Advanced Materials 11-18/06/2007 1

Part I + II
Advanced Materials 11-18/06/2007 2
Homogeneous Systems:
Bulk polymerization
Solution polymerization
Polymerization Techniques
Miniemulsion polymerization
Dispersion or Latex
Heterogeneous Systems:
Precipitation polymerization
Dispersion polymerization
Suspension polymerization
Emulsion polymerization
Bulk polymeric mass
Advanced Materials 11-18/06/2007 3
Mechanisms of Polymerization
Initiation in the presence of ion (cationic or anionic)
Group-transfer polymerization
Polyaddition, etc.
Initiation in the presence of free radicals
Applied to wide range of monomers
Broad scope of experimental conditions
Molecular weight can be controlled
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Free Radical Polymerization
Initiation (Start):
generation of free radicals
reaction with monomer to form growing chains
I
2 R
k
d
R + M R
1
k
i
k
d
is a first order rate constant; the values are in the range: 10
-4
10
-6
s
-1
Rate of radical production:
] I [ k 2
dt
] R [ d
d
=
H
3
C C
CN
CH
3
N N C
CN
CH
3
CH
3
Example of thermal initiators:
Advanced Materials 11-18/06/2007 5
Propagation (Growth):
monomer is added at the active center
growth of the polymer chain.
Free Radical Polymerization
M
i
+ M
k
p
M
i+1
] M ][ M [ k R
p p
=
Assumption:
the reaction rate constant k
p
is independent on chain length (after i=5-10)
Rate of reaction:
Termination (Stop):
chain growth stops by bimolecular reaction of two growing radicals
Termination by combination
Termination by disproportionation
M
i
+ M
j
k
tc
M
i+j
M
i
+ M
j
k
td
M
i
M
j
+
2
t t
] M [ k 2 R = Rate of termination:
Advanced Materials 11-18/06/2007 6
Emulsifiers/Stabilizers
Main actions: - reducing the interfacial tension between the phases
- forming a barrier between the phases
Emulsifiers (or soaps) small amphiphilic molecules that form discrete
nanometer size micelles after CMC concentration, e.g. sodium dodecyl
sulfate (SDS).
M
w
=288.38 g/mol
Stabilizers (suspension agents) polymeric or oligomeric molecules, e.g.
polyvinyl alcohol (PVA). Usually can't form regular shape micelles due to the
molecular weight distribution.
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Precipitation Polymerization
Monomer dissolves in continuous phase and does not swell polymer
Polymerization medium is a precipitant for the resulting polymer
e.g. - water-based polymerization of acrylonitrile
- polymerization of styrene in hexane or ethanol
Particles are polydisperse
Size range: 0.1 1000 m
Particle formation (Nucleation):
Homogeneous nucleation
Coagulative nucleation
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Dispersion Polymerization
Monomer dissolves in continuous phase and does not swell polymer
Polymerization medium is a precipitant for the resulting polymer
Presence of stabilizer
e.g. - water-based polymerization of acrylonitrile
- polymerization of styrene in hexane or ethanol
Particles are monodisperse
Size range: 0.1 10 m
from: J .-S.Song, M. A. Winnik, Macromolecules, 2005, 38, 8300
Particle formation (Nucleation):
Homogeneous nucleation
Coagulative nucleation
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Suspension Polymerization
Water insoluble monomer is dispersed in water
Initiator dissolved in monomer
Stabilization of droplets/polymer particles with non-ionic stabilizers,
e.g. polyvinyl alcohol
Equivalent to bulk polymerization, small droplets dispersed in water
Particles are polydisperse/monodisperse
Size range: 10 1000 m
Particle formation (Nucleation):
Droplets nucleation
Advanced Materials 11-18/06/2007 10
Emulsion Polymerization
Water insoluble monomer is dispersed in water
Initiator dissolved in water phase
Presence of emulsifier, i.e. micelle formation
Particles are monodisperse
Size range: 0.05 2 m
Particle formation (Nucleation):
Homogeneous nucleation
Micellar nucleation
Coagulative nucleation
NO nucleation inside the droplets
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Particle nucleation
Stage I
Particle growth
Stage II
Stage III
Monomer only in particles
NO secondary nucleation
Consumption of monomer rest
Emulsion Polymerization Stages
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Stage I Stage II Stage III
Stage I: Particle nucleation
Stage II: Particle growth at constant rate
Stage III: Consumption of the monomer rest
Three intervals (Harkins theory)
Emulsion Polymerization
M
o
n
o
m
e
r

c
o
n
v
e
r
s
i
o
n
,

%
Time
Stage I Stage II Stage III


R
a
t
e

o
f

p
o
l
y
m
e
r
i
z
a
t
i
o
n

(
R
p
)
S
u
r
f
a
c
e

t
e
n
s
i
o
n

(

)
Monomer conversion, %
Disappearance of
micelles
Disappearance of
droplets
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Advantages:
Efficient heat transfer
Low viscosity even at high solid content
High monomer conversion
High rates of polymerization
High molecular weights can be achieved
Direct application of the final product
High surface area of particles
Disadvantages:
Contamination of product with additives, e.g., surfactant
Not easy to control in the case of hydrophilic monomers
Suspension/Emulsion Polymerization
Advanced Materials 11-18/06/2007 14
6 . 0 4 . 0
) ( ) / ( AS k N
p
=
- rate of radical formation; - rate of increase in volume of polymer particle
Emulsion polymerization
Number of particles
A - interfacial area occupied by surfactant molecule
S - total concentration of surfactant in the micelle
Rate of polymerization
[ ]
p p p
M n k R =
k
p
- polymerization rate constant; n - corresponds to the radical concentration
[M
p
] monomer concentration in monomer-polymer particles
[ ]
*
~M R
p
Degree of polymerization
[ ]t M k P
p p p
=
t interval of successive entries of radicals into monomer-polymer particle
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Techniques of emulsion polymerization
A. Batch
B. Semicontinuous:
Stage I: production of defined number of reaction sites (seeds)
Stage II: addition of second monomer, ( starved feed condition)
M2
~ 40 nm
~ 200 nm
core-shell particle
M1
~ 200 nm
M1, M2
core-shell particle
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Raspberry-like
M1, seed polymer
M2, 2-nd stagepolymer
Multilayers
Core-shell
InverseCore-shell
Hemisphere
Sandwich
Confetti-like
Microdomains
Snowman-like
Two-phase particle morphologies
Thermodynamically driven Kinetically driven
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Applications of core-shell particles
Coating
Paints
Adhesives
Cosmetics
Pharmaceutical
Super-absorber (diapers)
Paper coating, etc.
high T
g
low T
g
vitamins, medicament
T, pH, UV sensitive shell
highly crosslinked core
low crosslinked shell
Polyacrylic acid
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Polymers via Emulsion Polymerization
Water based latex paints Polyacrylates
Engineering plastics, household
appliances,
Automobile parts, Luggage
Acrylonitrile-Butadiene-Styrene
(ABS)
Fuel tanks, Gasoline hoses, Adhesives,
Impregnated paper, leather and textiles
Butadiene-Acrylonitrile
(nitrile rubber)
Tires, Belting, Flooring,
Molded goods, Shoe soles, Electrical
insulation
Styrene-Butadiene Rubber
(SBR)
Applications
Polymer
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Nanodroplets:
stable
small
homogeneous in size
high shear
Phase II
Phase I
Reactions in miniemulsions
reaction
1:1 copy of droplets
(nanoreactors)
50-500 nm
Advanced Materials 11-18/06/2007 20
+
collision and
fusion of
oil droplets
coalescence:
diffusion of oil
through the
water phase
Ostwald ripening:
Suppression of Ostwald ripening:
Addition of a hydrophobic agent
With lowwater solubility:
Suppression of coalescence:
Effective surfactants
Growth of droplets
K. Landfester, Macromol. Symp. 2000, 150, 171-178.
Force: OSMOTIC pressure versus LAPLACE pressure
Force: OSMOTIC pressure versus LAPLACE pressure
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Reactions in droplets
Polymerization, e.g. radical, polyaddition, polycondensation, enzymatic, etc.
M
polymer particle
200 nm
50 nm 50 nm 50 nm
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Copolymerization
M1
M2
Phase
separation
or
Reactions in droplets
Advanced Materials 11-18/06/2007 23
100nm
Encapsulation of magnetite Encapsulation of fluorescent dye
under under
day light UV light
Reactions in droplets