POLYMERS

Group Members
Seda KOCA Bengi AYDLEK Didem Bra KABAKI Gzde ERGN

11.11.2009 Hacettepe University

The Outline
Reactions of polymers

Addition Polymerization Step Growth Polymerization

Kinetic Of Polymerization
Polymerization Processes

Bulk Polymerization Solvent Polymerization Suspention Polymerization Emulsion Polymerization Special Processes

The Outline
Chemical and Physical Structures of Polymers Polymers molecular structures

Confriguration and conformation of polymers Chain structures of polymers

Physical Structures of Polymers

Polymer crystallinity Crystallinity and amorphousness of polymers

Outline
Types of Polymers and Polymer Processing Members of Polymers

Definition of Thermosets & Thermoplastics Common products and their properties

Forming Techniques of Polymers

Extrusion of polymers Injection Molding Blow Molding Thermoforming Compression Molding Casting

The Outline
Recycling of Polymers

Definiton of Recycling Why is recycling important? Benefits Recycling of polymers

Addition Polymerization (Chain Growth) Step Growth Polymerization (Condensation)

Differences between step-growth polymerization and chain-growth polymerization

Step-growth polymerization Chain-growth polymerization

Growth throughout matrix

Rapid loss of monomer early in the reaction Same mechanism throughout

Growth by addition of monomer only at one end of chain

Some monomer remains even at long reaction times Different mechanisms operate at different stages of reaction (i.e. Initiation, propagation and termination) Molar mass of backbone chain increases rapidly at early stage and remains approximately the same throughout the polymerization Chains not active after termination Initiator required

Average molecular weight increases slowly at low conversion and high extents of reaction are required to obtain high chain length Ends remain active (no termination) No initiator necessary

Step of Radical Chain Polymerization

Initiation

Propagation
Termination

INITIATION

PROPAGATION

TERMINATION
Dead Polymer i.) Coupling or Combination;

ii.) Disproportionation

CHAIN TRANSFER REACTIONS

Transfer to monomer reaction

Transfer to initiator reaction

Transfer to solvent reaction

IONIC CHAIN POLYMERIZATION

Using catalyst, not initiator
Highest reaction rate Termination step is just disproportionation Environment must be pure Reaction occurs in the cold

Anionic Polymerization=Living Polymerization

If the starting reagents are pure and the polimerization reactor is purged of all oxygen and traces of water, polimerization can proceed until all monomer is consumed.

CONDENSATION POLYMERIZATION
Using catalyst Minumum two functional groups required Usually linear Molecular weight increases slowly at low conversion High extents of reaction are required to obtain high

chain length

KINETICS OF POLYMERIZATION
Reaction rate of ionic polimerization more than

radicalic polimerization
So kinetics of ionic polimerization are not calculated But kinetics of radicalic polimerization can be

analysed

Kinetic of Radicalic Polymerization

Initiation;

Propagation;

Termination;

Kinetic of Radicalic Polymerization

Ro = overall rate of

polimerization
Rp = rate of chain

propagation
Ri = rate of initiation

step
Rt = rate of termination

step

Kinetic of Condensation Polymerization

Equivalent reactivity

of functional groups.
It may be first, second

or third order by depending upon.

Kinetic of Condensation Polymerization

Assumption = a stoichiometry balance of monomer concentration

POLYMERIZATION PROCESSES
Bulk Polymerization Solvent Polymerization

Suspention Polymerization
Emulsion Polymerization Special Processes
Electrochemical Polymerization
Radiation Polymerization Grow-discharge (Plasma)

Bulk Polymerization
The simplest technique It gives the highest-purity polymer
Ingredients : monomer,

monomer-soluble initiator, perhaps a chain transfer agent Advantages High yield per reactor volume Easy polymer recovery Final product form Disadvantages Difficult of removing the lost traces of monomer Dissipating heat produced during the polimerization

Solution Polymerization
Heat can be removed by conducting the polymerization in an organic solvent or

water
Initiator or monomer must be soluble in solvent Solvents have acceptable chain-transfer characteristics Solvents have suitable melting or boiling points for the conditions of

polymerization
Ingredients : monomer

initiator solvent

Advantages Temperature control is easy Easy removed

Disadvantages Small yield per reactor volume Solvent recovery

Suspention Polymerization
Coalescense of sticky droplets is prevented by PVA Near the end of polymerization, the particles harder and they can be

removed by filtration, then washing

Ingredients : water-insoluble monomer,

water-insoluble initiator, sometimes chain transfer agent suspention medium (water-usually)

Advantages (according to bulk polymerization) Forming process not using Stirring is easy

Disadvantages Polymer purity is low Reactor capital costs are higher than for solution polymerization

Separation process is easy

Emulsion Polymerization
Particles are formed monosize with emulsion polymerization

Polymerization is initiated when the water-soluble radical enters

a monomer-containing micelles.

Ingredients : water-insoluble monomer,

water-soluble initiator, chain transfer agent, dispersing medium (water), fatty acid, surfactant such as sodium salt of a long chain

Molecular structure of polymers

Typical structures are : linear (end-to-end, flexible, like PVC, nylon) branched cross-linked (due to radiation, vulcanization) network (similar to highly cross-linked structures,termosetting polymers)

Figure1. Schematic representation of (a) linear, (b and c) branched, and (d and e) cross-linked polymers. The branch points and junction points are indicated by heavy dots (Plastic Technology Handbook-Manas Chanda Salil K. Roy)

Chemical Structure of Polymers

Molecular configuration of polymers
Side groups atoms or molecules with free bonds, called free-radicals, like H, O, methyl affects polymer properties.

Stereoregularity describes the configuration of polymer chains : Isotactic is an arrangement where all substituents are on the same side of the polymer chain. Syndiotactic polymer chain is composed of alternating groups Atactic the radical groups are positioned at random

Figure 2: Isotactic Syndiotactic and Atactic combinations of a stereoisomers of polymer chain

(http://www.microscopy-uk.org.uk/mag/imgsep07/atactic.png)

Molecular configuration of polymers

FIGURE.3. Diagrams of (a) isotactic, (b) syndiotactic, and (c) atactic configuration in a vinyl polymer. The corresponding Fischer projections are shown on the right. (Plastic Technolgoy Handbook)

Table 1. Properties of Polypropylene Stereoisomers

(Plastic Technology Handbook)

Molecular configuration of polymers

Geometrical isomerism:
The two types of polymer configurations are cis and trans. These structures can not be changed by physical means (e.g. rotation). The cis configuration substituent groups are on the same side of a carboncarbon double bond. Trans the substituents on opposite sides of the double bond.

Figure4.cis trans configurations of polyisoprene

( http://openlearn.open.ac.uk/file.php/2937/T838_1_019i.jpg )

Conformations of a Polymer Molecule

Conformation The two atoms have other atoms or groups attached to them configurations which vary in torsional angle are known as conformations (torsional angle:The rotation about a single bond which joins two atoms ) Polymer molecule can take on many conformations. Different conformation different potential energies of the moleculeSome conformations: Anti (Trans), Eclipsed (Cis), and Gauche (+
or -)

Other Chain Structures

Copolymers polymers that incorporate more than one kind of monomer into their chain (nylon) Three important types of copolymers: Random copolymer contains a random arrangement of the multiple monomers. Block copolymer contains blocks of monomers of the same type Graft copolymer contains a main chain polymer consisting of one type

of monomer with branches made up of other monomers.

Figure 5 :Block Copolymer Graft Copolymer Random Copolymer

http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/struct/struct.htm

Physical Characteristics of Polymers

The melting or softening temperature molecular weight The molecular shape of the polymer has influence on the elastic

properties. coils the elasticity of the polymer

The structure of the molecular chains has an effect on the strength

and thermal stability. crosslink and network structure within the molecule the strength and thermal stability.

Polymer Crystallinity
Crystallinity is indication of amount of crystalline region in polymer

with respect to amorphous content

X-ray scattering and electron microscopy have shown that the

crystallites are made up of lamellae which,in turn, are built-up of folded polymer chains

Figure.6 Schematic representation of (a) fold plane showing regular chain folding, (b) ideal stacking oflamellar crystals, (c) interlamellar amorphous model, and (d) fringed micelle model of randomly distributed crystallites
(Plastic Technology Handbook)

Polymer crystallinity

Crystallinity occurs when linear polymer chains are structurally

oriented in a uniform three dimensional matrix. Three factors that influence the degree of crystallinity are:
i) Chain length

ii) Chain branching iii) Interchain bonding

Figure 7: Crystalline chain
http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/orient/Orient.htm

Polymer cristallinity
Crystallinity influences: Hardness,modulus tensile, stiffness, crease, melting point of polymers. Most crystalline polymers are not entirely crystalline. The chains, or parts of chains, that aren't in the crystals have no order to the arrangement of their chains Crystallinity makes a polymers strong, but also lowers their impact resistance Crystalline polymers are denser than amorphous polymers, so the degree of crystallinity can be obtained from the measurement of density Wc=cc/ density of entire sample c density of the crystalline fraction. c volume fraction Wc mass fraction

Determinants of Polymer Crystallinity

The degree of crystallinity of a polymer depends on the rate of cooling

during solidification as well as on the chain configuration.

In most polymers, the combination of crystalline and amorphous

structures forms a material with advantageous properties of strength and stiffness.

Figure 8: Mixed amorphous crystalline macromolecular polymer structure (http://web.utk.edu/~mse/Textiles/Polymer%20Crystallinity.htm)

Polymer cristallinity
Polymer molecules are very large so it might seem that they could not

pack together regularly and form a crystal. Regular polymers may form lamellar crystals with parallel chains that are perpendicular to the face of the crystals.
amorphous portion. The crystalline portion is in the lamellae, and the amorphous portion is outside the lamellae .

A crystalline polymer consists of the crystalline portion and the

Figure 9. Arrangement of crystalline and amorphous portions

http://pslc.ws/mactest/crystal.htm#structure

Cristillanity and amorphousness

An amorphous solid is formed when the chains have little orientation

throughout the bulk polymer. The glass transition temperature is the point at which the polymer hardens into an amorphous solid. In between the crystalline lamellae,regions with no order to the arrangement of the polymer chains amorphous regions Polyethylene can be crystalline or amorphous. Linear polyethylene is nearly 100% crystalline. But the branched polyethylene is highly amorphous.

Figure 10.Linear and Branched Polyethylene

(http://pslc.ws/macrog/kidsmac/images/pe03.gif )

Examples...
Highly crystalline polymers:

Polypropylene, Nylon, Syndiotactic polystyrene.. Highly amorphous polymers: Polycarbonate, polyisoprene, polybutadiene Polymer structure and intermolecular forces has a major role of a polymers crystallinity.

Classification of Polymers
with regard to their thermal processing behavior ;

Thermoplastic Polymers (Thermoplastics)

soften when heated and harden when cooled

Thermosetting Polymers (Thermosets)

once having formed wont soften upon heating

Thermoplastics
have linear or branched structure

chains are flexible and can slide past each other

 have strong covalent bonds and weak intermolecular van der Waals bonds
elastic and flexible above glass transition temperature can be heat softened, remolded into different forms

reversible physical changes without a change in the chemical structure

Thermosets
chains chemically linked by covalent bonds
hardening involves a chemical reaction which connects the linear molecules together to form a single macromolecule.

Thermosets
once polymerization is complete, cannot be softened, melted

or molded non-destructively.
have higher thermal, chemical and creep resistance than

thermoplastics
Thermosets suitable materials for

Composites Coatings Adhesive applications

Common thermoplastics
Commodity Polymers
POLYETHYLENES POLYPROPYLENE POLYSTYRENE POLYVINYLCHLORIDE-PVC POLYMETHYLMETHACRYLATE-PMMA

Engineering Polymers(have a thermal resistance 100-150C)

POLYCARBONATE NYLON(POLYAMIDE) POLYETHYLEN TEREPHATALATE-PET

High Performance Polymers (have a thermal resistance >150C)

POLYTETRAFLUOROETHYLENE-teflon POLYARYLETHERKETONES-PEEK

POLYETHYLENE
prepared directly from the polymerization of ethylene (C2H4).
two main types are; low-density (LDPE) and high-density

polyethylene (HDPE)
Advantages

cheap good chemical resistance high impact strength

 Limitations

low heat resistance (upper temperature limit is 60) degrade under UV irradiation. high gas permeability, particularly CO2
Applications

extensively for piping and packaging chemically resistant fittings, garbage bags containers, cable covering

POLYPROPLYLENE
improved mechanical properties compared to polyethylene;

has a low density (900915 kg/m3), harder, and has a higher strength Good chemical and fatigue resistance
Disadvantages

Oxidative degradation, high thermal expansion, high creep poor UV resistance Applications medical components, films for packaging (e.g. cigarette packets)reusable containers, laboratory equipment

POLYSTYRENE
a light amorphous thermoplastic
Advantages

low cost, easy to mould, rigid, transparent no taste, odor, or toxicity, good electrical insulation Disadvantages sensitive to UV irradiation (e.g. sunlight exposure) chemical resistance is poor, brittle Applications CD-DVD cases, electronic housings, food packaging, foam drink cups and egg boxes

POLYVINYLCHLORIDE-PVC
was the first thermoplastic used in industrial applications
very resistant to strong mineral acid and bases, good electrical

insulators, flame-retardant
Two grades of the PVC material are available:

rigid PVC is used in the construction industry for piping cold water and chemicals flexible PVC is used in wire and cable coating, paints, signs

Common thermosets
EPOXIES UNSATURATED POLYESTERS

PHENOL FORMALDEHYDE (PHENOLIC)

POLYURETHANES

EPOXIES
Advantage

mechanically strong, highly adhesive good chemical and heat resistance electrical insulators Disadvantage expensive Applications as industrial adhesives, coatings or as matrices in advanced reinforced plastics and also as encapsulation media

UNSATURATED POLYSTERS
Advantage hard, high strength cheap compared to Epoxy good electrical insulator high heat resistance Disadvantage poor solvent resistance compared to other thermosets Applications molding or casting materials for a variety of electrical applications, matrix for composites such as fiberglass boats, fences, helmets, auto body components

PHENOLICS
most commonly used thermosets
high hardness, excellent thermal stability; low

tendency to creep
Applications wiring devices, bottle caps, automotive parts, plugs and switches, as adhesives coatings and molded components for electrical applications

POLYURETHANES
depending on the degree of cross-linking they behave as

thermosets or thermoplastics
low cost, high impact strength, high adhesion properties be processed into coatings, adhesives, binders, fibers and

foams

Methods of polymer fabrication

Extrusion of polymers Injection Molding Blow Molding Thermoforming Compression Molding Casting

Extrusion of polymers
method used mainly for thermoplastics
is a continuous process as long as raw pellets are supplied is a process of manufacturing mostly long products of constant

cross-section; i.e.. rods, sheets, pipes, films, wire insulation coating

 extrusion
pelletized material is successively compacted, melted and

formed into a continuous charge of viscous fluid temperature of the material is controlled by thermocouples
forcing soften polymer through a die with an opening

the product going out of the die is cooled by blown air or in

water bath

extruder

Injection Molding
most widely used technique for thermoplastics
highly productive method, profitable in mass production of

large number of identical parts

polymer in form of pellets is fed into machine and is pushed

forward into a heating chamber then the molten plastic is forced through a nozzle into the enclosed mold cavity pressure is maintained until solidification and then the mold opens and the part is removed

Blow Molding
is a process in which a heated hollow thermoplastic tube

(parison) is inflated into a closed mold disposable containers, recyclable bottles, automotive fuel tanks, tubs are produced involves manufacture of parison by extrusion, injection or stretching

 parison in a semi molten state is placed in a two piece mold

having the desired shape

parison is inflated by air blown, taking a shape conforming that

of the mold cavity

parison is then cut on the top, mold cools down, its halves

open, and the final part is removed

Thermoforming
is a process of shaping flat thermoplastic sheet
softening the sheet by heat, followed by forming it in the mold

cavity Thermosets can not be formed by the thermoforming because of their cross linked structure widely used in the food packaging industry; manufacturing of

Thermoforming methods
three thermoforming methods, differing in the forming stage:
1. Vacuum Thermoforming; shaping a preheated thermoplastic

sheet by means of vacuum produced in the mold cavity

2. Pressure Thermoforming;... by means of air pressure.

3. Mechanical Thermoforming;... by direct mechanical force

Thermoforming by vacuum and mechanical force

Compression Molding
used mostly for molding thermoset resins
pre-weighed amount of a polymer mixed with additives is

placed into the lower half of the mold polymer is preheated prior to placement into heated mold cavity ,half of the mold moves down, pressing on the polymer charge and forcing it to fill the mold cavity
suitable for molding large flat or moderately curved parts; side

panels for automotive, electric housings etc.

Casting
both thermosets and thermoplastics may be cast.
molten polymer is poured into a mold and allowed to solidify for thermoplastics solidification occurs upon cooling

while thermosets hardening is a consequence of polymerization reaction

REFERENCES
Franois Carderelli, Materials Handbook: A Concise Desktop

Reference,2nded.,Springer Donald Hudgin, Plastics Technology Handbook, 4th ed., Taylor & Francis Group J. A.Brydson, Plastics Materials, 7thed., Heinemann William D. Callister ,Materials Science and Engineering,7th ed., Wiley http://www.substech.com http://www.azom.com http://en.wikipedia.org

Recycling: A Sector of Solid Waste Management

http://environment.utk.edu/policy.html

What is Recycling?
Recycling refers to the process of collecting used materials which is usually considered as waste and reprocessing them. Recycling varies from re-use in the sense that while re-use just means using old products repeatedly, recycling means using the core elements of an old product as raw material to manufacture new goods.

Why Recycling is Important?

Recycling Saves Energy
Recycling Saves Environmental Conditions and Reduces

Pollution
Recycling Saves Natural Resources Economic Benefits Recycling Saves Space for Waste Disposal

Benefits
Conserves Resources Prevents emissions of greenhouse gasses & water pollutants Supplies valuable raw materials to industry Saves tax-payer dollars Creates jobs Stimulates development of greener technologies Reduces the need for new landfills and incinerators

Recycling of polymers
Recycling of Polymers

Chemical recycling Mechanical recycling Energy recycling

Chemolysis Glycolysis Methanolysis Hydrolysis

Thermolysis Pyrolysis Hydrogenation

Why do we use mechanical, chemical and energy recycling?

Hence mechanical recycling is realy best suited to clean plastic

waste,such as packaging material. Chemical recycling of waste plastics is important issue.

We have applied reaction in water or organic solvent in sub- or supercritical condition to convert polymers into its monomers.
Condensed polymers such as polyethylene terephthalate or nylon 6 were depolymerized to its monomers by hydrolysis of alcoholysis in supercritical water or alcohol.

Conclusive Facts
1 t = 20,000 plastic bottles
25,000 t of bottles recycled in the UK in 2003 saved approximately

25 million kWh of energy

25 recycled PET bottles can be used to make an adults fleece jacket Recycling a single plastic bottle can conserve enough energy to light

a 60 W lightbulb for up to 6 h

SOME PHOTOS

We have done it!!!

Ref: http://www.container-recycling.org/ assets/ppt/1PlasticDebrisConference9.ppt

Look at the changes you could make with recycling...

http://environment.utk.edu/policy.html

 http://www.buzzle.com/articles/why-is-recycling-important.html http://www.chevroncars.com/learn/wondrous-world/recycling-process

REFERENCES

www.container-recycling.org/ assets/ppt/1PlasticDebrisConference9.ppt
Franois Carderelli, Materials Handbook: A Concise Desktop

Reference,2nded.,Springer
Donald Hudgin, Plastics Technology Handbook, 4th ed., Taylor & Francis

Group

REFERENCES
J. A.Brydson, Plastics Materials, 7thed., Heinemann William D. Callister ,Materials Science and Engineering,7th ed., Wiley http://www.substech.com http://www.azom.com http://en.wikipedia.org

REFERANCES
Plastic Technology Handbook, 4th Edition, Authors: Manas Chanda,Salil K.

Roy
http://pslc.ws/mactest/crystal.htm#structure http://plc.cwru.edu/tutorial/enhanced/FILES/Polymers/struct/struct.htm