How To formulate alkyd emulsions for

VOC free coatings with MaxemulTM 7000 series

Crod oatings

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Contents Page
Introduction 2

Experimental 2

1. Alkyd resin characterisation 3

1.1 Acid value determination 3

1.2 Viscosity determination 4

2. Emulsification procedure 4-5

3. Useful comments 6-9

4. Emulsion testing 10

5. Paint formulations 11

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 Facing the VOC challenge!
Croda offers the expertise and products to develop water borne alkyd resins for zero-VOC,
high quality trim paints, varnishes and stains. Maxemul advanced surfactant technology for
alkyd resin emulsification allows for total elimination of solvents in alkyd based coatings.
This “how to” literature describes the emulsification protocol for long and medium oil alkyds with Maxemul
7000 series of emulsifiers. It is a general outline. Reaction conditions are resin dependent, optimisation is
required.
The preferred formulation route is via the phase inversion technique.The phase inversion techniques is an
emulsification procedure whereby water is added to a resin/surfactant mixture. At first, a water in oil (W/O)
emulsion is formed. With more water added, the viscosity of the emulsion increases. At a critical phase ratio, the
emulsion inverts from a W/O to an oil in water (O/W) emulsion.This happens when the dispersed phase - the
water before the inversion point - becomes the continuous phase after the inversion point.
Emulsification conditions before inversion are most critical as they determine water droplet size and subsequent
the final resin droplet size.
The phase inversion process is preferred over direct emulsification for making alkyd emulsions with external
emulsifiers on large scale. If offers excellent reproducibility, giving emulsions with smaller droplets and narrow
size distribution, at lowest surfactant levels.
Investment costs for this zero VOC solution are minimal. A stirred reactor is needed, with powerful motor to
cope with the high viscosities during the process. Good mixing conditions with an axial flow is required during
the process.

Formulation 1pbw
Resin 50
Demineralised water 46.8
KOH 0.2
Maxemul 7201 1.5
Maxemul 7101 1.5
Total 100

Details Pa.s
KOH on acid value (%) 40
Surfactant on resin (%) 6
Surfactant ratio anionic/nonionic 50/50
Particle size (nm, initial) 200-400
pH (initial) 4-7
Brookfield viscosity (mPa.s, initial) 5 rpm,#1 100-500

Table 1: A typical formulation for a long or medium oil alkyd resin with low acid value

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1.Alkyd resin characterisation
Brookfield viscosity of the resin in function of temperature and acid value are important in order to build the
formulation and choose operating conditions.
1.1 Acid value determination
Background:
Alkyd resins for decorative coatings will preferably have an acid value <10mg KOH/g. It is recommended to
neutralise a fraction (approx. 40%) of the acid value.The neutralised carboxylgroups contribute to the charge
density and interfacial tension reduction. It allows to minimise the level of surfactant required, therefore
making the process more economical. KOH in powder form is preferably used. LiOH powder can be used as
well.
Procedure:
25ml of ethanol/toluene (30/70) and 0.01% phenolphthalein indicator are mixed in a beaker.A 0.1M solution
of potassium hydroxide is prepared and titrated against the ethanol/toluene/phenolphthalein solution until a
pale pink end point colour is obtained.
The alkyd resin is mixed with the ethanol/toluene mix and heated to ensure the resin is well dissolved into
the solvent.
The solution is then titrated with the potassium hydroxide solution until the end point is reached.
The following calculation is used to determine the acid value of the resin:

Volume of titre x 56.1 x molarity of potassium hydroxide solution

Acid value =
Weight of Sample

Formula 1: Acid value calculation

The amount of KOH needed to neutralize 40% of the resin is calculated from above.

Amount KOH to neutralise Acid Value x grams of resin x 0.4

=
40% of the resin 1000

Formula 2: Calculation of amount of KOH needed to neutralise 40% of the resin.

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 1.2 Viscosity determination
Background:
High speed stirring is not needed, and not preferred. Low speed stirring minimises energy consumption and
foam formation.
The shear necessary for water droplet size reduction is preferably provided by the resin viscosity, which is
controlled by the temperature during emulsification. Usually a resin viscosity of 10-15 Pa.s provides good
shear.Therefore, a viscosity vs. temperature plot for the resin is generated.The temperature at which viscosity
is approx. 10-15 Pa.s is chosen as emulsification temperature. Further temperature adjustment might be
necessary during the optimisation process.
Procedure:
The Brookfield viscosity is measured at different temperatures.

70000

60000

50000
Viscosity (mPas)

40000

30000

20000

10000

0
60 65 70 75 80 85 90 95
Temperature (°C)
Graph 1: Typical viscosity profile of a medium oil alkyd resin, solvent free

2. Emulsification procedure
A mass of approx. 200 gram of alkyd resin is charged to a double jacketed flat bottomed reaction vessel of 500
ml in volume and 100 mm diameter. The reactor is equipped with an overhead stirrer and Intermig impeller
of diameter 92mm.
The resin is heated to emulsification temperature and stirring started at 175 rpm, which corresponds to a
peripheral speed of approx. 0.84m/s.The required mass of KOH needed to neutralise 40% of the acid value of
the resin is ground into a fine powder and added to the resin.The KOH is allowed to disperse in the resin for 30
minutes. Maxemul 7101 is heated (at 50-60°C) until molten.The masses of the two surfactants,
Maxemul 7201 and 7101, are weighted, added to the resin and allowed to mix for another 30 minutes.
Demineralised water is heated to emulsification temperature. Water addition is then started using a continuous
feed of 1.6 ml/min until the total volume of water required is charged. Mixing speed and emulsification
temperature is kept constant until all water is added.The product is allowed to cool to ambient temperature
while stirring and then discharged.

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 1

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3

Figure 1. Emulsification hardware

1. IKA Eurostar Power control-visc.

2. 500 ml flat bottomed reaction vessel with 100 mm internal diameter, cylindrical thermostatic jacket.
With flat flange lid Centre neck, 1 vertical and 2 oblique side necks. (LENZ). Equipped with condenser.
3. Intermig impeller: 92 mm diameter. (EKATO)
4. REGLO-CPF digital (ISMATEC) with pumphead RH00 CKC-LF (FMI).
5. Water bath - Setup connected via stopcocks (yellow circles) to allow disconnection of reactor vessel.

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 3. Useful comments
1. Resin choice
A resin with a low acid value is preferred, typically with A.V. below 10 mg KOH/g. Resins with higher acid value
are sensitive to hydrolysis and are more difficult to emulsify. Oil based alkyds with glycerine as main polyol are
more hydrophilic and again more sensitive to hydrolysis.
Emulsification of Long and Medium oil alkyds is straightforward if recommendations in this brochure are
followed. Short oil alkyds are more difficult to emulsify and usually require higher surfactant levels. Medium to
short oil alkyds are easier to emulsify when chain terminated with benzoic acid.
2. KOH neutralisation
The residual acid value of the alkyd is neutralised with powdered KOH before emulsification starts.The ionised
carboxylgroups in the resin contribute to the charge density. Small particle size emulsions can be achieved with
lower surfactant levels compared to non-neutralised resin. KOH has given consistenly lower particle sizes vs
LiOH or ammonia for neutralisation.
Although a 50% KOH aqueous solution has given similar results, KOH in powder form is preferred for neutralisation
in order to avoid any risk of hydrolysis of the resin. Alternative amines have not been tested as neutralisation
agents. Amines can contribute to yellowing. Also, it has been suggested that amines can deactivate the drier.
3. Surfactant choice
Anionic surfactant Maxemul 7201 and non-ionic polymeric surfactants, Maxemul 7101 and 7201, have been
specifically selected for their compatibility with the resin phase. The anionic component reduces the oil/water
interfacial tension and facilitates the emulsification process.The non-ionic polymeric surfactant controls shelf life
and compatibility with the mill base and pigment pastes. Maxemul 7101 is mostly used as non-ionic, where
Maxemul 7102 shows better performance when emulsifying at elevated temperatures (>85°C). Maxemul 7102
is used in the same way as Maxemul 7101 in the emulsification process.
4. Surfactant handling
Maxemul 7101 and 7102 are solid products at ambient temperature with melting points of approx. 30°C and
40°C respectively. It is recommended to heat the products on waterbath or in a hot air oven at 50-60°C until
molten before mixing with the resin. The resin should have a temperature of min. 40°C upon mixing with the
surfactant to assure optimal homogenisation.
Maxemul 7101 and 7102, as all non-ionic surfactants are sensitive to heat exposure. Products will discolour and
can chemically degrade via oxidation when exposed to heat for longer periods of time. It is advised to minimise
heat exposure. Maxemul 7201 is a viscous liquid. It can be handled at ambient temperature and mixed cold
with the resin at emulsification temperature.

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5. Surfactant level and combination
For long and medium oil alkyd resins, usually 6% by weight surfactant on resin is needed, with equal parts
of an-ionic and polymeric surfactant. For an unknown resin, once the preferred emulsification temperature is
determined (see above), a series of formulations would be prepared, starting at higher surfactant levels and if
successful, gradually reducing surfactant levels until failure. Usually, the optimum anionic/ non-ionic surfactant
ratio needs to be corrected with changing surfactant level, with relatively higher anionic levels at lower overall
surfactant level, e.g.

Surfactant level Surfactant ratio Anionic Nonionic

10% on resin 20 80
8% 30 70
6% 50 50

Table 2:Typical anionic/nonionic surfactant ratio’s require adjustment with reducing surfactant levels

6.Water quality
Demineralised water is preferred. Efficiency of the anionic surfactant depends on the water hardness, hence
variations in water quality will result in changes in particle size. In the worst case, inversion is not obtained.
7. Emulsification process
The phase inversion process is preferred, surfactants are mixed with the resin and water is gradually added.
A slow continuous feed of water is preferred. As only little mechanical shear is applied (see below), the
breakdown of big water droplets is a slow process.The total amount of water is added in approx. 2 hours.
At first a water in oil (W/O) emulsion forms. At a critical phase ratio, the emulsion inverts from W/O to
O/W when the dispersed water phase becomes the continuous phase.This process usually gives an excellent
reproducibility. It does not require high speed mixers. Since the surfactants are mixed with the resin phase, they
are less mobile during film formation, which results in dry film with better water resistance.

Oil phase Water phase

Figure 2: Emulsification via the phase inversion process

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 8. Stirring speed and emulsification temperature
A slow stirring speed, from 0.8-1.2m/s peripheral speed is preferred. Experimental work has shown that less
surfactant is needed when stirring speed is lower. In this case, the necessary shear to reduce the water droplet
size before the inversion point is provided by the resin viscosity.This implies that temperature choice and control
are vital for obtaining fine droplets and good reproducibility.
9. Impeller choice
The choice of impeller is quite critical. Anchor shaped stirrers only give a radial flow and poor emulsification
conditions. Impellers from Ekato have been compared. Axial flow with good mixing action, even at high
viscosities is critical. An Intermig stirrer, with a diameter filling >90% of the reactor shows best emulsification
efficiency.A Viscoprop tends to give slightly higher emulsion droplet sizes at identical operating conditions.

Figure 3: Imtermig Impeller and flow patterns (Images from Ekato website). Information is available at
http://www.ekato.com/en products /ekato-rmt/products ekatoimpellers/

10. Observations during the emulsification process

The viscosity of the emulsion gradually increases during water addition, until a paste like viscosity is obtained.
This is a good indication that a W/O emulsion with fine water droplet size is achieved.The water droplet
size before inversion determines the size of the resin droplets after inversion.Therefore temperature control,
addition speed of the water are only critical before the inversion point.Water can be added faster once
inversion has taken place. Sometimes the viscosity dramatically drops at the inversion point, sometimes, a
clear inversion point is not noticed, but viscosity gradually decreases until all water is added.

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11.Water in oil or oil in water?
The most reliable method to determine if a W/O or O/W emulsion is formed is with conductivity measurements.
A ‘milk’-like consistency should be obtained. An indication that an O/W emulsion is formed, is when the milky
emulsion readily dilutes in water. It should be mentioned that also W/O emulsions, close to the inversion point
can spontaneously invert when diluted in water.
12. A quick qualitative assessment
A thin film applied on glass should have a bluish/reddish semi-transparent appearance, comparable to the
appearance of a thin film of milk in a glass.This is a good indication that an emulsion with a droplet size below
500nm has been achieved. Preferably particle size is determined with static laser light scattering. Emulsions
with particle sizes below 400nm usually have a good shelf life without tendency to sediment upon storage.
13. In-can preservation
Alkyd emulsions are sensitive to bacterial contamination. ProxelTM BZ Plus or ProxelTM BD20 at 0.1% on
formulation as recommended and supplied by Arch Biocides can be used for preservation.

Figure 4. Consistency of the emulsion close to the inversion point

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 4. Emulsion testing
1. Particle size
An emulsion with size below 400-500 nm will not show sedimentation over time.The Brownian motion of
the particles counteracts gravitational forces. Particle size is best measured with static laser light scattering.
2. Storage stability
Emulsions are stored at 40-50°C and particle size monitored over 4-8 weeks. Stable emulsions should resist
tropical storage with no particle size growth.
3. pH
The emulsions are sterically stabilised. pH has no effect on emulsion stability itself. A neutral to slightly acidic
pH is preferred to reduce risk of hydrolysis of the resin. A pH shift to acidic values indicates the onset of
hydrolysis. Emulsion stability failure can result.
4. Viscosity
The emulsion should have a low ‘milk’ like viscosity.Viscosity should not change dramatically upon storage.
Emulsion stability is monitored with particle size analysis:

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12

10
Volume (%)

0
0.01 0.1 1 10 100 1000 3000
Particle size (um)
11 weeks at 50°C 11 weeks at 40°C 11 weeks at RT Original

Graph 2 : Emulsion droplet size, initial results and after ageing

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5. Paint formulations
1. Mix with mill base during let down
Unlike solvent borne alkyds, an alkyd emulsion cannot be used as grinding medium.The emulsion can not
resist the shear forces during ball milling.The emulsion will break.A resin free grind is made and mixed at
low shear with the emulsion during let down stage.The usual ingredients for producing emulsion paints can
be used.
2. Drier choice
Conventional driers for solvent borne alkyds do not mix well with the alkyd emulsion. Special driers that are
emulsified or emulsifiable should be used for obtaining good drying conditions.
3. Starting formulation

Grind Parts by weight Function Supplier

Demineralised water 6.16 Carrier
ZephrymTM PD3315 1.32 Pigment dispersant Croda
Acrysol RM8W 0.43 Rheology modifier Dow
Dispelair CF698 0.08 Anti-foam Blackburn Chemicals
TiPure R-902+ 25.50 Pigment

Let down Parts by weight Function Supplier

Grind 33.50
Alkyd emulsion (50% resin solids) 56.50 Binder
Acrysol RM 2020 3.09 Rheology modifier Dow
Acrysol RM8W 0.75 Rheology modifier Dow
Octa-Soligen 421 aqua (4% on resin solids) 1.13 Drier OMG Borchers
Byk 348 0.33 Leveling agent Byk
Monopropylene glycol 1.33 Leveling agent
Demineralised water 3.80 Carrier

Table 3: High gloss white trim coating

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