Dept of Chemical and Biomolecular Engineering

CN4203R Polymer y Engineering g g

Dr. Tong Yen Wah Dr Office: E5-03-15 Tel: 6516-8467 6516 8467 Email: chetyw@nus.edu.sg

Polymer Science vs Engineering

Polymer Science
Polymer chemistry and synthesis Polymer physics Structure and mechanical properties Characterization

Polymer Engineering
Post-synthesis processing of polymers Manufacturing of endproducts Reaction engineering

Class Schedule
Lectures : Tuesdays, 2 to 3 pm at E1 E1-06-01 06 01 Wednesdays, 9 to 11 am at E5-03-20 Tutorials T t i l : Tuesdays, T d 3t to 4 pm at E1-06-01

Course Outline
Week 1: Introduction
Basic concepts, definitions and nomenclature, types of polymers polymers, molecular weight

Week 1 - 3: Synthesis
Step-growth Step growth polymerization Chain-growth polymerization, i.e. free-radical, ionic and emulsion polymerization Copolymerization

Course Outline
Week 4 - 6: Physics
Structure and configuration, i.e. crystalline and amorphous amorphous, melting and glass transition Thermodynamics and molecular weight Characterization by GPC GPC, mass spectrometry spectrometry, NMR, IR, light scattering, viscosity Mechanical behaviour

Course Outline
Week 7 - 12: Polymer Processing Week 13: Review

Course Text
Principles of Polymer Processing (2nd Ed.), by Z. Tadmor and C.G. Gogos, 2006 Polymers: y The Elements of Polymer y Science & Engineering (3rd Ed.), by A. Rudin and P. Choi, 2013 Supplementary readings:
Introduction to Physical Polymer Science (4th Edition), b L.H. by L H Sperling S li , 2006 Introduction to Polymers (2nd Edition), by R.J. Young and P.A. P A Lovell, 1991

Course Assessment
Final exam:
May 6, 2014 (AM) 2 hours, all varieties of question types 50%

Quiz: Feb or March, 2013

During lecture 30 minutes, , short answer questions q 10%

Group Project

Group Design Project

Group work work, groups of 2 students each Form group and select topic by Jan 28, 2014 Presentation during last 6-7 weeks 40%

Course Website
On IVLE IVLE, search for module CN4203R Update your IVLE email, announcements will be made through IVLE Lecture notes and materials will be posted on IVLE workbin kbi IVLE forum is open to participation, questions and debate

Journals for Polymers

Macromolecules Advances in Polymer Science POLYMER A Acta Polymerica P l i Journal of Polymer Science, Part A (polymer chemistry) and Part B (polymer physics) Journal of Macromolecular Science Trends in Polymer Science Macromolecular Symposia Plastics Engineering

History of Polymers
Natural polymers 1820 natural rubber 1840 nitrocellulose it ll l 1870 celluloid 1910 first truly synthetic polymer : Bakelite 1930 to current present polymers

Names and numbers

mer mer - part of a repeating sequence Monomer molecule that combines with other monomers, , one basic repeating p g unit Polymer a large molecule that is composed of many y monomers ( (molecular weight g >5000?) ) Oligomer molecule with fewer monomers ac o o ecu e large a ge molecule o ecu e Macromolecule Repeat unit portion of polymer that is repeated

Names and numbers

How to name a polymer:
Look for monomer or repeat unit Identify y possible p p precursor Poly(precursor) H H eg. Polyethylene
C C H H n

P l (h Poly(hexamethylene th l adipamide) di id )
H N (CH2)6 ( H N C O (CH2)4 ( C O n

Names and numbers

Polymerization reaction of monomers to link up forming long chains Functionality number of bonding sites in a monomer available for polymerization Latent L t t functionality f ti lit functional f ti l groups that are not reacted during initial polymerization, l i ti eg. vulcanization, l i ti epoxy

Structure
Linear polymer straight chain Branched polymer with side chains bonded to main branch at branch points Network polymer 3D structure with many i t interconnected t d chains, h i d degree of f crosslinking

Homopolymers
Polymer from only one species of monomer, eg. polystyrene But also for p polymer y from one type yp of repeat p units, eg. poly(ethylene terephthalate) Structure:
A A A A
A n

Copolymers
Polymer from more than one species of monomer More commonly y used for p polymer y of more than one type of repeat unit, poly(A-co-B) p y distribution obeys y Statistical copolymer: statistics, poly(A-stat-B) Random copolymer: distribution is random, poly(A-ran-B)
A A A B A A B B B A

Copolymers
Alternating copolymer: repeat units alternate, poly(A-alt-B)
A B A B A B A B A B

Block copolymer: repeat units are in long sequences, polyA-block-polyB

A A A A A B B B B B

Copolymers
Graft copolymer: branch chains have different type of repeat units, polyA-graft-polyB
B B B B B B B B B B B B B B

A A A A A A A A A A

Other types of copolymers

Thermoplastics/Thermosets
Thermoplastic
polymer which soften and flows when heated cooling and heating cycle can be repeated

Thermoset
Rigid, normally are network polymers cooling and heating cycles very little

Elastomer
cross-linked rubbery polymer can be deformed (stretched) and recover quickly

Fibre
stretchable but breaks, only recovers partly

Plastic
intermediate tensile modulus, breaks when stretched

Natural Polymers
Poly(amino acids) Poly(saccharides) Poly(nucleotides) P l ( l tid )

Molecular Weight
Molar mass or molecular weight
Molar mass of one repeat unit multiplied by degree of polymerization (DPn or xn) M = xM0 A
n

Polymers have distribution of molar mass

Number average molar mass, Mn
Mn NM x M N
i i i i
2
i

Weight average molar mass, Mw

Mw NM N M
i i

wi M i

Molecular Weight
z-average g molar mass 3 N M i i Mw 2 N M i i

Polydispersity Index (PDI)

Breadth of molar mass distribution Typical polymer PDI = 1.5 2.0 Monodisperse M di polymer l PDI = 1 1.0 0

Mw PDI Mn

Also number-average DP, xn M n / M 0 Weight W i ht average DP, DP xw M w / M o