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Polymer Chemistry

Thermosetting Plastic

is a plastic material, polymer, that becomes pliable or moldable above a specific temperature and
solidifies upon cooling
associate through intermolecular forces, which weaken rapidly with increased temperature, yielding a
viscous liquid

2 classifications by structure:
Crystalline Polymers
Amorphous Polymers

Crystalline Polymers:
Have a relatively sharp melting point.
Have an ordered arrangement of molecule chains.
Generally require higher temperatures to flow well when compared to Amorphous.

Reinforcement with fibers increases the load-bearing capabilities considerably.

Shrink more than Amorphous, causing a greater tendency for deformation.
Fiber reinforcement significantly decreases deformation.
Usually produce opaque parts due to their molecular structure.

Amorphous Polymers:

Have no true melting point and soften gradually.

Have a random orientation of molecules; chains can lie in any direction.

Do not flow as easily in a mold as Crystalline Polymers.

Shrink less than Crystalline Polymers.

Generally yield transparent, water-clear parts.

Thermosetting Plastic
Also known as thermoset
Is a prepolymer material that cures irreversibly
made up of lines of molecules which are heavily cross-linked.

Heat (above 200 C)
Chemical reaction
Suitable radiation

Thermosetting Plastic
Curing process:
transforms the resin into a plastic or rubber by a cross-linking process.
Energy and/or catalysts are added that cause the molecular chains to react at
chemically active sites

Results to a rigid, 3-D structure.

Yields a molecule with a larger molecular weight, resulting in a material with a
higher melting point.

Thermosetting Plastic
Generally stronger than thermoplastic
Suited to high temperature applications
Good chemical resistance
More brittle
Not recyclable

Classifications of Plastics


Polyethylene Terephthalate

The most common thermoplastic polymer

Used in fibers for clothing, container for liquids and foods

Inexpensive, lightweight, and easy to recycle

May exist as an amorphous or as a semi-crystalline polymer

Polyethylene Terephthalate

Softdrink, water, mouthwash
Peanut butter containers
Salad dressing and vegetable oil

Polyethylene Terephthalate

Condensation Polymerization: esterification

Polyethylene Terephthalate

Stiffness and strength
Resilient to deformation
Naturally colourless
Fair moisture barrier

is a thermoplastic polymer consisting of long hydrocarbon chains.
Simplest polymer
Addition polymerization of ethylene CH2= CH2

High Density Polyethylene (HDPE)

Low Density Polyethylene (LDPE)

High Density Polyethylene (HDPE)

Catalyzed by organometallic compounds at moderate
pressure (15 to 30 atm)
Polymer chains are in great length
Linear molecules
Crystalline structure

High Density Polyethylene (HDPE)

Found in:
Milk jugs
Juice bottles
Bleach, detergent, and household cleaners
Shampoo bottles
Trash and shopping bags

High Density Polyethylene (HDPE)

Naturally white in color
Can withstand higher temp (above 100 C)
Carries a low risk of leaching
Good chemical resistance

Low Density Polyethylene (LDPE)

Prepared under very high pressures (about 350 MPa) and high
temperatures (about 350C)
Uses oxygen as initiator
Yields a hydrocarbon chains with side short and long side branches
Branches hinders the closely
packing of molecules
Amorphous structure

Low Density Polyethylene (LDPE)

Found in:

Squeezable bottles
Bread, frozen food, dry cleaning
and shopping bags

Low Density Polyethylene (LDPE)

Less strong
Lower melting point (75C)
Less chemical resistance

Polyvinyl Chloride
Third most used kind of plastic
Vinyl Chloride monomer is produced by combining ethylene with Chlorine
Addition polymerization of monomers to PVC
Amorphous structure

Polyvinyl Chloride
Found in:

Window cleaner and detergent bottles

Shampoo bottles
Wire jacketing

Polyvinyl Chloride
Fire retarding properties
Ignition temperature of 455C
Chemically stable
Resistant to oxidation (durable)
Chemical resistant to almost all chemicals except
for aromatics
Flexible physical properties depending on
Not safe with food use

Addition polymerization of propylene
One of the most versatile thermoplastic available

Found in:
Yogurt containers
Syrup bottles
Ketchup bottles
Medicine bottles

High melting point (170C)
Prone to oxidation


Is a synthetic aromatic polymer

Can be solid or foamed
Formerly foamed with chlorofluorocarbon
Addition polymerization of styrene
Long chain hydrocarbon where alternating carbon center are attached to phenyl group

Found in:

Disposable plates and cups

Meat trays
Carry out containers
CD cases


Solid PS is transparent
Hard and brittle
High gas permeability and good water vapor transmission
Chemical resistant to acid and bases
Good insulator


Natural Resins
Synthetic Resins

Pigments and Dyes
Blowing Agents

-are group of sticky, liquid, organic substances that usually hardens into brittle, amorphous, solid
substances upon exposure to air

-Insoluble in water, soluble in ether, alcohol, and other solvents

-Derived from plants or vegetable matter
- Oils from seeds
- Starch derivatives

-Three classifications:
- Hard Resins
- Oleoresins
- Gum Resins

Hard Resins

-hard, brittle, odorless, and tasteless resins that exhibit a glasslike fracture
-Ex. Amber, copals, sandarac
-obtained by distillation of oleoresin turpentine, which is a stick, amorphous semisolids that
contain essential oils.
-Ex. Balsam, Dragons Blood, Copaiba.

Gum Resins
-Mixtures of both true gums and resins

-Occur naturally as a form of tears on plants and trees

Petrochemical Resins (synthetic)

-Derived from oil, coal, and natural gas (crude oil)

- Distillation of Crude oil to produce Naphtha
- Naphtha cracking - breaking down of naphtha into smaller molecules
- Usually in the form or pellets and granules

Distillation of Crude Oil

Naphtha Cracking

-are ingredients added to the resin to produce a more stable plastic

-are often used in plastics to produce some desired characteristics

-Plasticizer is the most important additive.
-It is an organic liquid chosen to increase flexibility of the plastic.


-Fillers or extenders are added usually to thermosetting plastics to make them less brittle and to
reinforce mechanical strength.
Pigments and Dyes
-Pigments and dyes are added to give color to the plastic.


-To counteract decomposition during manufacture

Blowing Agents
-Commonly found in foamed plastics wherein self-generated or external heat converts blowing
agents into gas bubbles expanding the resins into foam plastics
-A catalyst, either a chemical or simply applied heat, helps to start the chemical reaction of


-Fire-retardants are added to the mixture to produce fire-retarding grades of plastics.

-The effect of oxygen on some plastics during manufacture can cause degradation that is why
anti-oxidants are incorporated to the process.


-is the process of building up continuous molecular chains from individual identical monomer

Two main methods:

-Addition Polymerization
-Condensation Polymerization

Addition Polymerization
-Occurs when an unsaturated monomer molecule opens a double/triple bond to free a valence

-Head to tail linking of monomers

-Produces thermoplastics such as polyethylene, polypropylene, and polystyrene

Condensation Polymerization
-is the process linking up monomer molecules of different compounds that
can result with the loss of some simple molecules like water or HCl

-produces both thermoplastics and thermosetting plastics such as

polyesters and nylon.

Thermoplastic and Thermoset

Processing Methods

Extrusion Blow Molding


Rotational Molding

Film Blowing

Compression Molding

Injection Molding


Blow molding


Expanded Bead Blowing

Plastic material as granules, pellets, or powder, is first loaded into a hopper and then fed into a
long heated chamber .

The plastic is melted by the mechanical work of the screw and the heat from the extruder wall.
At the end of the heated chamber, the molten plastic is forced out through a small opening
called a die to form the shape of the finished product.
As the plastic is extruded from the die, it is fed onto a conveyor belt for cooling or onto rollers
for cooling or by immersion in water for cooling.


An extension of film extrusion.

The still warm extrudate is chilled on polished, cold rolls to create sheet.
The thickness is well maintained and surface made smooth by the polished rollers.
Calendering is used for high output and the ability to deal with low melt strength.


Film Blowing
This process continuously extrudes vertically a ring of semi-molten polymer in
an upward direction.
A bubble of air is maintained that stretches the plastic axially and radially into
a tube many times the diameter of the ring.

The diameter of the tube depends on the plastic being processed and the
processing conditions.
The tube is cooled by air and is nipped and wound continuously as a flattened

The tube can be processed to form saleable bags

Film Blowing

Injection Molding
This process can produce intricate three-dimensional parts of high quality and great

It is predominately used for thermoplastics but some thermosets and elastomers are also
processed by injection molding.
In injection molding plastic material is fed into a hopper, which feeds into an extruder.
An extruder screw pushes the plastic through the heating chamber in which the material is then

At the end of the extruder the molten plastic is forced at high pressure into a closed cold
mold. The high pressure is needed to be sure the mold is completely filled. Once the plastic
cools to a solid, the mold opens and the finished product is ejected.

Injection Molding

Blow Molding
Blow molding is a simple process where compressed air is introduced underneath a warmed
sheet of thermoplastic material forcing the material into a mold cavity, or allowing it to expand
freely into the shape of a hemisphere.

Blow Molding

Expanded Bead Blowing

This process begins with a measured volume of beads of plastic being placed into a mold.

The beads contain a blowing agent or gas, usually pentane, dissolved in the plastic.
The closed mold is heated to soften the plastic and the gas expands or blowing agent generates
The result is fused closed cell structure of foamed plastic that conforms to a shape, such as
expanded polystyrene cups.

Expanded Bead Blowing

Extrusion Blow Molding

This is a combination of extrusion and blow moulding

Used where the article to be made has a narrow neck, such as a bottle.
The plastic material is first extruded as a tube shape into an open die.
The die is then closed to seal the ends of the tube and air is blown in forcing the plastic tube to
take up the shape of the die cavity.

Extrusion Blow Molding

Rotational Molding
Consists of a mold mounted on a machine capable of rotating on two axes simultaneously.

Solid or liquid resin is placed within the mold and heat is applied.
Rotation distributes the plastic into a uniform coating on the inside of the mold then the mold is
cooled until the plastic part cools and hardens.
This process is used to make hollow configurations.

Rotational Molding

Compression Molding
This process has a prepared volume of plastic placed into a mold cavity

A second mold or plug is applied to squeeze the plastic into the desired shape.

Compression Molding

This process is the low pressure, often just pouring, addition of liquid resins to a mold.

Catalyzed thermoset plastics can be formed into intricate shapes by casting.


Films of thermoplastic are heated to soften the film

Then the soft film is pulled by vacuum or pushed by pressure to conform to a mold or pressed
with a plug into a mold. Parts are thermoformed either from cut pieces for thick sheet or from
rolls of thin sheet.
The finished parts are cut from the sheet and the scrap sheet material recycled for manufacture
of new sheet.


Rigid Plastic

PET Bottles
Polyethylene terephthalate is used as a raw material for making packaging materials such as
bottles and containers for packaging a wide range of food products and other consumer goods.
Examples include soft drinks, alcoholic beverages, detergents, cosmetics, pharmaceutical
products and edible oils. PET is one of the most common consumer plastics used.

PET Bottles

Much cheaper than other alternatives


PET Bottles
When the PET bottles are returned to an authorized redemption center,
or to the original seller in some jurisdictions, the deposit is partly or fully
refunded to the redeemer. In both cases the collected post-consumer PET is
taken to recycling centers known as materials recovery facilities (MRF) where it is
sorted and separated from other materials such as metal, objects made out of
other rigid plastics such as PVC, HDPE, polypropylene, flexible plastics such as
those used for bags (generally low density polyethylene), drink cartons, glass,
and anything else which is not made out of PET.

PET Bottles

HDPE Packaging
High density polyethylene (HDPE) was first developed for packaging as a
film before being introduced as a bottle for milk in 1964. Its use for packaging has
increased because of its low cost, flexibility, durability, ability to withstand the
sterilizing process, and resistance to many chemicals.
As a food packaging, HDPE is most commonly associated with milk, oil,
and juice bottles. Non-food packaging uses include supermarket bags, cleaning
product containers, motor oil containers, agricultural films and chemical
containers, paper bag liners, bags, crates, drums, and pails.

HDPE Packaging

Plastic Pallets
These are HDPE plastic molds used mainly for storage
and transportation of goods. Plastic pallets can be made
using virgin or recycled resin.

Plastic Pallets - Stackable pallets

Stackable pallets are pallets that include bottom runners or picture frame bottoms,
allowing the pallets to sit safely on top of each other when the pallets are empty. Stackable
pallets allow for the safe double stacking of multiple pallets with product on them during the
shipping process. Since they have a consistent bottom deck, these pallets allow for a very steady

Plastic Pallets - Stackable pallets

Although there are many benefits for their use, it should be noted that empty stackable
pallets can take up a lot of space in storage. In addition, it should be taken into consideration that
the shipping process to the manufacturer for the first use or on a back haul to the shipper can
result in higher costs. Since stackable pallets are generally a very durable style of pallet, they are
most often considered for use in a closed loop or returnable type of environment.

Plastic Pallets - Rackable pallets

Rackable pallets - Rackable pallets are pallets that include bottom runners or picture
frame bottoms, allowing for the pallets to sit safely on top of a rack. Rackable plastic pallets allow
for storing the unit load above the floor, ultimately saving space. The bottom deck of a rackable
pallet can consist of many different configurations.

These configuration variations include:

Picture frame
Picture frame with a crossbar in the center of the base

Plastic Pallets - Rackable pallets

Rackable pallets are usually heavy duty in nature due to their load capacities and weigh more due to
the additional structure on the underside of the pallet. As a result of this increased structure and stability,
rackable plastic pallets are also stronger pallets.

Plastic Pallets - Nestable pallets

Nestable pallets - An alternative to a stackable pallet is a nestable pallet. Nestable
pallets fit together when empty and reduce the amount of space needed for storage.

Plastic Crates/Baskets/Bins
Plastic Crates/Baskets/Bins a container used for storage or
shipping of goods

Plastic Crates/Baskets/Bins Collapsible Crates

Collapsible Crates - Collapsible plastic crate were originally developed for the
automotive industry years ago to carry Original equipment manufacturer (OEM) parts to the
assembly lines.
These crates are collapsible in order to save on space in both the warehouse or in
transit. They include access doors for easy accessibility to any of your parts or other materials.

Plastic Crates/Baskets/Bins Rotomolded Plastic Bins

Rotomolded Plastic Bins - rotomolded plastic bins were originally designed for seafood,
meat, poultry, and other food processing environments. Now, they are used in many other
different applications such as recycling and bulk storage. Rotomolded bins are the toughest
plastic bins on the market making it economically viable for customers.

Plastic Crates/Baskets/Bins Plastic Crates for Agriculture

Plastic Crates for Agriculture - They were developed for harvesting, storage, cooling, and
transportation of produce from the field to the packaging shed. They are available in different
sizes depending on the produce that you are harvesting.

Plastic Crates/Baskets/Bins Plastic Hopper Bins

Plastic hopper bins are extremely popular in areas of processing products in bulk such
as: nuts, grains, seeds, resins etc. They are reusable and designed to be stacked and lifted by a
forklift. Plastic hopper bins have been recognized for their durability and ease of sanitation.

Plastic Crates/Baskets/Bins Attached lid containers

Attached lid containers - Attached lid containers are the workhorse of the distribution
industry. These containers are used widely in retail distribution to ship small packaging to and
from distribution centers and stores. The attached lid containers can nest when the lids are
opened making them efficient for return freight.

Plastic Crates/Baskets/Bins - Hand

held plastic crates
Hand held plastic crates - are high quality stackable/nestable handheld containers that
can be used in supermarkets or your home.

Hand held plastic crates - are high quality stackable/nestable handheld containers that can be
used in supermarkets or your home.

Plastic Liquid Containers

Plastic liquid containers are containers used as an intermediate or final packaging for
products/materials in liquid form.

Plastic Liquid Containers - Pails

Pails - this round, open-head pails made from injection molding technology, are
engineered to satisfy the stringent requirements of many industries such as chemicals, dairy,
cleaning, and food processing.

Plastic Liquid Containers - Drums

Drums - Made from high-density polyethylene, these injection-molded plastic drums are
extremely strong and rigid allowing for easy handling and a low shipping cost.

Flexible Plastic

Flexible Plastic Packaging

Flexible plastic packaging is a major group of materials that includes plastic films that can be
used to make labels, wrappings, sacks, packs, pouches and sealed or unsealed bags.

Flexible Plastic Packaging

Ability to protect foods and extend the shelf-life;
Tough and durable to withstand rough handling during transport and

Handling convenience for both processors and customers,

Adds very little weight to the product which reduces transport costs;

Flexible Plastic Packaging

Easily printed on as labels to inform customers about
the product
Fit closely around the product which reduces space for
Attractive appearance to the mass consumers;
Mostly inert and unreactive
Good barrier properties to moisture and air.

Flexible Plastic Packaging

Barrier Properties
Barrier properties are the resistance that a package has to moisture, air,
light, micro-organisms, puncturing, etc.
It gives an indication of the amount of protection that is given to a food
by a particular packaging material.
Two Factors:
Water Vapor Transmission Rate (WVTR)
Oxygen Transmission Rate (OTR)
The higher the value of WVTR or OTR, the more permeable the material is to moisture or air.

Flexible Plastic Packaging

The polymers that are most commonly used for flexible plastic packaging
are low density polyethylene (LDPE) and linear low density polyethylene

Polyethylene (PE) films

It is the oldest thermoplastic film
It is the cheapest and most used plastic films used for food

Excellent heat sealability

It allows moisture and air to pass through at a higher rate than
many films.

It has very low barrier properties

It has poor resistance to oils
Susceptible to damage by sunlight which leads brittleness and
It is used as single layer to pack products requiring low protection
like: Frozen vegetables, Frozen Fish

Low Density Polyethylene (LDPE)


Low Density Polyethylene (LDPE)

Poor barrier properties to moisture and air;
Poor resistance to puncturing, although it does not tear
Does not protect foods against mechanical damage, thus,
require outer cartons or boxes for transport and distribution;
It has low melting point which makes it easily heat sealable.
However, the plasticizers used to make the film flexible can be absorbed by fats in foods
and may be linked to nerve damage to eyes and development of cancers. LDPE should not
therefore be used to package fatty foods (including cooking oils, butter, cheese or biscuits)
for long periods of time.

Low Density Polyethylene (LDPE)


High Density Polyethylene (HDPE)


Thick Polyethylene ;
Good barrier against moisture, air and odours;
Stronger, less flexible and more brittle than LDPE;
It has a higher softening temperature (121C);
It is a strong film that gives a strong heat seal
Ability to withstand puncturing, tearing and stretching;
Use as sacks for rough handling;
However, it is more slippery than jute, paper or other natural
Poor resistance to sunlight

Polypropylene (PP) films

A clear, glossy, transparent and sparkling film;
It is strong, heat sealable and withstands puncturing and
It does not stretch as much as Polythene
It has good barrier properties to moisture, air and odours
It is not damaged by sunlight nor affected by drying out by
low temperatures.
Suitable for larger heavy duty packs or as stronger packages(
e.g. pasta, pulses, dried fruits and cereal products)

Polypropylene (PP) films

There is no movement of plasticizers into fatty foods unlike polyethylene.
It has a higher sealing temperature than polyethylene
Because of its attractive, glossy appearance and better barrier properties, it is replacing
polyethylene in many applications. However it is more expensive than polythene.
Polypropylene is also woven into sacks for bulk transport of both fresh and processed
PP sacks are very tough and resist puncturing, tearing and stretching.
Allow moisture and air to pass through the weave (in contrast to HDPE sacks) and they
are therefore more useful for fresh produce or for foods that do not require protection
against these factors.

Cast Polypropylene (CPP) films

Better machinability properties than PE
Thickness range between 20 to 40
It is transparent with a more crystal-like
view than PE
It has very low protection barrier
Better printability properties than PE, but
still must be printed in flexo
Not used as laminating layer

Bi-Oriented Polypropylene (BOPP)


It is the most used thermoplastic film

Thickness range: 15 to 40 (most between 20-30)
It can be : transparent, white, opaque, metallized,
lacquered, pearly
It has very low heat sealing properties
Better barrier properties than PE or CPP
Excellent printability in flexo or rotogravure
Used as simple- or laminated layer
Used in snacks, pasta, dish was powders, biscuits, frozen

Flexible Plastic Packaging

Metalized Films
-application of a layer of aluminum to a polymers

-Lower cost and tare weight makes metalized films

a popular choice in the food and confectionary
-resistant to both water and oxygen transmission
as well as providing a metallic and glossy

Based on Erin Hoppes Flexible Packaging: Innovations and Developments

University of Wisconsin-Stout

Flexible Plastic Packaging

Smart packaging employed in plastic films:

Active packaging

Intelligent packaging

Based on Erin Hoppes Flexible Packaging: Innovations and Developments

University of Wisconsin-Stout

Flexible Plastic Packaging

Active Packaging Films

-employs moisture absorbers, temperature control packaging, preservative

releasers, oxygenscavenging, and carbon dioxide absorbers
-controls and reacts to outside influences that occur inside of the package:
light water, oxygen, microbial and chemical contamination

Based on Erin Hoppes Flexible Packaging: Innovations and Developments

University of Wisconsin-Stout

Flexible Plastic Packaging

Modified Atmosphere Packaging Films

-it modifies the internal environment of the package;

slows down natural deterioration; preserves the
products fresh state for a longer period of time
-Controls the transmission rate of oxygen and carbon
dioxide as well as the quantity of oxygen both inside and
outside of the package

Based on Erin Hoppes Flexible Packaging: Innovations and Developments

University of Wisconsin-Stout

Flexible Plastic Packaging

Intelligent Packaging Films

-involves a smart material that is capable of detecting a change in its

environment through any combination of indicators, sensors, and processors
-an automatic response takes place resulting in neither the product, package,
or consumer being compromised.

Based on Erin Hoppes Flexible Packaging: Innovations and Developments

University of Wisconsin-Stout

Flexible Plastic Packaging

Intelligent Packaging Films

-Antimicrobial films capable of controlling the growth of microorganisms in food

-conductive polymers and the lightemitting properties they posses
-it could be possible for the film to produce advertisements or signal lights

Based on Erin Hoppes Flexible Packaging: Innovations and Developments

University of Wisconsin-Stout

Future Innovations for Flexible Plastics

An ongoing trend in the packaging market is the development of materials which posses
highbarrier properties.

There is continuing research regarding biodegradable/compostable films and the push to make
them more widely available and utilized.
A recent application of foodgrade flavor molecules added to polymer structure has resulted
in the development of a film that releases odors/aromas on the inside or outside of a package

Based on Erin Hoppes Flexible Packaging: Innovations and Developments

University of Wisconsin-Stout