ChE 543: Brief Review of Material After Mid-term Exam

Chapter 4- Chain Growth Polymerization-Part 3: industrial processes

Polyethylene (PE)

PE types: LDPE, HDPE, LLDPE, etc.

LDPE process & applications

Polymethyl methacrylate (PMMA)

PMMA process & applications

Polyvinyl chloride (PVC)

PVC process & applications

Polystyrene (PS)

PS process & applications

Chapter 4- Chain Growth Polymerization-Part 4: free radical copolymerization

Monomer reactivity ratios

r1

k11
k12

r2

k22
k21

r= 0: no homo-propagation, r > 1: homo-propagation is preferred, r < 1: cross-propagation is

preferred

Mayo-Lewis model

Relates the instantaneous copolymer composition of monomer 1, F1, bound in the copolymer,
to the mole fractions of unreacted monomers, f1 and f2, via monomer reactivity ratios, r1 and
r2.

Instantaneous copolymer composition vs. monomer composition plot (Mayo-Lewis model)

Cumulative copolymer composition (Skeist equation)

Composition drift

Vertical distance between the instantaneous copolymer composition curve and the 45-line.

 Azeotrope (azeotropic) point

A point where no composition drift exists

Feed composition at azeotropic point

Determining reactivity ratios

Mayo-Lewis and Meyer-Lowry models

Error-in-Variables-Model (EVM) approach

Copolymer composition analysis

Elemental analysis

Residual monomer analysis

Spectroscopy

Copolymer sequence distribution

Copolymerization applications

Chapter 5- Emulsion Polymerization

Emulsion polymerization definition
Emulsion polymerization recipe components

Water (continuous phase), monomer, initiator, emulsifier (surfactant)

Stages (intervals) of emulsion polymerization

I. Polymer particle nucleation

Initiation (in the water phase)

Particle nucleation (Micellar/heterogeneous nucleation vs. Homogeneous nucleation)

At the end of stage 1: free micelles disappear & # polymer particles remains constant.

II. Polymer particle growth

Polymer particles grow by rapid diffusion of monomer from monomer droplets via
the aqueous phase into polymer particles

At the end of stage 2: separate monomer droplets disappear.

III. End of reaction: Polymerization goes into final stages

 Emulsion polymerization rate

Emulsion average chain length (molecular weight) or degree of polymerization

Emulsion polymerization benefits

Chapter 6- Polymer Properties & Characterization

Polymer physical states & transitions

States: Crystalline & amorphous

Transitions: glass transition temperature (Tg) & melting temperature (Tm)

Factors affecting Tm & Tg

Tg in polymer mixtures

Tg w1Tg .1 w2Tg .2

Differential scanning calorimetry (DSC)

Can measure Tg, Tm, Tc, degree of crystallinity, heat capacity, latent heat of crystallization &
melting

Chemical properties determination

Spectroscopy: 1H-NMR and C13-NMR spectroscopy

Chromatography: GPC

Elemental analysis

DSC

Tensile test

Stress-strain plot:
Yield stress, Tensile strength, Elongation at break, Youngs modulus, toughness
Stress-strain various behaviors:
Brittle vs. plastic vs. elastomer

Creep

Measures the change in length of sample (strain) with time under a constant stress

Stress relaxation

Measures the change in stress with time under a constant strain

Fatigue

Measure of sample performance as a result of the application of a prolonged cyclic or

intermittent stress
Reasons for failure:
Crack initiation & propagation
Thermal failure due to localized heating within sample

Hardness

Measures resistance of a sample against surface indentation/deformation

Impact

Measures resistance to breakage when the sample is dropped or struck by an object at high
velocity