POLYETHYLENE

INTRODUCTION
 INTRODUCTION

  Known as polythene
  Primary use in packaging

  The chemical formula of PE is (C2H4)nH2

  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

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 :
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

  Thechain is initiated by free radicals, Ra,

produced by reaction between some of the ethene
and the oxygen initiator.
STEP 3. PROPAGATION
  Thenewly 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.

Ra . + CH2=CH2  →  RaCH2CH2 .

RaCH2CH2 . + CH2=CH2  →  RaCH2CH2CH2CH2 .
STEP 4. TERMINATION 
  Finallythe reaction is terminated when two
radicals react with each other to produce a
product with paired electrons:
Chain termination

  Eventuallytwo 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

  Becausechain 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)
  Theprocess 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

  manufacturingprocess used to make pipes, hoses,

drinking straws, curtain tracks, rods, and fibres
  Shapesthat 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 cause serious thermal
be irritating to the eye burns
INHALATION

Nuisance dusts can be Irritating vapors may

irritating to the upper form when the
respiratory tract polyethylene is 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
CH2=CH2 C + CH4
SAFETY MEASURE
Fines and Dust
Steamers
-Can create feed and
product quality problems
-Can plug filters, feeders,
silo outlets, and reduce
resin flow
- Regrind, dry colorants
and additives in powder Static
form can bring in Electricity
hazardous dust particles
-ungrounded metal
- Dust particles piece of conveying
dispersed equipment can present
in air can form explosive significant hazard
dust cloud -it can get charged
from the polyethylene
resin to a high voltage
-discharge entire
metal surface in a
single spark.
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.
  Thewide 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.
  Polyethyleneis not considered biodegradable, as it takes
several decade until it is efficiently degraded.