2. Some of our biggest brand are
Company Overview
Established in 1959, Pidilite Industries has become a dominant player in consumer and specialty chemicals
Pidilite is market leader in Construction chemicals, Art and craft materials
Some of our biggest brand are
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EFFECT OF DISPERSION PROCESS AND ANIONIC TO NON-IONIC RATIO ON PROPERTIES OF WATERBORNE POLYURETHANE DISPERSIONs
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4. CONTENTS Process flow for PU dispersion Experimental Design4
CONTENTS
Process flow for PU dispersion
Experimental Design
Critical Phase dispersion Process and impact of anionic: non- ionic ratio on phase inversion time
Effect of ionic content and process variation on:
Dispersion Properties
Particle size and viscosity, Electrolytic stability , shear stability
Molecular weight , Drying, Loss and storage modulus
Polymer Film properties
Drying time, Gloss, water, alkali and solvent resistance
Hardness , Tensile strength
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5. Process Flow for PU dispersion
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Schematic representation from -DSM resin Gail Pollano

6. Experimental Design 6 6 Critical Parameters
PUD by W/O dispersion Process (Water added into the polymer)
EXP 1
EXP 2
EXP 3
EXP 4
EXP 5
EXP 6
EXP 7
EXP 8
Anionic : Non-ionic
Non-ionic:Anioinic
% NCO 5
Ratio
1 : 0
1 : 0.5
1 : 1
1 : 1.5
1 : 2
1:0.5
PUD Solids (%) 40
Critical Parameters
PUD by O/W dispersion Process (Pre-polymer added into the water)
EXP 9
EXP 10
EXP 11
EXP 12
EXP 13
EXP 14
EXP 15
EXP 16
Anionic : Non-ionic
Non-ionic:Anioinic
% NCO 5
Ratio
1 : 0
1 : 0.5
1 : 1
1 : 1.5
1 : 2
PUD Solids (%) 40
Terminology in abstract used was direct process -W/O and Reverse process O/W 6 6

7. Critical Steps-Phase W/O Process,
Phase inversion phenomenon begins when water extends into the hydrophobic areas and their mobility decreases due to the occurrence of hydrophobic associates in the polymer matrix
The polymer -water interfaces then restructure and finally disintegrate into spherical dispersion particles enclosed by a continuous aqueous phase.
Ref. Technical seminar, Delhi Feb. 2009
by Dr Dirk Reichel, Evonik
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8. The Phase inversion phenomenon is observed only in W/O process
The Phase inversion phenomenon is observed only in W/O process. In O/W process this phenomenon was not prominent or not observed.
Time required to invert the phase (W/O to O/W) decreased with increasing the non-ionic and increases with increasing anionic
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9. With increasing anionic content the particle size decreases and corresponding viscosity increases.
At 1:1 concentration of non-ionic and ionic, PUD made with O/W process displayed finer particle size and lower viscosity
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10. Effect of Process and Anionic: Non-ionic content
on Shear
In both the process composition having higher content of non-ionic shows maximum viscosity increase, hence least stable.
Similar phenomenon observed in higher anionic content, however, the extent of viscosity pickup is low in case of W/O process.
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11. Molecular weight and polydispersity
PUD by W/O DISPERSION PROCESS
PUD by O/W DISPERSION PROCESS
Anionic:Non-ionic
Non-ionic:Anionic
Ratio
1 : 0
1 : 0.5
1 : 1
1 : 1.5
1 : 2
1:0.5
Molecular Weight (Mn)
13912
15291
14514
15105
12600
13500
16268
20028
18230
20736
23163
20993
17799
15435
22630
24989
Molecular Weight (Mw)
21397
20416
18916
20981
16021
16875
21089
25163
27430
29278
36533
31465
25143
19430
29600
33235
Polydispersity
1.54
1.34
1.30
1.39
1.27
1.25
1.26
1.50
1.41
1.58
1.31
1.33
No specific trend observed in Mol.Wt. w.r.t. increase in non-ionic
There is an increasing trend in Mol. Wt. with increasing the anionic content
PUD made with O/W process displayed higher Mol. Wt. and higher polydispersity
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* Higher the coagulum lesser is the stability
In all the cases electrolytic stability (especially in HCL) of the PUD made with O/W process are more stable than W/O process.
As expected the ionic stability increases with increase in non-ionic concentration and decrease with increasing anionic
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13. Drying Time, Gloss @60º, Viscoelastic Properties
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14. Water , alkali and solvent resistance of the polymer film
Spot Test ASTM 1308
Spot test on glass plates with 1 hour recovery: observations based on rating 0=no visible damage, 5=coating completely destroyed
In both the process the water resistance of the polymer film decreases with increasing the concentration of anionic and non-ionic.
The water resistance is highest in absence of non-ionic and lowest at higher non- ionic content.
In O/W process after 1:1 ratio decreasing trend was observed in alkali and water resistance.
In both the process the solvent resistance improved with increase in non-ionic content and decreases with increasing an-ionic
Polymer film of PUD made by O/W process displayed marginally higher solvent resistance than W/O process
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15. Pendulum Hardness, Tensile strength and Elongation
Pendulum hardness of the polymer film decreases with increasing the non –ionic in both the process . However, the trend is more prominent in O/W process than W/O.
The hardness is found to be highest when the anionic concentration became double. Interestingly, PUD made with W/O process are more harder in all cases
Irrespective of the process the Tensile and elongation are the highest in absence of non- ionic and lowest at 1:1 ratio of non-ionic and anionic.
In W/O process elongation increases with non-ionic /anionic content
In W/O process increase in elongation is more prominent with increase in ionic/non - ionic content
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16. SUMMARY
It was also observed that change in Anionic: Non-ionic ratio of the dispersion has significant impact on the mechanical properties such as hardness, elongation and tensile, as well as surface properties like drying time, gloss.
Solvent , water and alkali resistance are highly dependent on ionic content than process variation
In all the compositions the viscoelastic properties such as storage and loss modulus are independent of the process or Anionic: Non-ionic ratio and showed highly resilient properties.
There were no cross over in loss and storage modulus hence no distinct transition observed. This indicated highly amorphous nature of the polymer
It is possible to alter the properties and performance of the polyurethane dispersion using different dispersion process.
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17. Acknowledgement Pidilite Industries limited for their support.
The authors are grateful to
Pidilite Industries limited for their support.
Thanks to the Analytical team for valuable inputs, and Yashika for assisting in experimental work.
08/31/15
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18. Thanks
For your attention
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19. References
Phase W/O in polyurethane prepolymer-water dispersions, Ph. D. Thesis by Saw, Lin K, Loughborough University, August 2000
Barni, A.; Levi, M. J Appl Polym Sci 2003, 88, 716.
M. J. Ferna´ndez-Berridi et al. J. Appl Polym Sci, 2011, 120(4)
4. ASTM D523-89(1999) Standard Test Method for Specular Gloss
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