UNIT 3 Synthetic Organic Polymers

By Asmita J. Kulkarni
Head of Engineering Sciences Department

Introduction
Natural Polymers
Proteins, Wood is cellulose Bones are polyphosphates Rocks are polysilicates DNA etc.

Synthetic polymers in the twentieth century

Today many are used on tonnage scales.

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Important Properties
Low density Resistance to chemical attack Electrical insulation Flexibility and good plasticity Ability to absorb shock, sound, vibrations Can be given attractive colors Can be strengthened by reinforcement Can act as good adhesives Can be transparent Can be drawn into strong fibers

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Disadvantages/Limitations
Combustible Soft and have high cost Limited temperature stability Limited mechanical strength Create problem of pollution

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Definitions and Important Terms

1. Polymer: It is a macromolecule having high MW, consisting of many repeating units of monomer, joined together in a regular fashion by covalent bonds. 2. Monomer: The individual low MW molecule having at least two reactive sites, used for synthesis of polymer, is known as a monomer. 3. Polymerization: It is the chemical process in which a large number of monomer molecules get linked to form the polymer molecules.
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3. Degree of Polymerization (DP): It is the number of monomers present in a polymer.

PE having DP 800 will have MW= 80028 = 22400 Strength of polymer increases with increase in DP. But too high DP causes high melt viscosity, and hence difficulty in processing.

4. Functionality Of Monomers: It is the number of reactive sites in the monomer molecule.

Molecule to behave as a monomer should have at least 2 reactive sites/functionality.
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Bifunctional monomer
Bifunctional: The number of reactive sites in the monomer molecule is two. On polymerization it forms linear polymer. Example:

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Trifunctional monomer
Trifunctional: The number of reactive sites in the monomer molecule is three. On polymerization it forms branched with some cross linked polymer.

Example:

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Tetrafunctional monomer
Tetrafunctional: The number of reactive sites in the monomer molecule is four. On polymerization it forms cross linked polymer. Examples:

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Polymerization reaction
Polymerization reactions are of two types:
A. Addition Polymerization or Chain Polymerization
i. Free radical mechanism ii. Cationic mechanism iii. Anionic mechanism

B. Condensation Polymerization or Step Growth Polymerization

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Addition Polymerization
Addition Polymerization is the chemical chain reaction in which a large number of monomer molecules get linked to form the polymer molecules. Features of addition Polymerization:

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Monomer contains double bond or triple bond. Initiator is required to start polymerization reaction. Reaction is exothermic and fast. No by-products formed. Polymer is exact multiple of monomer. Linear or branched polymer with dead ends is formed. Polymer formed has high MW
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Free Radical Mechanism

Definition:
Addition polymerization which is initiated by a free radical is known as free radical chain polymerization.

Free radical mechanism involves three steps:

Initiation
Propagation Termination

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Initiation of reaction
Initiation involves :
1. Initiator free radical: Initiators produce free radicals by homolytic dissociation induced by heat or light energy.

2. Production of monomer radical: Free radicals generated from initiator, attacks a monomer molecule and transfers free radical site to it.

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Propagation
Active monomer formed attacks the fresh monomer and transfers its active (radical) site on to next monomer. Successive addition of large number of monomer molecules take place

For every cleavage of pi-bond, 20 kcal energy is evolved.

Therefore this step is highly exothermic in nature.

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Termination
Growth of polymer is stopped / arrested by
a) Coupling: Two growing polymers couple to form a macromolecule. b) Disproportionation: One live polymer chain get oxidized while other get reduced simultaneously. c) Chain transfer: Live polymer abstracts a atom to terminate the reaction and forms dead polymer.

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Coupling
Coupling of active polymers: Two growing active/live polymer chains collide by their active sites to couple and convert them into dead polymer.

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Disproportionation
Disproportionation: One H atom of a radical centre is transferred to another radical centre, resulting in the formation of two polymer molecules, one saturated and the other unsaturated.

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Chain transfer
Chain transfer: Active polymer abstracts a atom from initiator, solvent or impurity to terminate the reaction and form dead polymer. At the same time new free radical is formed.

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Condensation Polymerization
A polymerization reaction in which monomers undergo intermolecular condensation in steps with continuous elimination of byproducts . Features of condensation polymerization:
Monomer contains functional groups. Reaction is endothermic and process is slow. By-products like H2O, NH3, CH3OH are eliminated Polymer is different from the monomers Linear, branched/cross-linked polymer with alive ends are formed. Polymer has comparatively low MW
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Step growth
Monomer + Monomer Dimer

Dimer
Trimer

+ Monomer Trimer
+ Monomer Tetramer

Tetramer + Monomer
And so on

Pentamer

Each reaction is associated with elimination of small molecule like H2O, HCl, CH3, CH3OH, NH3 etc
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H2N (CH2)6 NH2 + HOOC (CH2)4 COOH Hexamethylene diamine Adipic Acid NH2(CH2)6NHCO(CH2)4COOH + H2O Dimer + H2N (CH2)6 NH2 NH2(CH2)6NHCO(CH2)4CONH(CH2)6NH2 + H2O Trimer + HOOC (CH2)4 COOH NH2(CH2)6NHCO(CH2)4CONH(CH2)6NHOC(CH2)4COOH + H2O Tetramer [NH(CH2)6NHCO(CH2)4CO]n + nH2O Nylon 6,6
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Finally
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Comparison
Sr. No Addition/Chain Polymerization Condensation/Step Polymerization

Monomer has double bond.

Monomer has functional groups.

2
3 4 5

Initiator required
Exothermic reaction Polymer ends are dead No by-products

initiator not required

Endothermic reaction Polymer ends are alive By-products like H2O, NH3, CH3OH

6
7

Polymer is exact multiple of monomer. Produces linear or branched polymer. Fast process
Polymer has high MW E.g. PE, PVC

Polymer is different from the monomers Produces linear, branched or crosslinked polymer. Slow process
Polymer has comparatively low MW E.g. Nylon, polyester

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Molecular Weight of Polymer

Molecular Weight = DP MW of monomer

During polymerization, a number of polymer chains start growing and

Polymer molecules having different number of monomer units are formed. They have different MWs Polymer molecules differ in length and size Hence average value of the MW is considered.

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Average molecular weight

Polymer molecules, come in different sizes/chain lengths, so the average molecular weight will depend on the method of averaging.

Number average MW Weight average MW Viscosity average MW

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Number average MW
It is the ordinary arithmetic mean or average of the MWs of the individual macromolecules. It is determined by measuring the molecular weight of n polymer molecules, summing the weights, and dividing by n. The number average MW of a polymer can be determined by gel permeation chromatography, viscometry, and colligative methods like depression in freezing point, elevation in boiling point.
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Assume n number of molecules in a polymer sample P. n1 number of molecules have MW M1 , n2 number of molecules have MW M2 n3 number of molecules have MW M3 , n4 number of molecules have MW M4 And so on, ni number of molecules having MW Mi Total number of molecules is n =n1+n2+n3+n4+.. = ni Number fraction of fraction 1 = n1/n =(n1/ ni) Number fraction of fraction 2 = n2/n =(n2/ ni) and so on
Molecular weight contribution by fraction 1 = number fraction 1 MW = (n1/ ni) M1 = (n1 M1 / ni) Molecular weight contribution by fraction 2 = number fraction 2 MW = (n2/ ni) M2 = (n2 M2 / ni) Molecular weight contribution by fraction 3 = number fraction 3 MW = (n3/ ni) M3 = (n3 M3 / ni)

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Molecular weight contribution by fraction i = number fraction ith MW = (ni/ ni) Mi = (ni Mi / ni) Number average molecular weight of whole polymer will be sum of MW contribution by all fractions

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Weight average MW
It is the total contribution of all weight fractions of molecules towards the total mass of polymeric mass. It is determined by summing the weight fraction of each species multiplied by their molecular weight.

The weight average MW is determined by light scattering and ultracentrifugation methods.

In light scattering, the larger molecules contribute more because they scatter light more effectively.

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Assume a polymeric sample having weight W. W1 is the wt of polymer molecules having MW M1 W2 is the wt of polymer molecules having MW M2 W3is the wt of polymer molecules having MW M3 And so on, Wi is the wt of polymer molecules having MW Mi
Total weight of polymer is W =W1+W2+W3+.. = Wi Weight fraction of W1 fraction = W1 /W =(W1 / Wi) Weight fraction of W2 fraction = W2 /W =(W2 / Wi) Weight fraction of W1 fraction = W1 /W =(W1 / Wi) MW contribution by fraction 1 = Weight fraction 1MW = (W1M1 /Wi) MW contribution by fraction 2 = Weight fraction 2MW = (W2M2 /Wi) MW contribution by fraction 3 = Weight fraction 3MW = (W3M3 /Wi)
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MW contribution by fraction i = Weight fraction I MW = (WiMi /Wi) Weight average MW of whole polymer will be sum of MW contribution by all fractions

If W1 fraction has n1 molecules then W1 =n1w1 If W2 fraction has n2 molecules then W2 =n2w2 and so on Hence Wi = niwi
Thus,

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Viscosity average MW
Oldest method.

MW measured on the basis of viscosity of polymer solution.

The value of is obtained from [] = KM where

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K is constant, specific for given polymer is constant specific to polymer/solvent pair Value of lies between 0.5 to 1.0 [] is intrinsic viscosity
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 Relative viscosities r of the polymer solutions of known concentrations are determined by Ostwald viscometer

From the graph intrinsic viscosity is found

The graph helps to find

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if for the polymer is known.

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Relation between the MWs

The ratio of the weight average MW to that of number average MW is known as polydispersity index (PDI)

The values of molecular polydisperse polymer are

weights

for

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Significance of Average MW
Properties of polymers like melt viscosity, impact strength, tensile strength are directly dependent on average MW or DP of polymer.

For example,
tensile or impact strengths increases with MW The increase is limited to certain point Further it remains constant
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Significance of Average MW
Melt viscosity of polymer
rises more rapidly at high MW while at low MW it rises very slowly. Melt viscosity should be low for easy processing, with good strength.

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 Every polymer has a threshold value for its MW

Below which polymer does not possess any strength It exist as friable powder or liquid resin.

Experimentally observed that

Polymers do not possess any strength for DP < 30. Optimum strength for polymer at DP 600. The useful range of DP = 200 to 2,000 with approximate MW is 20,000 to 2,00,000. Solubility of polymer in a particular solvent decreases with increase in MW of polymer. Tg, Tm depend on MW of polymer.

Color, dielectric constant, refractive index are not changed by molecular weight.
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Crystallinity of Polymers
The extent to which polymer molecules are arranged in ordered pattern is known as crystallinity of Polymers. Polymers exhibit partial crystallinity- expressed as % crystalline. Polymer crystallinity is measured by differential scanning calorimeter DSC, X-ray diffraction, IR spectroscopy.
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Crystallinity of Polymers
Linear polymers show more compact and orderly arrangement.
They are hard, rigid, strong, brittle with high density & sharp MP.

Branched polymers are amorphous and have random arrangement of polymer molecules.
They are mechanically weak with broad softening temp.

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Factors affecting crystallinity

a) Branching of polymer
HDPE, linear polymeis is 90% crystalline, while LDPE, branched polymer 40% cystalline

b) Geometry of polymer
Isotactic (grps on one side), Syndiotactic (grps on eitherside) some crystalline, while Atactic (grps randomly placed) very less crystalline or amorphous (eg., polystyrene) Cis-polyisoprene less crystalline, trans polyisoprene more crystalline
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Factors affecting crystallinity

c) Intermolecular forces
Hydrogen bonding between the increase crystallinity. E.g., nylon 6,6 molecules

d) Bulky side groups

Bulky side grps leads to less crystallinity

e) Rate of cooling during crystallization

Fast cooling gives less time for macromolecules to arrange in a pattern
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Properties affected by crystallinity

Properties that increase with crystallinity
Density, hardness, stiffness, TS, Tg, chemical resistance,

Properties that decrease with crystallinity

Toughness, permeability to liquids or vapours, solubility in suitable solvent, optical clarity

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Glass Transition Temperature

Glass transition temperature (Tg):
The temperature below which polymers are hard and brittle and above which they become soft and flexible is called as glass transition temperature.

Melt temperature
Above certain temperature (Tm) the kinetic energy of polymer molecules is high such that it can flow like liquids. This state is called as visco-fluid state.

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Effect of Temp on specific volume

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Factors affecting Tg
Increase in Crystallinity increases Tg of polymers. Hence Amorphous polymers have lower Tg Cross linking and coiling leads to high Tg Branching in polymer reduces Tg

Plasticizer addition decreases crystallinity- hence Tg decreases

Straight chain polymers indicates high flexibility and hence low Tg
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Factors affecting Tg
Increase in MW leads to increase in density hence high Tg Bulky side groups on polymer chain increases Tg Functional group in polymer increases the intermolecular forces of attraction between the chains high Tg

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Significance
Polymer selected for any commercial application should have
Tg value far below the working temperature and Tm value far above the working temperature

If polymers are cooled below glass transition temp (Tg),

the polymer chains get entangled in each other, the polymer becomes hard and brittle behave like a glass and is brittle

Tg = Tm (for Symmetrical polymers) Tg = 2/3 Tm (for Unsymmetrical polymers)

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Thermoplastic Polymers
The polymers which become soft on heating and hard on cooling are known as thermoplastic or thermo softening polymers. Repeated heating and cooling do not alter the chemical nature of polymer. Changes involved are purely physical. Polyethylene (PE), Polyvinylchloride (PVC), Nylon, etc.
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Thermosetting Polymers
The polymers which get converted into infusible mass and insoluble mass on heating are called thermosetting polymers. Once the polymer has solidified (during preparation) cannot be softened on heating. Acquire 3-D cross-linked structure during molding process. Usually harder, stronger & brittle than thermoplastics. Phenol formaldehyde, Melamine formaldehyde, Urea formaldehyde, etc.
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Comparison
Thermoplastic resins Thermosetting resins Formed by condensation polymerization. 3-D network, prominent cross-links

1. 2. 3. 4. 5.

Formed by addition polymerization. Long chain linear, less cross-links

Can be molded and remolded again and again

Secondary bonds can be broken by pressure or heat.

Once molded cannot be remolded

Bonds do not break pressure or heat. on applying

Soften on heating & stiffen on cooling. Retain their original shape on heating

6.
7. 8.

Can be reclaimed from wastes

Soft, weak, and less brittle. Soluble in organic solvents

Cannot be reclaimed from wastes

Strong hard and more brittle. Insoluble in organic solvents

9.

E.g. PE, PVC, PMMA

E.g. PF, MF, epoxy resins

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