2 - Features of Emulsion Polymerization

Features of Emulsion Polymerization
Professor José M. Asua
Institute for Polymer Materials (POLYMAT)

The University of the Basque Country
Donostia-San Sebastián, Spain
September 12, 2005
Emulsion Polymerization Processes Course

September 2005, Donostia-
Donostia-San Sebastián
Latexes
Polymer particles dispersed in a continuous medium (water)

Stabilized with surfactants
Particle diameter from 50 to 1000 nm, more commonly from 80 to 300 nm
Solids content 50 – 65 wt%
Particles mostly spherical, but often showing morphology
Some figures:
50 wt% solids, dp = 120 nm
Number of particles: Np = 5.5 x1017 particles / Llatex
Surface area: 25000 m2 (2.5 soccer fields)
Distance between particles: 10-15 nm

Latex Applications
Film forming dispersions: paints, adhesives, paper coatings
Dr J.L. Keddie, Film Formation, Friday, September 16
Coagulated: rubber for tires Spray-drying: impact modifiers for plastics

redispersable powders

A = butyl acrylate B = styrene AABABBABABBAABABAB

ABABAABBAAAB sticky!! AAAAAAAAABBBBBBBBB
BBABBABABBBA non-adhesive!!
Prof. Bernadette Charleux, CFRP, Wednesday, September 14
• Polymer Composition
• CCD
Latex 2
0,8
• MWD 0,6
• Branching
b30
0,4
• Crosslinking 0,2
• Gel content
0
3 4 5 6 7 8
logM
• Particle morphology
• Particle size distribution
dp
Course on
Emulsion Polymerization Processes
Emulsion polymers are “product by process”, whose properties are determined

In the reactor.
The course will focus on:

1. Understanding the fundamental basis of emulsion polymerization.
2. Usage of this understanding to manipulate process conditions to
achieve a consistent production of improved products.
3. Key fundamental aspects of the application of emulsion polymers
• Latex rheology
• Film formation
• Adhesion

Typical formulation
Monomer(s) 50-60 wt%

Styrene
Methyl methacrylate “hard monomers”
Vinyl chloride
Vinyl acetate
Butadiene
Butyl acrylate
2-ethyl hexyl acrylate “soft monomers”
Veova 10
Ethylene
(Meth)acrylic acid “functional monomers”

Crosslinking Monomers
Deionized Water 40-45 wt%
Initiators 0.5 wt%
Emulsifiers 0.5-3 wt%
Chain Transfer Agents

INITIATORS
Thermal Initiators:
Persulfates (water-soluble, more common choice)
∆
S O= → 2SO* −
2 8 4
Azobisisobutyronitrile (oil-soluble)
CH3 CH3 CH3
∆ + N2
CH3 C N = N C CH3 2 CH3 C*
CN CN CN

Thermal initiator decomposition rates
half-life (h)*
Initiator
50 ºC 70 ºC 90 ºC 110 ºC 130 ºC 150 ºC
Ammonium persulfate 192 8.4 0.55
Dilauryl peroxide 50 3.2 0.29
t-butyl hydroperoxide 570 100 70
* Approximate values. pH and other components of the formulation may affect decomposition rate
Thermal initiators should be used within the appropriate temperature range
M.A. Taylor, in Polymer Dispersions and Their Industrial Applications, D. Urban and K. Takamura Eds,
Wiley-VCH, 2002.

Redox Initiators
water-soluble:
S O= + S O= → SO* − + SO − − + S O* −
2 8 2 5 4 4 2 5
TBHP + ascorbic acid

CH3 CH3
· -
2 R C OOH + 2 e- 2 R C O + 2 OH
CH3 CH3
O O
+ -
O C CH CHOH CH2OH O C CH CHOH CH2OH + 2H + 2e
C C C C
OH OH O O
CH3 O CH3 O
O C CH CHOH CH2OH O C CH CHOH CH2OH
· -
2R C OOH + 2R C O + + 2H+ + 2OH
C C C C
CH3 OH OH CH3 O O
2H2O

Redox Initiators
oil-soluble:
benzoyl peroxide + dimethylaniline
interface:
t-butyl perbenzoate (o-s) + ascorbic acid (w-s)
Sarac, Prog Polym Sci 24, 1149 (1999)
Misra and Bajpai, Prog. Polym. Sci., 8, 61 (1982)

Redox Initiators
High radical generation rates even at low temperatures (20-30 ºC)

Their concentration in the reactor decreases rapidly
At least one (or both) of the redox components should be continuously
added into the reactor
conversion
Redox shot addition (batch)

Redox continuous addition
Thermal, batch
time
The stoichimetry is not always well known

The radical generation rate is not known

colloid
unstable
aggregate
Reaction Coordinate

Emulsifiers:
* Ionic
* Non-ionic
G kinetically
stable
Ea
colloid
unstable
aggregate
Reaction Coordinate
Stability of Polymer Colloids, Professor Jacqueline Forcada (Tuesday, September 13)

EMULSIFIERS
Ionic
Anionic C12 H25 SO4- Na+
Cationic C12 H25 N+ Me3 Br-
Zwitterionic C12 H25 N(Me2)+C3H6 SO3-
Nonionic C12 H25 - (CH2-CH2O)nH

Emulsifier in Water
micelles
70
σ (mN/m)
30
cmc Amount of emulsifier

cmc: critical micellar concentration

70
σ (mN/m)
presence of polymer particles
no polymer particles
30
cmc Amount of emulsifier
In the presence of polymer particles, a much higher amount of surfactant is needed

to form micelles

Emulsifier in Latex
Langmuir-like isotherm
k[E]w
Θ=
1 + k[E]w
1
emulsifier
Θ aS=area/mol
Adsorbed
emulsifier [Ε]ω
micelles Amount of emulsifier required to stabilized

appear a latex Control of Np in nucleation
Prof. María J. Barandiaran, Tuesday, September 13
Batch reactor
Monomer(s)
Deionized Water
Emulsifiers

M
M
Monomer Micelles
droplet M
M
M
[M]droplets [E]droplets [E]aqueous phase [E]micelles
[M]aqueous phase [E]interfaces
[M]micelles
S2O8= M
M
S2O8=
S2O8 = M
Monomer
droplet M
+M
S2O8 = *- SO4-MMM*
2 SO4
+M Micellar
entry
SO4-
SO4-MMMMMM*
Precipitation
+ SO4-
emulsifier adsorption
+
monomer diffusion
Micelles
Polymer particles
S2O8 =
M S2O8=
S2O8= M
Monomer
droplet
M M M
[M]droplets [E]particles
[M]aqueous phase [M]particles [E]droplets [E]aqueous phase [E]micelles
[M]micelles [E]interfaces

S2O8= M
S2O8=
S2 O 8 = M
Monomer
droplet M
Polymer particles
M
[E]particles
[M]droplets
[E]droplets [E]aqueous phase
[M]aqueous phase [M]particles

[E]interfaces

S2O8= M
S2O8=
S2O8= M
M
Polymer
M particles
[M]aqueous phase [M]particles
[E]particles [E]aqueous phase [E]interfaces

Batch reactor
Conversion
Interval for end of interval Np Rp
I 0.05-0.10 increasing increasing

II 0.25 (VAc), 0.4(S) constant about constant
III 1 (Tg<T), <1(Tg>T) constant decreasing
conversion
I II III
[M]p
Np
time
Radical Compartmentalization
S2O8= M
R* R*
R* R*
S2O8= M
M
M
R*
M
R*
R*
Radicals in different particles cannot undergo bimolecular termination

• Longer life-time of the radicals, which leads to higher Mw.
• Overall radical concentration higher than in homogeneous
polymerization, which leads to a higher Rp.

Number of particles and Mw
50 wt% solids
Rate of radical production: 1x1016 (radicals/ Llatex s)
dp = 150 nm dp = 80 nm
Np = 2.8x1017 particles/Llatex Np = 1.8x 1018 particles/Llatex
Frequency of radical entry: 28 s Frequency of radical entry: 180 s
Increasing the number of particles Mw increases

Number of particles and overall radical concentration
Emulsion polymerization
50 wt% solids, dp = 120 nm
Number of particles: Np = 5.5 x1017 particles / Llatex
Assumptions:
1. Radicals are formed in the aqueous phase, and enter into the
polymer particles.
2. Instantaneous termination occurs when there are two radicals in
the same particle
Result:
Half of the particles contain one radical, the rest none
Total radical concentration = 0.5 Np/NA=4.5 10-7 M
Total radical concentration increases with the number of particles
Bulk polymerization
[R ] =  fk I [I ] 
0.5 0.5
   0.5 × 1.58 ⋅10 − 4 × 3 ⋅10 −3 
=   = 4.5 ⋅10 −8 M
 kt   1. 16 ⋅ 10 8

Reactors
Tank reactors
Batch Semicontinuous Continuous (CSTR)

(S-BA, all acrylics) (SBR,SAN)
Tubular reactors
Loop
(VAc-Veova 10)
Emulsion Polymerization Reactors, Dr María Paulis (Thrusday, September 15)

Semicontinuous reactor
Slow monomer feed. Slow surfactant feed
S2O8= M
S2O8=
S2O8= M
M
Polymer
M particles
M
Common conditions
in semicontimuous operation

Slow monomer feed. Fast surfactant feed
Micelles
Polymer particles
M S2O8=
S2O8= M
M M M
Secondary nucleations

Fast monomer feed. Slow surfactant feed
S2O8= M
S2O8=
S2O8= M
Monomer accumulation
Monomer
droplet
(e.g, due to inhibition) Polymer particles

Advantages of emulsion polymerization
Low viscosity.
Easy heat removal.
Good temperature control.
High polymerization rate.
No solvents used.
Easy to remove unreacted monomers.
High molecular weights at high polymerization rates.
Easy to process the polymer into dry polymer.
New products to meet market needs.
Disadvantages: Impurities in the polymer

Alternative Polymerization
Techniques
• Inverse emulsion polymerization
• Miniemulsion polymerization
• Microemulsion polymerization
• Dispersion polymerization

Inverse Emulsion Polymerization
Polymer particles
Micelles (aqueous solutions)
S2O8=
M S2O8=
S2O8= M
Aqueous Monomer
Solution
Droplet M M M
Organic Continuous Phase
Polymerization of water-soluble monomers: acrylamide, acrylic acid

Monomer Emulsion
S2O8= M
S2O8=
S2O8 = M
Monomer Micelles
droplet M
M
M
M
S2O8= 2 SO4*-

MONOMER EMULSIONS
Power
Volume
Sonifier
Colloidal Mill
High Pressure Homogenizer
Droplet Stabilization
Sonication
200
160 Magnetic stirrer
120
dd (nm)
80 – System:
• MMA/BA/AA (49/50/1)
40 20%organic phase • Dowfax 2A1
40%organic phase
0 • HD
0 10 20 30 40
Time (min) – Sonication: 8(70%)

Monomer Miniemulsion
M M
M
M
M Monomer
droplets
M
M

Monomer Miniemulsion Polymer Dispersion
M
polymerization

Applications of Miniemulsion
Polymerization
• High solids low viscosity latexes

• Stable continuous reactors
• Controlled free radical polymerization
in dispersed media
• Catalytic polymerization
• Inorganic-organic nanocomposites
• Incorporation of hydrophobic monomers
• Hybrid particles
• Step polymerization in aqueous
dispersed media
Miniemulsion Polymerization, Dr. Abraham Chemtob

(Wednesday, September 14)

MICROEMULSION POLYMERIZATION
Agitation of two non-miscible liquids in the presence of emulsifier yields a emulsion:

•Polydisperse spherical particles.
•Several microns in diameter.
•Thermodynamically unstable.
•Kinetically stabilized by the emulsifier.
•Degrades by diffusion.
•Turbid.
If an alcohol (n-pentanol, cosurfactant) is added to this emulsion, it becomes transparent.

A microemulsion has been formed.
•Small and narrow particle size distribution.
•Transparent.
•Spontaneous formation.
•Thermodynamically stable.
•Both w/o and o/w can be formed.

Mechanism of Microemulsion Formation
The free energy change (neglecting entropic effects) is:

∆G ≈ σ ∆A
i
Spontaneous formation requires negative interfacial energy!!
Gibbs adsorption isotherm:
dσ = − ∑ Γ dµ ≈ − ∑ Γ RTd[ln c ]
i j j j j
j j
σ
cosurfactant
cmc log(E)
Structure of Monomer Microemulsions

MICROEMULSION POLYMERIZATION
a)
S2O8= M
M
S2O8= polymerization
M
M b)
S2O8 =
High molecular weight polymers (floculants)

A key issue is to maintain the size of the latex similar to that of the microemulsion

DISPERSION POLYMERIZATION
~ = stabilizer = unstable nuclei

~ = oligomers
~ ~
~
~ ~
O
= stable particles
l
= grafted stabilizer
~
~
~
~ ~ ~
~ ~
~ ~ ~ ~
~ I2 2 I· ~
O
~
~ ~ ~ ~ ~ ~ ~ ~
~ ~ ~~
~
~
l
~ ~
~
l
~ ~ ~ l
~ ~~
~ ~ ~
~
~ ~ ~
~
~ ~~
~ ~ ~ ~ ~ ~ l
~ ~ ~ ~ ~ ~
~
~ ~
O
~ ~ ~ ~ ~
l
~
~
O
~
1) Homogeneous solution 2) Nuclei formation 3) Formation of 4) Capture of oligomers
Monomers (unstable) stable particles and unstable nuclei
Initiator
Stabilizer
Solvent

DISPERSION POLYMERIZATION IN POLAR MEDIA
Emulsion DISPERSION Suspension
0.1 0.8 50 1000 dp (µm)
Micron Size Monodisperse Polymer Particles
Chromatographic columns
Calibration standards
Toners

Emulsion Polymers
Film-Forming Dispersions:
Market: Polymers: Applications:
9.9 MM tons/year SBR 34% Coatings 26%

North America 33.3% Acrylics 24% Paper 23%
Europe 32.5% VAc 10% Adhesives, sealants 22%
Asia/Pacific 25.9% EVA 7% Carpet 11%
Rest of the World 8.3% Vinyl esters 3% Textiles 7%
Nonwoven 5%
Annual growth: 4.5 %
Coagulated Emulsion Polymers:
SBR 9.5 MM tonnes/year (tires 80%, mechanicals goods 11%)

ABS
SAN
PVC 1.3 MM tonnes/year (plastisols)

Adhesives
Polymers Markets
www.freedoniagroup.com

Adhesives
1. Pressure sensitive adhesives

1. Self-adhesive labels Products are formulated
2. Electrical tapes 1. Polymer dispersion
3. Self-adhesive tapes (still mostly 2. Tackifying agents (improve tack)
solvent based) 3. Plasticizers (improve polymer
2. Laminating adhesives flow)
1. Flexible packaging (e.g., coffee bags) 4. Thickeners (rheology control)
2. Glossy films (e.g., book cover) 5. Wetting agents
3. Furniture and automotive 6. Antifoam agents
(dashboard) 7. Fillers
3. Construction adhesives 8. Biocides (protection against
1. Floor covering microorganisms)
2. Polymer modified mortars
3. Ceramic tile adhesives
Actions based on:

1. Wetting the solid surfaces and adhere to them
2. Cohesion (internal strength)

Adhesives
Pressure Sensitive Adhesives (PSA)

They adhere to virtually all surfaces when pressed down gently
30-40 % of PSAs are aqueous dispersions ( rest: solvent based and hot melts)
Mostly acrylic dispersions
Performance:
Tack
Resistance to peel
Resistance to shear
Application rate on solid surfaces (e.g., self adhesive labels): 600-1000 m/min

Effect of Polymer Microstructure on Adhesive Properties
Tack: Limiting value of the adhesion as the contact time approaches zero
Adhesive layer
Rolling ball test (the longer the distance the tacky the adhesive)
Effect of molecular weight

P-BA
Gel % 3 0
MW 168000 58000
Tack (cm) 1.7 0
Chauvet et al., JPS Polym Chem, accepted

Urban-Takamura, “ Polymer dispersions and their industrial applications”,
Wiley-VCH, 2002


Wiley-VCH, 2002

Shear resistance: Ability to hold a weight (related to cohesive properties)
Shear Resistance
2º p-BA
Gel % 1 33 57
Shear (s) 45 1820 40
1 kg 1 kg

Wiley-VCH, 2002

Latex 1
Latex 2
0,8
0,8
0,7
0,6
0,6
0,5
sc85
0,4
b30
0,4
0,3
0,2 0,2
0,1
0 0
3 4 5 6 7 8 3 4 5 6 7 8
logM logM
Properties Latex 1 Latex 2

Tack 12.54 7.43
Shear 3100 247
Peel 2.7 9
Polymer microstructure affects all properties


Wiley-VCH, 2002
Blends of latexes may not bring improvements in performance


Influence of the shear rate and PSD
S-20% L-80%
S-50% L-50%
S-80% L-20% dp
0,02
Viscosity (Pa.s)
0,01
0,009
0,008 dp
0,007
500 1000 1500 2000 2500 3000
Shear rate (1/s) f
dp
Latex Rheology (Wednesday, September 14)

Coatings
Decorative
Homes, offices
They provide color, texture, sheen and protection to interior and exterior
Vinyl acetate/butyl acrylate

Vinyl acetate/Veova 10
Styrene/butyl acrylate
Methyl methacrylate/butyl acrylate
Protective/industrial
Applied to large structures (bridges, factories) and to products in industrial
production processes
Mostly all acrylics

Coatings
Formulation
Binder (emulsion polymer)

Pigments (organic/inorganic – TiO2- provide color)
Fillers (calcium carbonate, talc, clays – opacity) Pigment volume content (PVC)
Thickeners (water soluble polymers -rheology)
pigment and filler volume
Wetting agents (surfactants –reduce surface tension) PVC =
total solids volume
Coalescent (film formation)
Defoamer (reduce foaming)
Biocide (avoid microorganism growth) Critical PVC (CPVC)
Value of the PVC at which the polymer
film is not well formed
PVC < CPVC

Gloss, low porosity, good
barrier properties
PVC > CPVC
Cheap interior paints

Binder
The binder should have the adequate Tg (copolymer composition) for film formation
Vinyl acetate/butyl acrylate 80/20 wt/wt
Vinyl acetate/Veova 10 75/25 wt/wt
Styrene/butyl acrylate 50/50 wt/wt
Methyl methacrylate/butyl acrylate 50/50 wt/wt
Minimum film formation temperature (MFFT) lower than Tg

Tg = 10 – 15 ºC to allow film formation at ambient temperature
VOC
CONFLICT:
Film formation requires low Tg Coalescent: Plasticizes the “hard”
Blocking and mechanical strength polymer during film formation (low MFFT)
need higher Tg and latter evaporates (leaving a film of
hard polymer – strong)
Blocking is a measure of the tack of the dried paint

Reducing Coalescent: Particle morphology
Soft polymer
BA/MMA
66/34 wt/wt
Hard polymer
MMA
Film formation
When two painted bodies are pressed together, the hard polymer
prevents adhesion

B. Schuler et al., Progress in Polymer Coatings, 40, 139 (2000)


soft/hard* MFFT Block test**
100/0 <0 5
85/15 <0 3
70/25 <0
70/30 <0 1
65/35 6
60/40 10 0
50/50 > 50 0
40/60 > 50
* Soft BA/MMA=66/34: hard=MMA

** 5: very tacky; 0: no tacky at all

Binder
Main monomers (MMA, S, VAc, BA, Veova 10, …)

Acidic monomers (acrylic acid, methacrylic acid, - stability and rheology)
Crosslinker
Adhesion promoters
O
OH
H3C R
O P
O
CH2 HO
Sipomer PAM 100

(Rhodia)

Effect of Adhesion Promoter
ASTM D3359A
5A 4A 3A 2A 1A 0A
ASTM D3359B
Amount of Amount of
SIPOMER ASTM D 3359 A ASTM D 3359 B SIPOMER ASTM D 3359 A ASTM D 3359 B
PAM100 PAM100
0 0A 0 0 1A 0
1 1A 1 1 3A 3
2.5 2A 1 2.5 5A 5
5 4A 4 5 5A 5
aluminium steel
I. González, PhD Dissertation, University of the Basque Country, 2005

Further Reading
I. Piirma, Ed., Emulsion Polymerization, AcademicPress, 1982.
R.G. Gilbert, Emulsion Polymerization. A Mechanistic Approach, Academic Press, 1995
J.M. Asua, Ed., Polymeric Dispersions: Principles and Applications, Kluwer Academic Publishers;
Dordrecht, 1997
P.A. Lovell, M.S. El-Aasser, Eds., Emulsion Polymerization and Emulsion Polymers, Wiley, 1997
H. Warson, C.A. Finch, Applications of Synthetic Resin Latices., 3 vols, John Wiley, 2001
D. Urban, K. Takamura, Eds., Polymer Dispersions and Their Industrial Applications, Wiley-VCH,
Weinheim, 2002
de la Cal et al, in T. Meyer, J. Keurentjes Eds., Handbook of Polymer Reaction Engineering, Wiley-
VCH, Chapter 6, 2005.
W.V. SmithR.H. Ewart, J. Phys. Chem.16, 592 (1948)

Harkins, W.D., J. Chem. Phys., 13, 381 (1945)
Harkins, W.D., J. Am. Chem. Soc., 69, 1428 (1947)
Ugelstad, J., Hansen F.K., Rubber Chem. Technol, 49, 536 (1976)


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2 - Features of Emulsion Polymerization

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Features of Emulsion Polymerization

Professor José M. Asua

Institute for Polymer Materials (POLYMAT)

September 12, 2005

Emulsion Polymerization Processes Course

Polymer particles dispersed in a continuous medium (water)

Emulsion Polymerization Processes Course

Film forming dispersions: paints, adhesives, paper coatings

Dr J.L. Keddie, Film Formation, Friday, September 16

Coagulated: rubber for tires Spray-drying: impact modifiers for plastics

Emulsion Polymerization Processes Course

A = butyl acrylate B = styrene AABABBABABBAABABAB

Emulsion polymers are “product by process”, whose properties are determined

The course will focus on:

Emulsion Polymerization Processes Course

Monomer(s) 50-60 wt%

(Meth)acrylic acid “functional monomers”

Deionized Water 40-45 wt%

Initiators 0.5 wt%

Emulsifiers 0.5-3 wt%

Chain Transfer Agents

Emulsion Polymerization Processes Course

Persulfates (water-soluble, more common choice)

CH3 CH3 CH3

Emulsion Polymerization Processes Course

Thermal initiator decomposition rates

Ammonium persulfate 192 8.4 0.55

Dilauryl peroxide 50 3.2 0.29

t-butyl hydroperoxide 570 100 70

Thermal initiators should be used within the appropriate temperature range

Emulsion Polymerization Processes Course

TBHP + ascorbic acid

Emulsion Polymerization Processes Course

benzoyl peroxide + dimethylaniline

t-butyl perbenzoate (o-s) + ascorbic acid (w-s)

Sarac, Prog Polym Sci 24, 1149 (1999)

Misra and Bajpai, Prog. Polym. Sci., 8, 61 (1982)

High radical generation rates even at low temperatures (20-30 ºC)

Redox shot addition (batch)

The stoichimetry is not always well known

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Stability of Polymer Colloids, Professor Jacqueline Forcada (Tuesday, September 13)

Emulsion Polymerization Processes Course

Anionic C12 H25 SO4- Na+

Cationic C12 H25 N+ Me3 Br-

Zwitterionic C12 H25 N(Me2)+C3H6 SO3-

Nonionic C12 H25 - (CH2-CH2O)nH

Emulsion Polymerization Processes Course

cmc Amount of emulsifier

Emulsion Polymerization Processes Course

presence of polymer particles

cmc Amount of emulsifier

In the presence of polymer particles, a much higher amount of surfactant is needed

Emulsion Polymerization Processes Course

micelles Amount of emulsifier required to stabilized

Emulsion Polymerization Processes Course

[M]droplets [E]droplets [E]aqueous phase [E]micelles

[M]aqueous phase [E]interfaces

[M]aqueous phase [M]particles [E]droplets [E]aqueous phase [E]micelles

Emulsion Polymerization Processes Course

[M]aqueous phase [M]particles

Emulsion Polymerization Processes Course