Use of Novel Polyetheralkanolamine

Comb Polymers as Pigment Dispersants

for Aqueous Coating Systems

Duy T. Nguyen, Ph.D

Huntsman Performance Products
 Outline

ƒ Fundamental Structure-Property Relationship of

Polyetheralkanolamine Copolymers
¾ Optimization of Polyetheralkanolamines
¾ Stabilization mechanisms: steric and charge

ƒ Comparison with other conventional

dispersants
¾ Resin-containing pigment concentrates
¾ Resin-free pigment concentrates

ƒ Conclusions
 Why use dispersants?

Good Dispersants

Flexibility Production capacity Quality

-VOC-free - Reduced milling time - Better dispersion stability

-APE-free - Decreased dispersion viscosity - Increased color development
-Compatible with binder to allow higher pigment loading - Maximun color acceptance
types of all bases
Polyetheralkanolamine Comb
Polymers

Adsorption of a comb polymer at the pigment surface

P ERFANCE S PECIALTIES T ECHNOLOGY

Soluble chain
Hydrophilic
Chains
Anchoring group
Hydrophobic
Backbone
Pigment

An effective dispersant should have:

1) Anchoring groups
2) Soluble chains
3) Linkers
Polyetheralkanolamine Comb
Polymers (Patents Pending)

R O N O
OH OH 2-3

Hydrophilic teeth
O
x
R is aromatic or aliphatic

O
y
Nomenclature: CH3
P7E : x = 3 and y = 7
P19E : x = 3 and y = 19
P41E : x = 3 and y = 41
P58E : x = 8 and y = 58
 Pigment Adsorption Studies

1) Fill the sample holder (made of

aluminum and has small holes in
bottom) with pigment
2) Compact with piston
3) Suspend the holder from the
balance just above the surface of a
liquid
4) The liquid is raised until it touches
the bottom of the porous sample
5) Mass vs. time is then collected as
the liquid penetrates into the solid

Kruss K12 Surface Tensiometer

Particle Size and Zeta Potential
Analysis

1) No dilution required (0.1- 50% by

volume )
2) Wide particle size range ( 5nm – 1000
microns)
3) Small sample volume (20-110 ml)
4) Use of ultrasound technologies

DT-1200 Acoustic Spectrometer

 Outline

ƒ Fundamental Structure-Property Relationship of

Polyetheralkanolamine Copolymers
¾ Optimization of Polyetheralkanolamines
¾ Stabilization mechanisms: steric and charge
Effect of EO on Surface Tension

50
Surface tension, dyne/cm

4% solution
48 P58E

46
P41E

44 P19E

42
P7E Increasing water solubility
40
0 20 40 60 80
Moles of EO
Effect of EO on Interfacial Tension
Dispersed phase: Mineral Oil
Flow rate: 1ml/hr
Interfacial Tension, dyne/cm

15
P58E
14
P41E
13
12
11 P19E
1% solution
10
9 Increasing water solubility
8
0 20 40 60 80
Moles of Ethylene Oxide
Effect of EO on Wetting Effectiveness for
4% Polymer Solutions on Carbon Black
Wetting Effectiveness,

1200
1000 P41E P58E
P19E
800
mg

600
400
P7E
200
0 20 40 60 80
Moles EO
Wetting effectiveness = max amount of liquid gained into the carbon black column
 Effect of EO on Wetting Rate for 4%
Polymer Solutions on Carbon Black

5
Wetting rate, mg/s

4
P41E P58E
3

2
P19E
P7E
1
0 20 40 60 80
Moles of EO
Wetting rate = (weight of liquid gain at half saturation) / (time required for half saturation)
Effect of Ethylene Oxide on Carbon
Black Dispersion Viscosity

37% Carbon Black ; 15% Dispersant on Carbon Black

10000
Viscosity @ 0.8/s, cP

P7E

1000
P58E

P19E
100
P41E
(Highest wetting rate: dynamic)

10
0 20 40 60 80
Moles of EO
 STERIC STABILIZATION:
Adsorption Layer Thickness and Effective Volume Fraction

δ δ

nl 5 / 3
δ = Eq. (1) R

s 2 /3 δ = adsorption layer thickness (5-10 nm)

• Where n is the number of EO units, l is the EO length (0.369 nm), and s is the average
distance between the grafting points (1.6 nm)

• The adsorbed polymer layer can increase the particle radius and add to the volume
fraction of the solid particles, φ, to yield an effective volume fraction, φeff

Reffective = R +δ Eq.(2) Reff

δ

φ effective= φ (1+ δ/R) 3 Eq. (3) R

Where δ is the adsorption layer thickness and R is the radius of the carbon black
particles (24nm)
 Calculation of steric thickness and
effective volume fraction

• Adsorbed layer thickness of 5-10 nm is usually considered sufficient

to screen the attractive Van der Waals forces

EO content δ (nm) φ eff φ µ, cp

7 (P7E) 1.39 0.29 0.24

19 (P19E) 3.05 0.35 0.24

41 (P41E) 6.11 0.48 0.24 100

58 (P58E) 9.16 0.65 0.24 2,000

NP 40 * 2.3

Note: Length of each EO unit is about 0.35 nm. For 41 EO’s, the length is 14.35 nm, compared
to 6.11 nm. It is concluded that the EO chain may loosely coil at the solid/liquid interface
rather than extend straight into the water
∗ C. Ma, Colloids Surfaces, Vol 66, pg 215, 1992
 CHARGE STABILIZATION
Zeta Potential of 5% Carbon Black as a
Function of pH
10 Untreated
With P41E (15% on
8 pigment)

6 IEP
Zeta Potential, mV

4 IEP IEP
IEP
2
0
-2
-4
-6
0 2 4 6 8 10 12 14
pH
 Particle Size Distribution

5% carbon black (untreated)

2.0
Bimodal:
1.8

1.6
Size 1 0.523 micron
1.4 Standard deviation 1 0.12
PSD, weight basis

1.2 Size 2 16.9 micron

1.0
Standard deviation 2 0.12
0.8
Fitting error % 18.2
0.6

0.4
Cumulative
0.2 10% 0.3637 micron
0.0
-1 0 1 2
16% 0.3936 micron
10 10 10 10
Diameter [um] 50% 0.5971 micron
84% 16.5313 micron
90% 18.5258 micron
 Particle Size Distribution

5% carbon black with 20% active P41E on pigment

2.0 Unimodal
Median 0.0924 micron
1.6 Standard deviation 0.187
Fitting error % 5.8
Cumulative
PSD, weight basis

1.2
10% 0.0551 micron
16% 0.0621 micron
0.8 50% 0.0924 micron
84% 0.1392 micron
0.4 90% 0.1549 micron

0.0

-2 -1 0
10 10 10
Diameter [um]
Total Concentration vs. Adsorbed
Concentration For P41E on Carbon Black
250
Adsorbed Concentration, ppm

200
y = 0.9167x
2
R = 0.9975

150

100

50

0
0 50 100 150 200 250 300
Total Concentration, ppm
 Outline

ƒ Comparison with other conventional

dispersants
¾ Resin-containing pigment concentrates
™ Modified SMA : a styrene maleic anhydride modified
with polyethers
™ Acetylenic Diol surfactant
™ P41E : Polyetheralkanolamine comb polymer
Receding Contact Angle of Carbon
Black Treated with Dispersants

90
Contact Angle, Degrees

80

70

60

50
40
30
Untreated Modified SMA P41E
P.B 15:3 Dispersion Viscosities
37% Pigment, 5.3% Dispersant on Pigment; P:B =4.7

30000
Viscosity, cps

25000 Acetylenic Diol

20000 P41E
Modified SMA
15000 Polyethermonoamine

10000
5000
0
0 20 40 60 80
Brookfield RPM
PY 14 Dispersion Viscosities
36% Pigment, 5.2% Dispersant on Pigment, P:B =4.7

100000 Acetylenic Diol

V is c o s ity , c p s

P41E
Polyethermonoamine
10000

1000

100
0 20 40 60 80
Brookfield RPM
Carbon Black Dispersion Viscosities
38% Pigment, 5.3% Dispersant on Pigment; P:B =4.7
6100

5100
Viscosity, cps

4100

3100
Modified SMA
2100

1100
P41E
100
0 10 20 30 40 50 60 70

Brookfield RPM
 PR 57:1 Dispersion Viscosities
36% Pigment Loading, P:B = 4.7

2100
1900 P41E (2.78% on pigment)
1700
Acetylenic Diol (2.78% on pigment)
V is c o s ity , c p s

1500
1300
1100
900
700
500
300
100
0 10 20 30 40 50 60 70
RPM
Yellow dispersion viscosities- aged three weeks

unmeasurable
Viscosity, cps at 12 rpm

100000

10000

1000
Initial
100 Aged

10

1
P41E Acetylenic Diol
Tint Strength: Blue Pigment (PB 15:3) in
Interior Latex Extra White (1:99 TiO2 White Reduction)

108
107
Color Strength

106
105
104 MSMA is reference (100%)
103
102
101
100
P41E Acetylenic Diol MSMA
Tint Strength : Carbon Black in Interior
Latex Extra White (1:99 TiO2 White Reduction)

112
110 Acetylenic Diol is reference (100%)
Color Strength

108
106
104
102
100
P41E MSMA Acetylenic Diol
 Outline

ƒ Comparison with other conventional

dispersants
¾ Resin-free pigment concentrates
™ Modified SMA : a styrene maleic anhydride modified
with polyethers
™ P41E : Polyetheralkanolamine comb polymer
™ Styrene Acrylate copolymer
Resin-free lithol rubine initial dispersion viscosity
45% pigment loading, 10% P41 E on pigment
60

50
Viscosity, cP

40

30

20

10

0
0 100 200 300 400 500 600 700
Shear rate, 1/s
Note: Dispersion with a modified SMA was too thick to mill
Viscosity of Resin-Free Pigment Concentrate
45% PB 15:3; 20% dispersant on pigment

12000
10000
Viscosity (cP)

P41E
8000 Styrene Acrylate
6000
4000
2000
0
0 20 40 60 80
RPM
Viscosity of 30% carbon black resin-free
dispersion: 20% dispersant on pigment

800
700
Viscosity @ 11/s, cP

600
500 Styrene acrylate
400 P41E

300
200
100
0
Fresh One week at 50C
Color Strength of Carbon Black in High
Gloss Latex Acrylate Paint

114 113
112
Color Strength

110 40% active on

carbon black
108
106
104 102.8
102
100
100
MSMA P41E Styrene acrylate

Resin-Free Carbon Black Concentrate: 30 % carbon black, 40% active dispersant on pigment
Color Strength of Carbon Black in Semi
Gloss Latex Acrylate Paint

120 115.6
100
100
Color Strength, %

30% active on carbon black

80
56.6
60

40

20

0
MSMA P41E Untreated

Resin-Free Carbon Black Concentrate: 30 % carbon black, 30% active dispersant on pigment
Color Strength of Carbon Black in
Alkyd Resin Paint

140 128
120 40% active on carbon black
Color Strength

100
100 91.2

80
60
40
20
0
Styrene acrylate P41E Untreated

Resin-Free Carbon Black Concentrate: 30 % carbon black,40% active dispersant on pigment

Gloss 60oAngle of Carbon Black in
Alkyd Resin Paint

80 74.2
70 40% active on carbon black
60 59
Gloss

50 46.3
40
30
20 16.4
10
0
MSMA P41E Styrene Untreated
acrylate

Resin-Free Carbon Black Concentrate: 30 % carbon black, 40% active dispersant on pigment
Compatibility of P41E in Different
Binder Systems

Binder system Compatibility

2 Pack Epoxy Good

Polyester resins Good

Alkyd resins Good

PU dispersions Good

Acrylic dispersions Good

Melamine resins Good

Properties of lithol rubine containing
various dispersants in semi gloss latex paint

Dispersant Dosage on ∆E Color Water

lithol rubine strength resistance

P41E 10% 0.49 111.09 Good

MSMA 20% 2.20 110.59 Good

Styrene 20% 0.67 100 Good

acrylate

P41E is two times more effective than other dispersants!

Properties of lithol rubine containing
various dispersants in high gloss paint

Dispersant Dosage ∆E Gloss Color Water

on blue strength resistance
P41E 10% 0.15 33.83 100.55 Good

MSMA 20% 0.27 30.2 101.48 Good

Styrene 20% 0.20 30.03 100 Good

acrylate

P41E is two times more effective than other dispersants!

Properties of lithol rubine containing
various dispersants in alkyd resin semi gloss paint

Dispersant Dosage ∆E Gloss Color Water

on blue strength resistance
P41E 10% 1.00 28.93 263.98 Excellent

MSMA 20% 5.07 26.2 100.00 Excellent

Styrene 20% 0.87 10.6 180.01 Excellent

acrylate

P41E is two times more effective than other dispersants!

Properties of phthalo blue containing
various dispersants in flat latex paint

Dispersant Dosage on ∆E Color Water

blue pigment strength resistance
P41E 20% 0.09 104.90 Good

Styrene 20% 0.47 100 Blisters

acrylate

MSMA 20% 0.16 102.9 Good

CONCLUSIONS

Polyetheralkanolamine
P41E

Flexibility Production capacity Quality

-VOC-free - Reduced milling time - Better dispersion stability

-APE-free - Decreased dispersion viscosity - Increased color development
-Compatible with binder to allow higher pigment loading - Maximun color acceptance
types of all bases
Special Thanks To:

Judy Perez
Lisa Fine

Thank you for your kind attention!

www.huntsman.com/cpr
Email:duy_t_nguyen@huntsman.com