POLYETHYLENE

INTRODUCTION
 INTRODUCTION

 Known as polythene
 Primary use in packaging

 The chemical formula of PE is (C2H4)nH2 (n is the repeating

ethylene numbers)
 Obtained by polymerizing ethylene gas, H2C=CH2

 The two most widely used grades of polyethylene are LDPE

and HDPE.
 A new LDPE grade has been introduced. It is LLDPE which
produced like the high-density polymer at low pressures.
Physical properties

• Thermoplastic polymer
• the melting point is typically in the range 120
to 180 °C
• LDPE exhibits high flexibility

Chemical properties

• have excellent chemical resistance (not

attacked by strong acid or strong bases)
• burns slowly with a blue flame and gives off
an odour of paraffin
REACTION
AND
MECHANISM
 BASIC PROCESS

Crude
Oil

Ethylene Polyethylene

Intermediate for
polyethylene

Natural
Gas
 Ethylene production

2CH4 + O2 → C2H4 + 2H2O

Polymerization

catalyst
n H2C=CH2 --------------> (CH-CH)n
high pressure
 POLYMERIZATION

 One of the most common and useful reaction for

making polymers is free radical polymerization.
 It is used to make polymers from vinyl monomers, that
is, from small molecules containing carbon- carbon
double bonds.
 REACTION MECHANISM
Polymerization of Ethylene Monomer

Polymerized by a radical mechanism with the

addition of an organic peroxide radical
initiator/Zielger Nata catalyst.
STEP 1. INITIATION
 Dissociation of the peroxide's oxygen bonds then
quickly converted into carbon dioxide and 2 radicals :

Organic Peroxide
STEP 2. INITIATION
 These radicals can then act as electrophiles and attack
the double bond of ethylene forming a stabler
intermediate:
 MECHANISM OF POLYETHYLENE
POLYMERIZATION

Chain initiation
 The chain is initiated by free radicals, Ra, produced by
reaction between some of the ethene and the oxygen
initiator.
STEP 3. PROPAGATION
 The newly formed radical can add on to itself by
attacking another ethylene molecule:

 The polyethylene molecule can be controlled by the

reaction temperature, the type of catalyst employed,
and the radical concentration.
Chain propagation

 Each time a free radical hits an ethene molecule a new longer

free radical is formed.

. + CH2=CH2 .
Ra → RaCH2CH2

RaCH2CH2 . + CH2=CH2 → RaCH2CH2CH2CH2 .

STEP 4. TERMINATION
 Finally the reaction is terminated when two
radicals react with each other to produce a
product with paired electrons:
Chain termination

 Eventually two free radicals hit each other producing a final

molecule. The process stops here because no new free radicals
are formed.

Ra(CH2)m .+ . (CH2)n Ra →
Ra(CH2)m(CH2)mRa

 Because chain termination is a random process,

polyethylene will be made up of chains of all sorts of
different lengths.
PROCESS FLOW
DIAGRAM
CATALYST USED
Ziegler-Natta Catalyst

 German Karl Ziegler had discovered the first titanium-

based catalysts, and Italian Giulio Natta, for using them to
prepare stereoregular polymers.
 have been used in the commercial manufacture of
various polymeric materials since 1956.
 used in the synthesis of polymers of 1-alkenes (α-
olefins).
 Used to polymerize terminal 1-alkenes .
 Employed in solid and supported catalysts based on titanium
compounds. They are used in polymerization reactions in
combination with cocatalysts, organoaluminium compounds.
Phillips catalyst

 Is used in polymerization process

 Composed of chromium oxide supported on an

amorphous material such as silica, e.g : Cr/SiO2

 Prepared by impregnation of chromium oxide on a

wide pore silica.

 Chromium – based catalyst able to produce
different type of HDPE.
WHAT IS THE
PRODUCTS FROM
POLYETHYLENE?
GARBAGE CONTAINERS BOTTLES

BAG PLASTIC PACKAGING FILM

 LDPE
-produced under high
pressure in the presence
of a free radical initiator
-a density range of 0.910–
0.940 g/cm3
-Use for both rigid
containers and plastic film
applications : plastic bags,
HDPE
- produced by a low-pressure
process in the presence of the
Ziegler-type catalyst
-density of greater or equal to
0.941 g/cm3
-Use in packaging products :
detergent bottles, garbage
container, water pipe
LLDPE
- produced in the gas
phase under low pressure
-a density range of 0.915–
0.925 g/cm3.
-Use in gas pipe and
fittings, packaging film,
carrier bags, film wrap
 Polyethylene products include packaging (largest market),
bottles, irrigation pipes, film, sheets, and insulation materials.
 Because LDPE is flexible and transparent, it is mainly used to
produce film and sheets.
 HDPE is important for producing bottles and hollow objects
by blow molding. Approximately 64% of all plastic bottles are
made from HDPE.
HDPE
HDPE
LDPE
LLDPE
LOW DENSITY POLYETHYLENE (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 is compressed and passed into a reactor together with
the initiator. The molten polyethylene 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.
 For example:

 It can be represent by:

HIGH DENSITY POLYETHYLENE
 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 : chromium(VI) oxide on silica
 HDPE is produced by three types of process. All operate at
relatively low pressures (10-80 atm) in the presence of a
Ziegler-Natta.
 In all three processes, hydrogen is mixed with the ethene
to control the chain length of the polymer.
 I) SLURRY PROCESS
 The Ziegler-Natta catalyst, as granules, is mixed with a
liquid hydrocarbon. 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 . 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
 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 .
 Ethene polymerizes to form grains of HDPE, suspended
in the flowing gas, which pass out of the reactor when the
valve is released.
 The HDPE powder coming out of any of the reactors is
separated from the diluent and is extruded and cut up into
granules.
 The polymer chains can be represented :

 strong intermolecular bonds, denser and more rigid than

LDPE. The polymer is not transparent.
LINEAR LOW DENSITY POLYETHYLENE (LLDPE)

based on both Ziegler-Natta and inorganic catalysts to
produce linear low density polyethylene LLDPE, which has
also 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 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.
 Example:
with but-1-ene, CH3CH2CH=CH2, the structure of the
polymer is

- Low density
- Better resilience, tear strength and flexibility.
PROPERTIES AND USES OF POLYETHYLENES
 Polyethylene is an inexpensive thermoplastic that can be
molded into almost any shape, extruded into fiber or filament,
and blown or precipitated into film or foil. Polyethylene
products include packaging (largest market), bottles, irrigation
pipes, film, sheets, and insulation materials.
 Currently, high density polyethylene is the largest-volume
thermoplastic. The 1997 U.S. production of HDPE was 12.5
billion pounds.
 LDPE was 7.7 billion pounds and LLDPE was 6.9 billion
pounds.
 Because LDPE is flexible and transparent, it is mainly used to produce
film and sheets. Films are usually produced by extrusion.
 Calendering is mainly used for sheeting and to a lesser extent for film
production.
 HDPE is important for producing bottles and hollow objects by blow
molding. Approximately 64% of all plastic bottles are made from
HDPE. Injection molding is used to produce solid objects.
 Another important market for HDPE is irrigation pipes.
 Pipes made from HDPE are flexible, tough, and corrosion resistant.
They could be used to carry abrasive materials such as gypsum.
THE IMPORTANT PROPERTIES OF
POLYETHYLENE
PLASTIC EXTRUSION PROCESS

 manufacturing process used to make pipes, hoses,

drinking straws, curtain tracks, rods, and fibres
 Shapes that can result from extrusion include T- sections,
U-sections, square sections, I-sections, L- sections and
circular sections.
Material is fed into a heated barrel, mixed, and forced into a mold
cavity where it cools and hardens to the configuration of the mold
cavity
CALENDERING MACHINE FOR FOIL AND SHEET
PLASTIC FILM CALENDERING MACHINE
PROCESSES AND PRODUCTS PRODUCE
Process HDPE LDPE LLDPE

Making film Food packaging Cling film Stretch film

Shopping bags Milk carton
lining

Injection Dustbins Buckets Food boxes

moulding Crates Bowls

Blow moulding Detergent bottles Squeezable

Drums bottles

Extrusion Water pipes Flexible water Cable coating

pipes
SAFETY MEASURE
 HAZARD IDENTIFICATION

 POTENTIAL HEATLH
EFFECT
Dust may cause mechanical
irritation to eye

Eyes
Vapours formed when Heated polyethylene can
polyethylene is heated may be cause serious thermal burns
irritating to the eye
INHALATION

Nuisance dusts can be Irritating vapors may form

irritating to the upper when the polyethylene is
respiratory tract processed at high
temperatures
SAFETY MEASURES
 When ethylene is polymerized, the reactor temperature
should be well controlled to avoid the endothermic
decomposition of ethylene to carbon, methane, and
hydrogen:
CH2=CH2 2C + 2H2
C + CH4
CH2=CH2
SAFETY MEASURFEinesand Dust
- Regrind, dry colorants
and additives in powder Static
form can bring in Electricity
hazardous dust particles
Steamers -ungrounded metal piece
- Dust particles of conveying equipment
-Can create feed and dispersed can present significant
product quality problems
in air can form explosive hazard
-Can plug filters, feeders, silo dust cloud -it can get charged from
outlets, and reduce resin flow the polyethylene resin to a
high voltage
-discharge metal entire
surface in
single spark. a

Potential
Hazards
EXPOSURE CONTROL/ PERSONAL
PROTECTION
 Engineering control-Local exhaust ventilation of
process equipment is recommended for control of
airborne dusts, fumes and particularly in confined
areas.
 Respiratory equipment

 Personal protection-wear safety glasses with

the side shields. Where contact may occur with hot
material, wear thermal resistant gloves, arm protection
and a face shield.
EXPOSURE CONTROL/PERSONAL
PROTECTIVE –CONT.
 Workplace Exposure Guidelines-OSHA
regulation 29CFR1910.1000 requires the
following permission to exposure limits:
-5mg/m3 (respiratory dust), and 15mg/m3 (total dust)
based on the OSHA PEL for nuisance dust.
Handling
 Pneumatic material handling and processing
equipment may generate dust of sufficiently
small particle size that when suspended in air may
be
explosive.
 Dust accumulations should be controlled through a
comprehensive dust control program
 This includes source capture, inspection and
repair of leaking equipment, routine housekeeping
and
employee training in hazards
Packaging & Shipping
 Used dense phase system for conveying and transportation -
minimizes dust contamination

 Used stretch hood – provide maximum stability during

transportation and protection of bags from external agents
(rain,dust)
Storage
 Ensure storage area is under the protection of a deluge system – dust free and
dry with adequate ventilation and absence of sunlight.
 Keep storage temperatures preferably below 40°C.
- to avoid moisture condense inside the packed bag
 Pallets of LLDPE grade should be stacked in a single layer - no double stacking
 HDPE resin Pallets should be stacked two high maximum
ENVIRONMENTAL
ISSUES
BIODEGRADABLE
PLASTICS

Polyethylene without special treatment it is

not readily biodegradable
Burning plastics

Synthesizing biodegradable plastics has been

developed

Buried the plastics

Require sunlight to speed up degrade

POLLUTION
CONTROL
POLLUTION CONTROL
Polyethylene pollutions means polluting environment by
burning or disposal of polyethylene material
HOW TO CONTROL THIS
POLLUTION?
 Massive awareness campaign and enlightenment about
the danger polythene
 Government should provide public waste bins in

strategic positions for the collection of wastes.

 The government and individuals should look

at recycling option of polyethylene

 Segregate plastic waste from other solid
waste
WASTE
MANAGEMENT
WASTE MANAGEMENT
Waste generated
during start-up,
breakdowns or
machinery
problems

Using a contract Polyethylene film

recycler to turn the SOLID manufacturers
waste film back into recycle this waste
pellets for re-use WASTE
WASTE MANAGEMENT - AIR
 Stack emission monitoring of different categories
plastic waste such as
(i) 100% Polyethylene Waste
(ii) 80% Polyethylene + 20% PVC Waste
 the emission of toxic pollutants such as dioxins and

furans is lower than the norms set for incinerator

 CONCLUSION
 Polyethylene is also known as plastic.
 The wide use of polyethylene makes it an important
environmental issue.
 Although it can be recycled, most of the commercial
polyethylene ends up in landfills and in the oceans.
 Polyethylene is not considered biodegradable, as it takes several
decade until it is efficiently degraded.