DSP36042_sppp.

qxd 10/2/06 11:35 AM Page 1

Specialty Elastomers from Dow

White Paper
Blow Molding TPOs with High Melt Strength Polyolefin Elastomers

Introduction As seen in Figure 2, ENGAGE 8150 has the lowest extensional

As the trend in blow molding toward larger and more complex
parts continues, there is an increased need for materials with the
combination of high melt strength for sag resistance and good
extensibility for high blow-up ratios. This is especially true for
processors of polypropylene (PP) and thermoplastic polyolefins
(TPOs). While these materials have very good extensional
properties, they are notorious for having poor sag resistance.
Therefore, their use has been limited to relatively small parts
(< 2 liters) and applications.
viscosity and flat response of viscosity with increasing strain. In
contrast, ENGAGE ENR 7086.01 and ENGAGE 7387 have very
similar extensional viscosities with extensional viscosity rising
with increasing strain levels. Finally, ENGAGE ENR 6386.00, the
product with the highest level of LCB, has the highest extensional
viscosity increase.
Figure 1: Comparison of Clarity Differences
Between HDPE and PP Blow Molded Bottles.

Processors of larger parts who are attracted to the relatively low

cost, reduced weight, high fill temperatures, clarity (see Figure 1),
higher modulus, enhanced impact (TPOs) and post-process
recyclability advantages of PP and TPO have had to resort to
other, often more expensive, processes or materials.

However, the incorporation of long chain branching (LCB) into

polyolefin elastomers (POEs) can improve the melt strength of
polymers, opening the door for the use of PP and TPOs in
larger parts.

The Effect of Higher LCB Levels

in POEs and PPs
Figure 2: Extensional Viscosity Behavior of
Long chain branching provides additional entanglements which
Polyolefin Elastomers
increase the extensional viscosity of the polymer as shown in
ENGAGE 8150 ENR 6386.00 ENGAGE 7387
Figure 2. Using proprietary catalyst and reactor technology, The ENR 7086.01

7,000,000
Dow Chemical Company has developed a series of materials that 190C, 0.1s-1

demonstrate the improved sag resistance achieved when high 6,000,000

levels of LCB are incorporated into polyolefin elastomers.

Extensional Viscosity (Poise)

5,000,000

Comparison of POEs shows the effect of higher levels of long chain 4,000,000

branching on material viscosity. ENGAGE 8150 is an ethylene- 3,000,000

octene polyolefin elastomer with low levels of LCB while ENGAGE

2,000,000
ENR 7086.01 and ENGAGE 7387 are ethylene-butene elastomers
with high levels of LCB and ENGAGE ENR 6386.00 is an ethylene- 1,000,000

propylene product with the highest level of branching. INSPIRE D

0
114.00 is a developmental PP material containing high levels of 0.000 0.500 1.000 1.5000 2.000 2.500 3.000 3.500 4.000 4.500

He nc ky Stra in (cm /cm )

LCB. Typical properties for these materials are shown in Table 1.

Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow.

DSP36042_sppp.qxd 10/2/06 11:35 AM Page 2

Long chain branching in PP is typically developed by lightly cross- Figure 3: Extensional Viscosity Behavior of Polypropylene
linking the PP in a post reactor process. As was the case for the h-PP D 114.00

polyolefin elastomers, higher levels of LCB results in higher melt 3,500,000

230C, 0.1s-1
strength as shown in Figure 3. Here the extensional viscosity of the 3,000,000

developmental PP, INSPIRE D 114.00, which contains high levels

Extensional Viscosity (Poise)

2,500,000
of LCB, is compared to a conventional homopolymer PP (h-PP). The
higher extensional viscosity and strain hardening characteristics 2,000,000

for INSPIRE D 114.00 compared to the h-PP is obvious. 1,500,000

For hard TPOs applications the POE content is typically 10-30 wt.% 1,000,000

of the total polymer content depending upon the impact require-

500,000
ments of the applications. In these applications the lower density
ENGAGE 7387 and ENGAGE ENR 6386.00 products can act as 0
0.000 0.500 1.000 1.5000 2.000 2.500 3.000 3.500

modifiers that enhance both low temperature (-30C) impact and He nc ky Stra in (cm /cm )

melt strength performance of the TPO. The refractive index of

ENGAGE ENR 7086.01 is similar to that of PP. As such, ENGAGE
ENR 7086.01 can be used as a temperature impact modifier and
melt strength enhancer in blends in which clarity is important.
For soft TPO applications, the POE is the majority component being
used at levels between 60-80 wt.%. In these applications the PP is
present primarily to help increase the upper service temperature of
the compound.
Compounding
Mixing with a twin screw extruder typically provides the best
formulation results. This is especially true if there are large
mismatches between the viscosity of the PP and the POE. However,
if the PP and POE are well matched, good results can be obtained
using internal batch mixers and other standard compounding. For
simple blends with low levels of fillers and additives or none at
all, compounding can also be done in a single screw extruder,
provided a mixing screw is used or the extruder utilizes a static
mixing device.

Table 1: Typical Properties for Polyolefin Elastomers and Polypropylene

Density Melt Index 190C, DSC, Tm (C) Flexural Modulus

(g/cm3) 2.16 kg (dg/min) (MPa)
ENGAGE 8150 0.868 0.5 55 11
ENGAGE ENR 7086.01 0.901 <0.5 93 75.3
ENGAGE 7387

0.870 <0.5 48 11.5
ENGAGE ENR 6386.00 0.875 <0.2 55 22.0
INSPIRE D 114.00

0.900 0.5* 164 1483
Conventional h-PP 0.900 1.9* 160 1300
*230C, 2.16 kg

Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow.

DSP36042_sppp.qxd 10/2/06 11:35 AM Page 3

Figure 4: Demonstrative Parison Sag Curves Blow Molding Results

Low Melt Strength High Melt Strength No Sag
125
In order to test the sag resistance of the POEs and TPOs made
with them, a Battenfeld FHB-106-2S blow molder with a 60mm
100 single screw extruder and a Maddox mixing screw was modified to
measure the position of the tip of the extruded parison with time.
Parison Tip Position (cm)

75 A series of laser switches was placed approximately 10 cm apart

down the length of the extrusion path. These switches were
50 interfaced with a timer in a computer. As the tip of the parison
makes its way down the path, the light path of a laser beam is cut,
25 stopping its associated timer. Thus, the position of the parison tip
can be plotted as a function of time (see Figure 4). If the polymer is
0
0 25 50 75 100 125
completely resistant to gravity, there will be no sag and the data
T im e (s) will follow a straight line. However, most polymers will sag and
deviate from straight line behavior. The higher the melt strength of
the polymer, the straighter its behavior will appear.
Figure 5: Comparison of Parison Sag Performance of
Various Polyolefins Adding high melt strength POEs to h-PP can enhance the melt
h-PP 30% Conv. EB 30% ENR 6386.00
strength behavior as shown in Figure 5. The addition of 30 wt.%
140 of a conventional ethylene-butene polyolefin elastomer marginally
120
improves the melt strength of the h-PP by about 2-3 seconds.
However, adding 30 wt% of ENGAGE ENR 6386.00 greatly
100
improves the sag resistance by as much as 15 seconds.
Sensor Position (cm)

80
Even greater improvements in sag resistance can be achieved by
60
combining high melt strength elastomers with a branched PP, such
40
as INSPIRE D 114.00 as shown in Figure 6. Using the branched PP
improves sag resistance by as much as 30 seconds.
20

0
0 10 20 30 40 50 60

D ro p T im e (s)

Figure 6: Comparison of Parison Sag Resistance of h-PP to

Branched PP Compositions
h-PP b-PP b-PP/ENR 7086.01 70/30
140

120

100
Sensor Position (cm)

80

60

40

20

0
0 10 20 30 40 50 60 70 80 90

D ro p T im e (s)

Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow.

DSP36042_sppp.qxd 10/2/06 11:35 AM Page 4

The improvement in sag resistance permits larger parts to be Figure 7: Hydraulic Lift Cover Blown From 100%
blown. The hydraulic lift cover shown in Figure 7 was blown using ENGAGE ENR 7086.01
ENGAGE ENR 7086.01 and is approximately 45 cm long with a
weight of 1100 g.

The dog-bone part shown in Figures 8 and 9 is an excellent

example of the ability to blow mold soft TPO formulations. This
demonstration part uses an elastomer rich formulation of
ENGAGE ENR 6386.00 with INSPIRE D 114.00. Not only was
the part readily blown but it picked up the details of the grained
surfaces very well, Figure 9.

Summary
New high melt strength POEs can provide dual functionality to
blow molders by acting as both an impact modifier and as a melt Figure 8: Soft TPO Dog-Bone Part, ENGAGE
strength enhancer. This gives processors the opportunity to use ENR 6386.00/D-114.00, 70/30
TPOs in larger more complex parts than in the past and to take
advantage of the attractive modulus, clarity, higher fill
temperatures and impact properties of PP and TPO compounds.

To Learn More
The global sales, technical and customer service team behind
Specialty Elastomers from Dow is standing by to support you. To
learn more about blow molding with high melt strength polyolefin
elastomers or to discuss your specific material or processing Figure 9: Detail on Grained Surface of Dog-Bone Part
requirements please call the number for your area below or visit
us online at www.dowplastics.com

To Learn More, Call:

U.S., Canada, Mexico: Latin America: Europe: Asia-Pacific: South Africa:

Toll-free Tel: 1-800-441-4369 Tel: (+55) 11-5188-9222 Toll-free Tel: +800-3-694-6367 Toll-free Tel: +800 7776-7776 Tel: +800-99-5078
Tel: +32 3-450-2240 Tel: (+60) 3-7958-3392

NOTICE: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from one location to another
and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customers use and for
ensuring that Customers workplace and disposal practices are in compliance with applicable laws and other governmental enactments. Seller assumes no obligation
or liability for the information in this document. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE ARE EXPRESSLY EXCLUDED.

Published October 2006

Printed in U.S.A. Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow
TM
Form No. 774-01401-1006AMS