowadays is 100 Mio Euro per year and it is
increasing
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Available Polymer Processing Aids (PPA)
Available PPA on the market are mostly fluorinated:
"Viton

FreeFlow" - DuPont,
"Dynamar

" - Dyneon (3M),

"Kynar

" - Atofina Chemicals,

"Metablen A" - Mitsubishi Rayon Co., Ltd.
Disadvantages:
Expensive
Environmentally harmful
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Alternative Polymer Processing Aids
Use of < 500 ppm of thermoplastic elastomers (TPE-U) based on block
copolymers of diisocyanates, i.e. urethanes and polyols
Elastollan" Elastogran
Baymod Bayer

Use of < 500 ppm Silicone Elastomers
TPSE Wacker Chemie

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Action of processing aids
Traditional (fluorinated) PPA
Molecules of fluorinated PPA flow along the wall
Conception is based on the use of materials with low surface energy
(lubrication layer)
Novel PPA (TPE-U)
TPE-U are immiscible with PE resins but adhere well to metals and
oxides
Molecules of novel PPA are strongly bonded to the die wall
The additives accumulated at the wall (coating of the die) slowly flow
along the wall to the exit of the extrusion die so that the product surface
is enriched by the additives.
Hypothesis: Polyethylene slips on PPA-film
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Extrusion (film blowing)
outside appearance as
result of film blowing of
m-LLDPE
Comparison of film
processed with and
without novel PPA at
the same processing
velocity
Results: less opacity,
less pressure at the
die exit
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Appearance of flow instabilities during extrusion
Extrusion of m-PE-LLD at 165 C
averaged product velocity [mm/s]
p
r
e
s
s
u
r
e
[
b
a
r
]
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Extrusion with additive (postponing of flow instabilities)
Extrusion of m-PE-LLD & Baymod at 165 C
p
r
e
s
s
u
r
e
[
b
a
r
]
averaged product velocity [mm/s]
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Benefits of novel PPA
Delay of melt flow instabilities
Faster extrusion (increase in processing velocity)
Positive impact on printability and adhesion (presence of polar
molecules at the product surface)
TPE-U which is entrapped inside a PE film also acts as an antiblocking
agent
Cheaper then traditional additives
Lower environmental impact
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Outlook
TPE-U and TPSE offer a great potential to substitute fluorinated PPA
because of their additional benefits
Challenge and potential for optimizing:
choosing the right Polymer Processing Aid (PPA) for a particular
application (e.g. regarding FDA compliance or stability under heating)
Research has to be done to understand the specific mode of action and
physical origin how the sharkskin effect is postponed to a higher
processing velocity
Thank you
for your attention!