Equistar

Technical
Tip

tech.topic
Introduction to Polyethylene

INTRODUCTION

Polyethylene (PE) resins are a general class of

thermoplastics produced from ethylene gas.
Ethylene gas is derived from the cracking of
natural gas feedstocks or petroleum byproducts. Under broad ranges of pressures,
temperatures and catalysts (depending PE type),
ethylene generally polymerizes to form very long
polymer chains.
By utilizing techniques such as using different
reactor technologies, operating multiple reactor
configurations, or polymerizing other gases such
as vinyl acetate or other olefins (butene, hexene,
octene) in conjunction with ethylene to form
copolymers, different types of PE resins can be
produced. The ability to produce so many
variations of a basic material permits the
manufacturer to tailor PE resins for diverse
applications, such as packaging films, rigid food
containers, milk and water bottles, large toys,
etc. Following is a review of the three basic
categories of PE resins, how they are produced
and their key properties.
Polyethylene products are typically classified by
their melt index and density. The melt index
provides a general indication of a products
molecular weight (MW) and processability. A
higher melt index resin will typically have a lower
molecular weight and process (flow) easier;
however, it usually has decreased physical
properties as a result of the lower MW. Density
measures crystallinity. As density and
crystallinity increase, stiffness increases and
impact decreases.

POLYMERIZATION OF POLYETHYLENE
RESINS
When comparing the polymerization processes
among the PE family of resins, they vary
significantly, which result in the wide range of
physical properties associated with PE.
However, in all cases, the resultant PE products
are pelletized on compounding extruders where
additives such as antioxidants, processing aids,
etc. are incorporated.
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Low density polyethylene (LDPE) is produced

by autoclave or tubular reactor technology.
Each reactor type operates at high pressures
(up to 45,000 psig). The resulting polymer is
highly branched, which results in its low
density and unique physical properties. Vinyl
acetate (VA) can be added to produce
copolymer products that can have increased
clarity (at low VA levels) and increased
flexibility.
Linear low density polyethylene (LLDPE) is
typically made by using a transition-metal
catalyst in a gas-phase reactor that operates at
low pressures relative to the high pressures
used in the manufacture of LDPE.
Comonomers, such as butene, hexene or
octene are added with ethylene to create linear
polymer chains with short chain branches and
low densities. Solution and some slurry
reactor technologies can be utilized to produce
LLDPE as well.
High density polyethylene (HDPE) can be
polymerized by using slurry, solution, or gasphase reactor technologies. HDPE
manufacturing processes also use transitionmetal catalysts to make linear polymer chains
with less branching than LLDPE. Butene,
hexene and octene are typical HDPE
comonomers. Polymerizing ethylene without
any comonomer produces HDPE
homopolymer. The resulting products exhibit
the highest density and crystallinity in the PE
family.
LOW DENSITY POLYETHYLENE
The high level of long-chain branching (LCB),
as shown in Figure 1, of LDPE causes the
polymer to have low crystallinity and low
density ranging from 0.915 to 0.935 g/cc. As a
result of the low crystallinity of LDPE, the enduse applications are flexible and soft.

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tech.topic

Equistar
Technical
Tip

Introduction to Polyethylene
In the production of film, LCB aids in
processability because of higher melt strength
(better bubble stability); however, this typically
decreases tear and impact film properties.

Figure 1. LDPE Polymer Molecule

In the production of film, LCB aids in
processability because of higher melt strength
(better bubble stability); however, this typically
decreases tear and impact film properties.
As shown in Figure 2, over half of the 7.98billion pound 2000 LDPE market was used in
processes involving extrusion (film, extruded
products, extrusion coating).1 Typical
applications include high-clarity film, flexible
food packaging, heavy-duty films and caps and
closures.

Export
24%

Blow
Molding
1%

Third
Party
11%
Other
4%

Injection
Molding
4%
Film
37%

Extrusion
Coating
12%

Extruded
Products
7%

Figure 2. 2000 LDPE Market

(continued)

LINEAR LOW DENSITY POLYETHYLENE

While LDPE has high levels of LCB, there is
little LCB in LLDPE; however, there are high
levels of short-chain branching (SCB)
contributed by the incorporated comonomer.
This is illustrated in Figure 3.
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field codes.

Figure 3. LLDPE Polymer Molecule

Even though the densities of LDPE and LLDPE
(0.915 0.930 g/cc) are similar, LLDPE
displays better tear and impact film properties
than LDPE due to decreased levels of LCB and
narrower molecular weight distribution
(MWD). However, due to the lack of LCB and
narrower MWD, film processability decreases.
Figure 4 shows that almost half of 9.90-billion
pound 2000 LLDPE market goes into film
applications.1 Rotomolding of large parts such
as toys and tanks usually uses LLDPE resins.
Other typical applications include heavy-duty
shipping sacks, industrial packaging, flexible
food packaging, storage boxes and thin-wall
lids.
Export
22%
Third Party
12%

Blow Molding Injection

Molding
0.1%
6%

Film
48%

Other
2%
Rotomolding
4%

Extruded
Products
6%

Figure 4. 2000 LLDPE Market

(Continued on Page 3)
1

Source: APC Plastics Industry Producers Statistics Group, as compiled by Association Survey Resources, LLC

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Equistar
Technical
Tip

tech.topic
Introduction to Polyethylene
HIGH DENSITY POLYETHYLENE
With HDPE the MWD can vary depending on
the catalyst and reactor technology used in
production. For example, chromium-catalyzed
products typically produce broader MWD
products. The broader MWD is advantageous
for some applications such as blow molding
due to higher melt strength. Ziegler-Natta
catalysts usually produce narrow MWD
products, which help to increase impact
strength and decrease warpage in injection
molding.
Multi-reactor technologies, such as Lyondells
Matagorda and Victoria HDPE plants (see
Matagorda and Victoria Plant Profile Tech Tips
for more details), allow for precise tailoring of
the MWD. As a result, the appropriate balance
of processability and physical properties can
be achieved through control of the MWD at a
given average MW.

(continued)

Due to its higher crystallinity and resulting

higher density (0.940 0.965 g/cc), HDPE
products tend to show higher stiffness, which
makes them suitable for rigid packaging
applications. This branching is shown in
Figure 5.
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field codes.
Figure 5. HDPE Polymer Molecule
As shown in Figure 6, the 15.45-billion pound
2000 HDPE market shows significant levels in
blow molding, injection molding, and film.1
Typical applications consist of detergent
bottles, milk bottles, pails, thin-wall
containers, drink cups, cases and crates,
grocery bags and produce bags.

T hird Party
11%

Export
14%

Other

Blow Molding
28%

4%
Rotomolding
1%
Pipe
11%

Film
Sheet
4%

13%

Injection
Molding
14%

Figure 6. 2000 HDPE Market

The information on this document is, to our knowledge, true and accurate. However, since the particular uses and the actual
conditions of use of our products are beyond our control, establishing satisfactory performance of our products for the intended
application is the customer's sole responsibility. All uses of Equistar products and any written or oral information, suggestions or
technical advice from Equistar are without warranty, express or implied, and are not an inducement to use any process or product in
conflict with any patent.
Equistar materials are not designed or manufactured for use in implantation in the human body or in contact with internal body fluids
or tissues. Equistar makes no representation, promise, express warranty or implied warranty concerning the suitability of these
materials for use in implantation in the human body or in contact with internal body tissues or fluids.
More detailed safety and disposal information on our products is contained in the Material Safety Data Sheet (MSDS). All users of our
products are urged to retain and use the MSDS. A MSDS is automatically distributed upon purchase/order execution. You may
request an advance or replacement copy by calling our MSDS Hotline at (800) 700-0946.
Lyondell Chemical Company
1221 McKinney, Suite 700
P.O. Box 2583
Houston, Texas 77252-2583
(800) 615-8999
http://www.Lyondell.com
9815/0601

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