MS211

Ch. 13 Polymers

Spring 2009

Seokwoo Jeon
Department of Materials Science and Engineering
KAIST Institute for the NanoCentury

KAIST

Movie
 Introduction
• Polymers = “many mers”
= plastic (due to plastic deformation)
g y
• Chemical category
– Metal and ceramics : inorganic material
– Polymer : organic material

• Polymerization: the process by which long-chain

g or
network molecules are made from relatively small organic
molecules.
• Types of Polymerization
– Chain g
growth (additional
( polymerization)
p y )
– Step growth (condensation polymerization)
 Chain Growth
• Chain reaction of chemically activated monomers (i.e. from
reactive double bond to single bond)
Î additional polymerization by adding monomers
Ex 1. Vinyl
y chloride Æ ppolyvinyl
y y chloride

ƒ Polymerization is the joining of individual

monomers (e(e.g.,
g vinyl chloride,
chloride C2H3Cl) to
form a polymer [(C2H3Cl)n] consisting of
manymers (again, C2H3Cl).
 Chain Growth
Ex 2. ethylene Æ polyethylene H2O2 Æ 2OH-
initiator Hydrogen peroxide

Until ethylene monomers are fully

depleted
ƒ Detailed mechanism of polymerization by a chain growth
process (addition polymerization). In this case, a molecule of
hydrogen peroxide,
peroxide H2O2, provides two hydroxyl radicals,
radicals OH·
which serve to initiate and terminate. The polymerization of
ethylene (C2H4) to polyethylene -(C2H4)-n. (The large dot
notation ((·)) represents
p an unpaired
p electron. The jjoining
g or
pairing of two such electrons produces a covalent bond,
represented by a solid line(-).]

terminator
 Copolymer
A polymer derived from two or more monomers

Alternating copolymers
Periodic copolymers
(e.g.
(e g ((A-B-A-B-B-A-A-A-A-B-B-B))n)
Random copolymers
Block copolymers
Graft copolymers
p y

ƒ A copolymer of ethylene and

vinyl chloride is analogous to a
solid-solution metal alloy.

ƒ A blend of polyethylene and

polyvinyl chloride is analogous to
a metal alloy with limited solid
solution
Diblock copolymer

Prof. S. Kim’s work at KAIST

 Step Growth
Polymerization by reactive functional group (slower compared to chain growth)
Formation of phenol-formaldehyde
Two phenol molecules are linked by the formaldehyde molecule
Bifunctional Æ linear molecular structure
Polyfunctional Æ network molecular structure

Polyfunctional monomer

3-D network molecular structure

 Structural Features of Polymerization
Degree of polymerization length of the polymeric molecule, size of molecule, how
manyy mers, Viscosity,
y light
g scattering g

In case of 1D linear polymer

Root-mean-square length L = l m
109.5o
Extended length Lext = ml sin
2
 Structural Feature of Polymers
Higher degree of polymerization rigidity and melting point increases

Network molecular structure rigid, brittle

Linear molecular structure soft (due to Van der Waals bet. Chains)

Symmetry of chain

As the side groups become

l
larger and
d more irregular,
i l
Rigidity and melting point
Isotactic increases.
Why?
- Hindrance to molecular
Syndiotactic
sliding
- secondary bonding force

Atactic
 Interruption of Chain Structure

Branching Cross-linking

ƒ Transition from linear to network

structure. Vulcanization.
ƒ Branching involves adding a polymeric
Rubber+S2 Æ Polymerization
molecule to the side of the main
Accidently found by Charles Goodyear.
molecular chain.
 Thermal Behavior
Thermoplastic Polymers
Soft and deformable upon heating
Linear or branched polymeric molecules
General-use polymer
L
Low-density
d it polyethylene
l th l (LDPE)
Engineering polymer
high-density polyethylene (HDPE) ultra-high molecular-weight polyethylene
(UHMWPE) acrylonitrile-butadiene-styrene
(UHMWPE), acrylonitrile butadiene styrene (ABS)
Thermoplastic elastomers
Rigid elastomeric domains in a relatively soft matrix

Thermosetting Polymers
Hard and rigid upon heating
Network molecular structure formed by the step-growth mechanism
Enhanced by high temperature and irreversible
High strength and stiffness, not being recylable
Traditional elastomers
Adhesives
 Additives
1. Plasticizer
to soften polymer, low molecular weight

2 Filler
2.
to strengthen polymer, volume replacement to reduce cost.
short-fiber cellulose, asbestos, carbon black (tire rubber)
glass fiber (fiber glass reinforced plastic = FRP)

3. Stabilizer
to reduce polymer degradation by oxidation, thermal, or ultraviolet

4 Flame retardants
4.

5. Colorants
Pigment : insoluble
insol ble ~ TiO2, Al2O3-SiO
SiO2
Dyes : soluble ~ organic colorants