Unit II - Lesson Schedule POLYMERS AND COMPOSITES Objective To make the student conversant with the principles of polymer

chemistry and applications of polymers in industries

Lecture

Topics to be covered

Introduction Polymer definition Types of polymerization

2 &3

Classification Various Modes with appropriate examples

4 &5

Plastics Preparation , Properties and Uses of Thermoplastics Preparation , Properties and Uses of Thermosettes

Mechanism of Polymerization Free radical polymerization

7 Butyl rubber SBR Vulcanisation

Rubber

Composites 8 and 9 Polymer matrix Fiber Reinforced Plastics

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Polymers
Poly means many Mer means unit Polymers are macromolecules formed by the combination of many small molecules called monomers. The molecular weight of polymer ranges from 500 to 106. The process of formation of polymer from monomers is called polymerisation. Degree of polymerization (DP) is the number of repeating units (monomers) present in the polymer DP = mol.wt of polymer mol.wt of monomer Example: Polyethylene is made of repeated linkages of ethylene (monomer) n CH2 = CH2 Ethylene (monomer)

- ( CH2 CH2 - ) n polythene

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Functionality The number of reactive or bonding sites present in the monomer is called its functionality. Monomers which possess more than one reactive site alone can undergo polymerization.

Functionality

Examples

CH4 , CCl4 , C6H6 ROH , RCl , RCOOR, RNH2 Amino Acids , CH2 = CH2 (ethene), CH2OH CH2OH (glycol) CH2OH CHOH CH2OH (glycerol) C6H5OH (phenol) CH CH (acetylene)

All monomers are molecules but all molecules are not monomers For example Water is a molecule but does not undergo polymerization. On the other hand ethylene molecule, polymerises to give polyethylene hence it is a monomer. In other words for a molecule to become monomer it should have at least two bonding sites ie. Its functionality should be at least 2.

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Classification 1. Based on the Type of Monomer Homo polymer Prepared by the self polymerization of same type of monomers (A) - CH2 ( CH2 CH2 ) CH2 CH2 (polyethene)

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Types: based on the arrangement of monomers Linear homopolymer: (HDPE)

Branched homopolymer: (LDPE)

A A

Cross linked polymer (Poly Acetylene)

A A

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Heteropolymer / Copolymer: Prepared by cross polymerization of of two or more types of monomers Example: Nylon 6,6 , Urea formaldehyde , Buna S- rubber etc.,

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Het eropol ymer / copol ymer

Many mer mer mer mer mer mer mer mer mer

Co (toget her) polymer H H H H H | | | | | -C C = C C C | | | H H H m H | C | CN

Buna- N n

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Types of hetero pol ymer

mer

&

mer

combi ne i n different ways - can be li near, branched, cross-li nked random copol ymer mer mer mer mer A lternati ng

mer

mer mer mer

mer mer mer mer mer

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2. Block pol ymer

mermer mer mer mer mer mer mer mer mer mer mer mer mer

- A A A B B B B A- A A B B B B

Graft pol ymer - branched pol ymer - one ki nd of monomer ( A) in the mai n chai n and another ki nd ( B) in the si de chai n A A A
B B B
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2. Based on Origin Natural, Synthetic and Semi synthetic Natural: Cellulose, Starch, Proteins etc., Semi synthetic: Ethyl Cellulose, Cellulose Acetate, Carboxy methyl cellulose (CMC) Synthetic : PE , PS ,PVC , PVA etc., Silicone is an inorganic synthetic polymer

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3. Based on main chain (back bone/ skeleton) i) Homo chain: made up of single type of atom (ex) PE , Buna Srubber

ii) Hetero chain: made up of different types of atoms (ex) nylons,

polyesters, PVA, PVAc etc.,

4. Based on molecular forces (thermal behaviour)

Thermoplastics / Thermoforming Plastics: Ex. PE, PP, PVC, PS Thermosetting plastics: Ex. Bakelite, Urea- formaldehyde, Epoxy resins etc

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Thermoplastics (TP)

Thermosettes (TS)

They are formed by addition polymerization

They are formed by condensation polymerization

They are linear / branched long chain polymers

They consist of three dimensional network structure joined by strong covalent bonds

On cooling they get hardened

On heating they get hardened

Softens on heating , because Vander Waals forces existing between the individual chains can break easily by heat and pressure

They do not soften on heating because the covalent bonds retain their strength on heating

They can be remoulded any number of times

Once set, they cannot be remoulded

They are soft, weak and less brittle

They are hard, strong and more brittle

5. Based On Application (a)Resins: Half polymerized polymers are called resins They are used as ion exchangers and in the preparation of adhesives (b) Fibres: Usually polymers with high tensile strength will be drawn into wires. Examples: PET, nylons etc., (c) Elastomers (Ex) rubbers (d) Plastics ; TP and TS
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6.

Method of synthesis

Addition polymer: Polymers prepared by addition reaction Ex.: PE,PVC,PVA , PS, Buna S-rubber etc., Condensation polymer: Polymers prepared by condensation reaction. Ex.: Poly amides, Poly Esters, Poly Ethers, PET, Bakelite, PC, Poly Urethane etc.

Addition Polymerization / Polymers

Condensation polymerization / Polymers

Monomers add on to give polymers without the forming by prducts

Monomers condense to give polymers and by products like H20, HCl, MeOH etc. are formed.

Monomers must have atleast one double bond

Monomers must have atleast two identical or different functional groups

It is a chain forming reaction

It is a step wise reaction

The polymer product is formed at once

The polymer product is formed stepwise steadily

Molecular weight of the polymer is an integral multiple of the molecular weight of the monomers

Molecular weight of the polymer is less than the integral multiple of the monomers

Mostly Thermoplastics are obtained

Mostly Thermoset resins are obtained

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