Heterogeneous Polymerizations Polymer Synthesis

CHEM 421

• Precipitation
• Distinguished by:
– Initial state of the polymerization
• Suspension mixture
– Kinetics of polymerization
• Dispersion
– Mechanism of particle formation
• Emulsion – Shape and size of the final
polymer particles
 Free Radical Polymerizations Polymer Synthesis
CHEM 421

Particle Size
(µm) Precipitation Solution
0.01

Emulsion
0.1

1 Dispersion

10
Suspension
100
Medium
solvency
monomer: insoluble soluble soluble
polymer : insoluble insoluble soluble
Precipitation Polymerization Polymer Synthesis
CHEM 421

M M I M M
hν M
M I M M I or I
I
M
M I M Δ
M M Solvent I
I
Solvent M P P P PP P P P
• Solvent, monomer & initiator
• Polymer becomes insoluble in the solvent
(dependent on MW, crystallinity, rate of
polymerization
• Polymerization continues after precipitation (?)
Precipitation Polymerization Polymer Synthesis
CHEM 421

• Considerations:
– Ease of separation
– Used for:
» Vinyl chloride (solvent free)
» Poly(acrylonitrile) in water
» Fluoroolefins in CO2
» Poly(acrylic acid) in benzene
» Poly(acrylic acid) in CO2
– Traditionally, not too applicable…
» Rule of thumb, polymer must be insoluble in its
own monomer…
 Conventional Polymerization of Polymer Synthesis
Fluoroolefins CHEM 421

F F F F CO2
+ CF2 CF2 CF2 CF
F F initiator n
F ORf ORf
F H
CF2 CH2
F H initiator n

Aqueous Emulsion
or Suspension Non-aqueous Grades

• Uses water • Uses CFCs & alternatives

• Needs surfactants • Surfactant free
(PFOS / PFOA / “C-8”) • Stable end-groups
• Ionic end-groups • Electronic grades
• Multi-step clean-up
 Polymerization of Polymer Synthesis

Fluoroolefins in CO2 CHEM 421

F F F F CO2
+ CF2 CF2 CF2 CF
F F initiator n
F ORf ORf

Teflon PFA™, FEP™

Typical Reaction Tefzel™
• 10-50% solids PVDF
• 3-5 hours @ 35 °C (batch) Nafion™
Kalrez™
• Pressures 70-140 bar at 35 °C Viton™
• End group analysis (FTIR) shows
3 COOH, COF end groups per 106 carbons
• <Mn> ~ 106 g/mol without chain transfer agent

Romack, T. J.; DeSimone, J.M. Macromolecules 1995, 28, 8429.

GPC Traces - Effect of [VF2] on MWD Polymer Synthesis
CHEM 421

75 °C, 4000 psig,  = 20 minutes

2

1.1 M
1.5 1.7M
1.9 M
d w t/d (lo g M )

2.7 M
2.9 M
1

0.5

0
1.0E+03 1.0E+04 1.0E+05 1.0E+06 1.0E+07
Molecular Weight

Bimodal MWDs observed when [VF2]0

greater than about 1.9 M
Suspension Schematic Polymer Synthesis
CHEM 421
Suspension Polymerization Polymer Synthesis
CHEM 421

Aqueous Continuous phase

• Vertical flow pattern
• Presence of stabilizers

Addition of
monomer
dispersed phase
Suspension
polymerization in
• Controlled agitation polymer micro-droplets
• Coagulation prevented
• Particle diameter range Monomer beads
30m to 2mm Polymer beads
 Method of Separation Polymer Synthesis
CHEM 421

Particles after sieving

Copolymer particles separated into fractions
with US standard sieves using a sieve shaker

Broad size distribution

250m sieve

125m sieve

75m sieve

100m
45m sieve
100m
* All pictures are optical micrographs
Suspension Polymerization Polymer Synthesis
CHEM 421

• Considerations:
– Stabilizers used:
» water-soluble polymers: i.e. poly(vinyl alcohol)
– Hard to control particle size – separate with
sieves
– Two phase system only with shear, can’t
recover colloidal system
– Used for: styrene, (meth)acrylic esters, vinyl
chloride, vinyl acetate
» Chromatographic separation media, affinity
columns, etc
 Porosity Investigations Polymer Synthesis
CHEM 421

• Application to transition-metal catalysis and enzymatic catalysis

Highly porous particles (high specific surface area) will

permit an improved activity of the system by increasing the
density of actives sites per unit of volume

• Porosity potential by incorporating various porogens (solvent, non-

solvent or linear polymer)

Toluene has been successfully investigated

• Porosity evaluation by performing SEM and N2-BET

 Porosity Investigations Polymer Synthesis
Visual Appearance of Cross-linked fluoropolymer beads CHEM 421

1 mm 1 mm

1 m 1 m
m
Scanning electron micrographs

Sample Styrene (wt%) EGDMA (wt%) FOMA (wt%) Surface Area* (m2/g)

Non-porous 34 6 60 0.25

Porous 10 80 10 420**

* Surface area measured by N2-BET, error 1%, ** Toluene used as porogen (100% v/v monomer)
 Potential Utility of CO2 Polymer Synthesis
CHEM 421

• CO2 is non-toxic, cheap and readily available

• CO2 is a by-product from production of ammonia, ethanol, hydrogen

• CO2 is found in natural reservoirs and used in EOR

• Easily of separated and recycled

• CO2 has a low surface tension, low viscosity

• Liquid and supercritical states “convenient”

• Inert for many chemistries

 CO2 is a Variable and Polymer Synthesis

Controllable Solvent CHEM 421

• Like a gas - but high density

SCF • Like a liquid - but low surface tension
Pressure

Liquid
Pc • Low viscosity, high diffusivity
Solid
• Nonflammable, environmentally friendly,
Gas
cost effective, processes at moderate P, T

Tc
Temperature

Gas Gas/Liq. SCF

 Solubility in CO2 Polymer Synthesis
CHEM 421

CH3

Pressure
1- Phase CH2 C

O C n
Ideal coils critical point
O
Dilute globules
CH2
2- Phase C6F12
Concentration CF3

Scattering Studies
• Determined key molecular parameters (<Mw>, Rg, A2)
• CO2 found to be a “good” solvent for fluoropolymers
“Synthesis of Fluoropolymers in Supercritical Carbon Dioxide”
DeSimone et. al. Science 1992, 257, 945-947
“SANS of Fluoropolymers Dissolved in Supercritical CO2”;
DeSimone et. al. J. Am. Chem. Soc. 1996, 118, 917.
 Polymer Solubility in CO2 Polymer Synthesis
CHEM 421

“CO2-philic” “CO2-phobic”

Oleophilic Hydrophilic
1) Fluoropolymers
2) Siloxanes PPO PEO
PVAc PAA
3) Poly(ether carbonates)… PIB PVOH
Beckman et. al. Nature
PS... PHEA...

f(MW, morphology, topology, composition, T, P)

“Synthesis of Fluoropolymers in Supercritical Carbon Dioxide”

DeSimone et. al. Science 1992, 257, 945-947
“Dispersion Polymerizations in Supercritical Carbon Dioxide”
DeSimone et. al. Science 1994, 265, 356-359.
 “Synthesis of Fluoropolymers in Supercritical Carbon Dioxide”
Polymer Synthesis
DeSimone et. al. Science 1992, 257, 945-947 CHEM 421

R
R
CH2 C CO2
CH2 C
C O
C O n
O CH2 CF2 F
1,2 4-8 O CH2 CF2 F
1,2 4-8

• Homogeneous solution polymerizations (up to 65% solids)

• High molecular weights (ca. 106 g/mol)
• Supercritical or liquid CO2
• Low viscosities
• Wide range of copolymers
- solubility function of fluorocarbon content
Dispersion Mechanism Polymer Synthesis
CHEM 421

M M M
Δ M M
I M M
I M
initiation
M M
M M I I
particle
M I M
M nucleation M
I M M
M M
M

homogeneous
Particle growth

M monomer
I initiator
stabilizer
polymer

dispersed polymer particles grow

Dispersion Polymerization Polymer Synthesis
CHEM 421

• Considerations:
–Relatively large particle size (0.5-5 μm);
–Typically narrow Particle Size Distribution
–Resulting polymer in colloid (application
dependent)
–Not common, most examples synthesized
from organic solvents, not water
–Major application: xerography, ink jets
 “Dispersion Polymerizations in Supercritical Carbon Dioxide”
DeSimone et. al. Science 1994, 265, 356-359. Polymer Synthesis
CHEM 421

CO2
Monomer + Surfactant + Initiator Polymer
heat

• High conversion
• High molecular weights
• Stable latexes
• Dry powders
• Narrow particle size distributions
• Spherical particle morphology
• Different polymerization kinetics
• Composite latex particles possible
• Allows for new coating opportunities
 Structured Particles Containing a Polymer Synthesis
Reactive Functional Polymer CHEM 421

CH3 CH3

CH2 C CH2 C
n n
C O C O

O CH2CH CH2 O CH2CH2N=C=O

O
Poly(glycidyl methacryate) Poly(isocyanatoethyl methacrylate)
(PGMA) (PIEM)
• Reactive epoxy functionality • Reactive isocyanate functionality

• Can react with amines, enzymes… • Isocyanates react with water, alcohols…

• Can react in an epoxy resin • Difficult to synthesize in a aqueous

emulsion or dispersion

• Can form crosslinking polyurethane

linkages with an alcohol-containing polymer
TEM Images of PIEM/PS Polymer Synthesis
CHEM 421

CH3
CH2 CH
CH2 C n
n
C O

O CH2CH2N=C=O

100 nm
Composition:
14 mol% PIEM
86 mol% PS