Enhancing the performance of waterborne

coatings through the polymerization of

super-hydrophobic monomers

NVVT Studiemiddag
Javier Bohrquez
26 January 2016
Agenda/contents

1. Introduction and motivation for the technology implementation

2. Colloidal and kinetic analysis: synthesis of super-hydrophobic

monomer emulsions

3. Technology benefits for surface coatings

4. Summary

1
1. Introduction and motivation for the technology implementation

2
3
HYDROPHOBIC COATINGS

IN AQUEOUS MEDIA?

4
 Monomer Solubility Monomer Solubility
(ppm) (ppm)
Vinyl Acetate 42700 Isobornyl acrylate 3.12
Methyl methacrylate 22500 Lauryl methacrylate ----
Butyl acrylate 3380 Stearyl acrylate -----
Styrene 2370 Stearyl methacrylate -----
2-ethylhexyl acrylate 164 Perfluorodecyl acrylate -----
VeoVa 10 36
Chai, X.-S., Ind. Eng. Chem. Res. 2005, 44, 5256-5258

5
 Energy intensive High concentrations Longer/Complex
Scale up = Bottleneck Removal process processes
for industrialization associated Not yet fully zero
VOC

Miniemulsion Transport Secondary

Polymerization Catalyst Emulsions

6
I. To develop a process to polymerize superhydrophobic
monomers through emulsion polymerization w/o the aid of
miniemulsification steps, transport catalysts and/or organic
solvents.

II. To formulate into coatings the dispersions obtained and

evaluate their performance in water and/or weathering
associated tests.

7
2. Colloidal and kinetic analysis: synthesis of super-hydrophobic
monomer emulsions.

8
COMBINATION OF EMULSIFIERS

Name Description CMC

HYDROPHOBICITY
Anionic / Sodium Sulfosuccinate / Di-ester
EC1 1 ppm

EC2 Anionic / Sodium Sulfosuccinate / Half-ester 160 ppm

Sodium Lauryl Sulphate

SLS 2400 ppm

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 REFERENCE CONDITIONS
LMA/IBA Temperature 70C
EC-1 Stirring rate Mild
TBH SLS Solids content 40%
EC-2 AsAc Seed content 0.5 20%
H2O H2O Emulsifier content 1.5 3 %wbm
EC-1:EC-2 ratio 1:1.5
EC-1:EC-2 ratio 1:2.5
POLYMER
SEED

MAIN CONTROL VARIABLES

Number of particles Particle size distribution
Emulsifier content Total surface area
Emulsifier ratio Polymer composition

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TYPE I: HIGH NUMBER OF PARTICLES HOMOGENEOUS
DISTRIBUTION

TYPE II: LOW NUMBER OF PARTICLES DROPLET

NUCLEATION

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 230
TYPE I: HIGH NUMBER

Particle size (nm)

OF PARTICLES 200
170
Seed content 2.5 %wbm
140
Solids content 40%
110
Final particle size 200 nm dv
80
Emulsifier content 2.0 %wbm Theo
50
0 60 120 180 240 300
Time (min)
TYPE II: LOW NUMBER 100
40 min
OF PARTICLES
80 120 min

% Volume
200 min
Seed content 0.5 %wbm 60 Latex
Solids content 40%
40
Final particle size 300 + 450 nm
20
Emulsifier content 2.0 %wbm
0
0 200 400 600 800
Particle Size (nm)

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 LMA/IBA/MAA
EC-1 REFERENCE CONDITIONS
TBH SLS Temperature 70C
EC-2 AsAc Stirring rate 120 rpm
H2O H2O Seed content 0.5 20%
Emulsifier content 3 %wbm

IBA or Nu1
SEED

Dispersion dp (nm) S.C (%) Composition / Description

Nu1 84 43.1 Commercial dispersion with gradient morphology
HYFO 90 40.0 IBA Seed (20%) / IBA (48%) / LMA (31%) / MAA (1%)
H10 188 40.6 Nu1 (10%) / LMA (45%) / IBA (42%) / MAA (3%)
H20 120 40.0 Nu1 (20%) / LMA (40%) / IBA (37%) / MAA (3%)
H50 108 40.4 Nu1 (50%) / LMA (25%) / IBA (22%) / MAA (3%)

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3. Technology benefits for surface coatings

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REFERENCE CLEAR COAT FORMULATION FOR
Nu1 / HYFO / H10 / H20 / H50

COMPONENT (g)
Dispersion 83.0
Water 8.3
Butyl glycol 0.4
Butyl diglycol 0.1
Defoamer 0.5
Polymeric wax 2.0
Silicone surfactant 0.5
PU-thickener 5.2
ASR Variable

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 WEATHERING TESTS CHEMICAL RESISTANCE TESTS
(4h UVA + 4h H2O cycles)
Nu1
1.0
Relative Gloss 60

0.8
0.6
0.4 Nu1
H20 HYFO B HYFO A
0.2 HYFO A
HYFO B Water
0.0 Coffee
0 200 400 600 800 Wine
Exposure Time (h) Ethanol
Mustard
H20

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 Contact
Clear coatings Gloss 20 Gloss 60 Haze
Angle
Nu1 78 89 66 78
H10 55 78 92 87
H50 58 80 85 92

80
70
60
Hardness ( s )

50
40 Nu1
30 H10
20 H50
10
0
24 48 120 168
Time ( h )

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WATER BARRIER PROPERTIES

Nu1 H10 H50

Nu1 H10 H50

1 hour water immersion

Water vapor contact 1 h

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 PIGMENTED SYSTEM
COMPONENT (wt%)
TiO2 64.5
160
Water 8.1
140
Butyl glycol 1.7
120

Hardness ( s )
Butyl diglycol 1.0
100
Defoamer 0.2
80 Nu2
DBC-1 25.5
60 H10
Blue tint 3% v/v
40 H50
20
0
24 48 120 168
Time ( h )

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 Water immersion (4h) / Dry RT (4h)
cycles for 72 hours

Nu2 H10 H50

20
 Water vapor contact 4 h

Nu2 H10 H50

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4. Summary

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SUMMARY:

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 ACKNOWLEDGEMENTS:

Dr. Dirk Mestach

Marcel Meeuwisse

Prof. Mariaje Barandiaran

Prof. Maria Paulis
Freddy Boscan

This presentation has been prepared by Nuplex and is for general information only. Every effort has been made to ensure that it is
accurate, however it is not intended to be a complete description of the matters described.
This document was accompanied by an oral presentation, and is not a complete record of the discussion held.
No part of this presentation should be used elsewhere without prior consent from the author.

24
Enhancing the performance of waterborne
coatings through the polymerization of
super-hydrophobic monomers

THANKS A LOT FOR YOUR ATTENTION

QUESTIONS?