Polyethylene:

Polyethylene is made by addition or radical polymerization of ethylene (olefin) monomers.

(Chemical formula of Ethene - C2H4).

Ziegler-Natta and Metallocene catalysts are used to carry out polymerization of polyethylene.

Ziegler-Natta
Polymerization
Or Metallocene
Structure of PE Monomer Structure of Polyethylene
Catalysis
C2H4

In addition, PE is also available in other types such as: (not discussed in detail in this guide)

● Medium-density polyethylene (MDPE)

● Very-low-density polyethylene (VLDPE)
● High-molecular-weight polyethylene (HMWPE)
● Ultra-low-molecular-weight polyethylene (ULMWPE)
● Chlorinated polyethylene (CPE)
High Density Polyethylene (HDPE)

High Density Polyethylene (HDPE) is a cost-effective thermoplastic with linear structure and no
or low degree of branching. It is manufactured at low temperature (70-300°C) and pressure (10-
80 bar) & derived from either:

● Modifying natural gas (a methane, ethane, propane mix) or

● The catalytic cracking of crude oil into gasoline

HDPE is produced majorly using two techniques: Slurry Polymerization or Gas Phase
Polymerization.High density polyethylene is flexible, translucent/waxy, weather resistant, and
displays toughness at very low temperatures.

Properties of High Density Polyethylene

1. HDPE Melting point: 120-140°C

 2. Density of HDPE: 0.93 to 0.97 g/cm3
3. High Density Polyethylene Chemical resistance:
○ Excellent resistance to most solvents
○ Very good resistance to alcohols, dilute acids and alkalis
○ Moderate resistance to oils and greases
4. Poor resistance to hydrocarbons (aliphatic, aromatic, halogenated)
5. Continuous temperature: -50°C to +60°C, relatively stiff material with useful
temperature capabilities
6. Higher tensile strength compared to other forms of polyethylene
7. Low cost polymer with good processability
8. Good low temperature resistance
9. Excellent electrical insulating properties
10. Very low water absorption
11. FDA compliant

Disadvantages of HDPE
● Susceptible to stress cracking
● Lower stiffness than polypropylene
● High mold shrinkage
● Poor UV- and low heat resistance
● High-frequency welding and joining impossible

However, weathering resistance of HDPE can be improved by the addition of carbon black or UV
absorbing additives. Carbon black also helps to reinforce the material.

1. Consumer Goods – Low cost and easy processability make HDPE a material of
choice in several household/ consumer goods like garbage containers,
housewares, ice boxes, toys etc.
2. Fibers and Textiles – Thanks to its high tensile strength, HDPE is widely used in
ropes, fishing and sport nets, nets for agricultural use, Industrial and decorative
fabrics, etc.

Low-Density Polyethylene (LDPE) is a semi-rigid and translucent polymer. Compared to

HDPE, it has a higher degree of short and long side-chain branching. It is produced at high
pressure (1000-3000 bar; 80-300°C) via a free radical polymerization process. The LDPE is
composed of 4,000-40,000 carbon atoms, with many short branches. Two basic processes used
for the production of low-density polyethylene: stirred autoclave or tubular routes. The tubular
reactor has been gaining preference over the autoclave route due to its higher ethylene
conversion rates.
Properties of Low-Density Polyethylene
 1. LDPE Melting point: 105 to 115°C
2. Density of LDPE: 0.910–0.940 g/cm3
3. Chemical resistance of LDPE:
○ Good resistance to alcohols, dilute alkalis and acids
○ Limited resistance to aliphatic and aromatic hydrocarbons, mineral oils,
oxidizing agents and halogenated hydrocarbons
4. Temperature resistance up to 80°C continuously and 95°C for shorter times.
5. Low cost polymer with good processability
6. High impact strength at low temperature, good weatherability
7. Excellent electrical insulating properties
8. Very low water absorption
9. FDA compliant
10. Transparent in thin film form

Disadvantages of LDPE
● Susceptible to stress cracking
● Low strength, stiffness and maximum service temperature. This limits its usage in
applications requiring extreme temperatures.
● High gas permeability, particularly carbon dioxide
● Poor UV resistance
● Highly flammable
● High-frequency welding and joining impossible

Applications of Low-Density Polyethylene (LDPE)

Low-Density Polyethylene (LDPE) mainly revolves around manufacturing containers, dispensing

bottles, wash bottles, tubing, plastic bags for computer components, and various molded
laboratory equipment. The most popular application of low-density polyethylene is plastic bags.
Linear Low-Density Polyethylene (LLDPE)

LLDPE is produced by polymerization of ethylene (or ethane monomer) with 1-butene and
smaller amounts of 1-hexene and 1-octene, using Ziegler-Natta or metallocene catalysts. It is
structurally similar to LDPE. The structure of LLDPE has a linear backbone with short, uniform
branches (unlike longer branches of LDPE). These short branches are able slide against each
other upon elongation without becoming entangled like LDPE.

In the present-day scenario, linear low-density polyethylene (LLDPE) has been quite successful
in replacing Low Density Polyethylene.

Properties of LLDPE

● Very flexible with high impact strength

● Translucent and natural milky color
 ● Excellent for mild and strong buffers, good chemical resistance
● Good water vapor and alcohol barrier properties
● Good stress crack and impact resistance
Benefits of Polyethylene Films

● PE films burn to carbon dioxide and water with no residue. There are no toxic fumes or
gases and no cinders produced in this process
● PE films contain no plasticizers and no heavy metals. They are physiologically harmless
● No odor pollution or wastewater are produced in the manufacture of PE films

Ultra High-Molecular-Weight Polyethylene (UHMWPE)

Ultrahigh-molecular-weight polyethylene or UHMWPE has a molecular weight about 10 times

higher (usually between 3.5 and 7.5 million amu) than High Density Polyethylene (HDPE) resins.
It is synthesized using metallocene catalysts and ethane units resulting in a structure where
ethane units are bonded together resulting in UHMWPE structure typically having 100,000 to
250,000 monomer units per molecule. These molecules are several orders of magnitude longer
than those of familiar high-density polyethylene (HDPE) due to a synthesis process based on
metallocene catalysts, monomer units per molecule each compared to HDPE's 700 to 1,800
monomers.UHMWPE is processed variously by compression moulding, ram extrusion, gel
spinning, and sintering. Its melting point is around 144–152 °C.

● It has excellent mechanical properties such as high abrasion resistance, impact strength
and low coefficient of friction.
● The material is almost totally inert, therefore it is used in the most corrosive or aggressive
environments at moderate temperatures.
● Even at high temperatures, it is resistant to several solvents, except aromatic,
halogenated hydrocarbons and strong oxidizing materials, such as nitric acid.
● These special properties allow the product to be used in several high-performance
applications.
● UHMWPE is suitable for high wear applications such as tubes, liners, silos, containers
and other equipment.

Cross-linked Polyethylene (PEX or XLPE)

High-density crosslinked polyethylene, or XLPE, is a form of polyethylene with crosslinked

structure specifically designed for critical applications.
Cross linked polyethylene is produced from polyethylene under high pressure with organic
peroxides which creates a free radical. The free radical generates the crosslinking of the polymer
which results in a resin that is specifically designed for critical applications like chemical storage
pipework systems, hydronic radiant heating and cooling systems, and insulation for high voltage
electrical cables.

Key Features of XLPE

● High and low temperature

● Hydrolysis resistance
● High electrical and insulation properties
● High abrasion resistance
● Potable water approved
● High extrusion speed on standard lines
● Lower cost
● Mechanically tougher

Poly(ethene) is made by several methods by addition polymerization of ethene,

which is principally produced by the cracking of ethane and propane, naphtha and
gas oil.
A new plant is being constructed in Brazil for the production of poly(ethene), from
ethene, that is made from sugar cane via bioethanol. This is sometimes termed
bio-based poly(ethene) (bio-based polyethylene).
Low density poly(ethene) (LDPE)
The process is operated under very high pressure (1000-3000 atm) at moderate
temperatures (420-570 K) as may be predicted from the reaction equation:

This is a radical polymerization process and an initiator, such as a small amount

of oxygen, and/or an organic peroxide is used.
Ethene (purity in excess of 99.9%) is compressed and passed into a reactor
together with the initiator. The molten poly(ethene) is removed, extruded and cut
into granules. Unreacted ethene is recycled. The average polymer molecule
contains 4000-40 000 carbon atoms, with many short branches.
There are about 20 branches per 1000 carbon atoms. The relative molecular
mass, and the branching, influence the physical properties of LDPE. The
branching affects the degree of crystallinity which in turn affects the density of the
material. LDPE is generally amorphous and transparent with about 50%
crystallinity. The branches prevent the molecules fitting closely together and so it
has low density.
High density poly(ethene) (HDPE)
Two types of catalyst are used principally in the manufacture of HDPE:
● a Ziegler-Natta organometallic catalyst (titanium compounds with an aluminium alkyl).
● an inorganic compound, known as a Phillips-type catalyst. A well-known example is
chromium(VI) oxide on silica, which is prepared by roasting a chromium(III) compound at
ca 1000 K in oxygen and then storing prior to use, under nitrogen.

HDPE is produced by three types of process. All operate at relatively low

pressures (10-80 atm) in the presence of a Ziegler-Natta or inorganic catalyst.
Typical temperatures range between 350-420 K. In all three processes hydrogen
is mixed with the ethene to control the chain length of the polymer.
(i) Slurry process (using either CSTR (continuous stirred tank reactor) or a
loop)
The Ziegler-Natta catalyst, as granules, is mixed with a liquid hydrocarbon (for
example, 2-methylpropane (isobutane) or hexane), which simply acts as a diluent.
A mixture of hydrogen and ethene is passed under pressure into the slurry and
ethene is polymerized to HDPE. The reaction takes place in a large loop reactor
with the mixture constantly stirred (Figure 4). On opening a valve, the product is
released and the solvent is evaporated to leave the polymer, still containing the
catalyst. Water vapour, on flowing with nitrogen through the polymer, reacts with
the catalytic sites, destroying their activity. The residue of the catalyst, titanium(IV)
and aluminium oxides, remains mixed, in minute amounts, in the polymer.
(ii) Solution process
The second method involves passing ethene and hydrogen under pressure into a
solution of the Ziegler-Natta catalyst in a hydrocarbon (a C10 or C12 alkane). The
polymer is obtained in a similar way to the slurry method.

(iii) Gas phase process

A mixture of ethene and hydrogen is passed over a Phillips catalyst in a fixed bed
reactor (Figure 6).
Ethene polymerizes to form grains of HDPE, suspended in the flowing gas, which
pass out of the reactor when the valve is released.
Modern plants sometimes use two or more of the individual reactors in series (for
example two or more slurry reactors or two gas phase reactors) each of which are
under slightly different conditions, so that the properties of different products from
the reactors are present in the resulting polymer mixture, leading to a broad or
bimodal molecular mass distribution. This provides improved mechanical
properties such as stiffness and toughness.

his leads to strong intermolecular bonds, making the material stronger, denser and
more rigid than LDPE. The polymer is not transparent.
Linear low density poly(ethene) (LLDPE)
Low density poly(ethene) has many uses but the high pressure method of
manufacture by which it is produced has high capital costs. However, an elegant
technique has been developed, based on both Ziegler-Natta and inorganic
catalysts to produce linear low density poly(ethene) LLDPE, which has even
improved properties over LDPE. Any of the three processes, slurry, solution and
gas phase, can be used when a Ziegler-Natta catalyst is chosen. The gas phase
process is used when the inorganic catalyst is employed.
Small amounts of a co-monomer such as but-1-ene or hex-1-ene are added to the
feedstock. The monomers are randomly polymerized and there are small
branches made up of a few carbon atoms along the linear chains.
For example, with but-1-ene, CH3CH2CH=CH2, the structure of the polymer is:

The side chains are known as pendant groups, or short chain branching. The
molecule can be represented as:

The structure is essentially linear but because of the short chain branching it has a
low density. The structure gives the material much better resilience, tear strength
and flexibility without the use of plasticisers. This makes linear low density
poly(ethene) an ideal material for the manufacture of film products, such as those
used in wrappings.
The properties of the polymer, and hence its uses, can be varied by varying the
proportion of ethene and co-monomer and by using different co-monomers. All
this can be done without shutting down the plant, an enormous advantage.
 Metallocene linear low density poly(ethene)
(mLLDPE)
This poly(ethene), known as mLLDPE, is produced by a new family of catalysts,
the metallocenes. Another name for this family is single site catalyst. The benefit
is that the mLLDPE is much more homogenous in terms of molecular structure
than classical LLDPE produced by Ziegler-Natta catalysts. Each catalyst is a
single site catalyst which produces the same PE chain. Chemists have compared
the structure of metallocenes to that of a sandwich. There is a transition metal
(often zirconium or titanium) 'filling' a hole between layers of organic compounds.
The catalysts are even more specific than the original Ziegler-Natta and it is
possible to control the polymer's molecular mass as well as its configuration.
Either the slurry or solution processes are usually used.
Poly(ethene) produced using a metallocene can be used as very thin film which
has excellent optical properties and sealing performance, thus making them very
effective for wrapping foods. The real plus for the metallocene catalysts are the
enhanced mechanical properties of the films made out of mLLDPE.
Co-polymers
Ethene forms co-polymers with propene which have very useful properties.

Slurry Process:
The slurry loop reactor is a long tube, about 600 mm in diameter and a few hun-
dred metres long, of which the ends are connected to make it one closed loop.
Its volume is of the order of 100m3. It is totally filled with the slurry, which is
circulated through the loop by one single circulation pump. The larger part of
the reactor consists of an even number of vertical tube sections, or legs,
connected by short horizontal elbows at the top and the bottom. The outer
aspect of the reactor is that of a tubular reactor, one of the two main model
reactors known in chemical reactor engineering, where the reagents are fed at
one side of the tube and leave it at the other end. However, since the loop is
closed, and the reactor contents are circulated through the loop at a high speed,
the behaviour of the reactor is very close to that of the continuous stirred tank
reactor, that other model known from reactor engineering textbooks. Actually,
the loop reactor can be regarded as a stirred tank, where the circulation pump
has taken over the role of the agitator, and where the vessel has been lengthened
to obtain more external cooling surface, and a higher production capacity.
Indeed, the heat of reaction of the polymerisation of ethylene is quite high¹, and
the cooling surface of the reactor is one of the limiting factors to its production
capacity.

Difference Between Slurry And Gas Phase:

In gas-phase processes, no mass transfer limitation gas-liquid can occur, and
Therefore, there is no polyethylene, monomer, co-monomer and hydrogen
solubility concern in the solvent medium during the polymerization [18].
Therefore, more soluble PE, for example most medium density (MDPE) and
linear low density polyethylene (LLDPE), are produced in gas-phase
processes. These advantages allow the operation of gas phase plants as
multipurpose plants for producing a wide range of polyethylenes with different
densities and melt flow indexes (MFI). In addition, gas-phase processes create
no wall sheeting or fouling due to the polyethylene’s solubility in the solvent
medium which is the main problem in slurry processes. However, wall sheeting
is also a major problem in gas phase reactors, as described below. Still, there
remains a significant demand for slurry processes in the market, especially
because of its advantages:
• mild operating conditions
• high monomer conversion
• ease of heat removal
• relative ease of processing.