Virginia Tech: Polymer Materials and Interfaces Laboratory

Emulsion Polymerization of Styrene

EmulsionPolymerization
Emulsion Polymerization General Kinetic Features and Particle Mechanisms of Emulsion Polymerization Number of Polymer Particles Rate of Emulsion Polymerization
Size Ranges of Heterogeneous (Particle Initially 3 Components:
•ADVANTAGES Forming) Polymerization Processes 1. Colloidally dispersed soap micelles N = k (Ri/)2/5(asS)3/5 Rp = kp [M]N/2N A
- Faster Rates swollen with monomer, diameter ~50Å
Polymer (50 to 100 soap molecules per micelle) Rp = Rate of Emulsion Pzn
- Higher Molecular Weights N = Number of Particles

Nucleation and Growth

Emulsion Polymer Particles 2. Macrodroplets of Monomer stabilized by
- Good Heat Transfer soap, diameter ~15,000 Å S = Surfactant Concentration Kp = Rate Constant
- May be directly usable (Latex) Emulsifier Free Emulsion Polymer
3. Aqueous Phase Critical Micelle as = Interfacial Surface area [M] = Monomer Concentration

Rate of Polymerization
Concentration
- 500-5000Å Dispersion Polymerization A. Initiator Ri = Rate of Initiation N = Number of Particles
• DISADVANTAGES B. Electrolyte to stabilize latex = Avogadro’ Number
Precipitation Polymerization
Direct Conversion of
Monomer Droplets C. Possibly a Buffer
 = Rate of Increase of Volume
-Recovery of solid polymer more difficult
Suspension Polymerization
-Removal of emulsifier difficult High particle numbers associated with
0.01 0.1 1.0 10 100 1000 Soap Concentration small particle size
Particle Size Range (m)

EmulsionPolymerization
Emulsion Polymerization Scheme
Scheme Emulsion Polymerization Kinetic Stages C a te g o rie s o f S u rfa c ta n ts Polymerization Process
INTERVAL III • A n io n ic O

No Droplets
– C a r b o x y la te s (s o a p s ) R • Set up reactor apparatus and set oil bath to 75ºC
100

Monomer in Polymer Particles ONa

Constant Number of Particles
R S O 3N a
• Disperse 0.5 g sodium lauryl sulfate (surfactant)
Monomer Micelle Polymer
III – A lk y l b e n z e n e s u lfo n a te s in 55 mL oxygen-free H2O for 5 minutes in the
80

reactor (CMC is met)

Conversion (%)

Monomer INTERVAL II
No Micellar Soap
II Monomer in Droplets
• N o n io n ic R O • Add 22 mL styrene (monomer), wait 3-5 minutes
H
(diffusion into micelles) and add 0.05 g
60

I Monomer in Polymer Particles – A lk y l p h e n o l e th o x y la te s O

n
Continuous Constant Number of Particles potassium persulfate dissolved in 5 mL H2O
Phase:
I R. – E th y le n e o x id e / P r o p y le n e o x id e c o p o ly m e r s (initiate particle formation)
40

Water Monomer O OH • After polymerization, coagulate polymer in

Droplet INTERVAL I
Monomer in micelles (dia ~50 Å) • C a tio n ic H
n
O
m concentrated alum solution, wash with methanol,
filter by suction and dry in a vacuum oven
20

soap Monomer in droplets (dia ~ 106 Å) – B e n z y ltr im e th y la m m o n iu m b r o m id e CH 3

Monomer in polymer particles H 3C
CH 3
overnight.
Growing number of particles N +
B r-
Time (hrs) CH 3