Pigment & Resin Technology

Emulsion copolymerization latices for interior and exterior coatings

M.M.H. Ayoub
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M.M.H. Ayoub, (1997),"Emulsion copolymerization latices for interior and exterior coatings", Pigment & Resin Technology,
Vol. 26 Iss 1 pp. 6 - 11
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 Introduction
Articles The formation of latices by emulsion poly-
Emulsion merization has been the subject of a number
copolymerization of research papers[1-3]. Latices in use today
are derived from the free-radical initiation
latices for interior and addition polymerization of unsaturated
exterior coatings monomers of vinyl or maleic type. Emulsion
paints differ dramatically from oil and alkyd
paints in the mechanism of film formation.
M.M.H. Ayoub The economics of latex paint manufacture
have also become more favourable than those
of solvent-based alkyds, not only because of
the lower cost of raw materials, but also the
reduced manufacturing insurance and pollu-
tion control costs. Emulsion polymer film
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formation results simply from the evapora-

The author tion of water: after sufficient water has evap-
M.M.H. Ayoub is based at the Department of Polymers orated the polymer particles come in contact
and Pigments, National Research Centre, Dokki, Cairo, with one another. Brown[4] has postulated
Egypt. that a capillary pressure set up in the inter-
stices between particles of sufficient magni-
Abstract tude causes the particles to deform, filling
Details the preparation of emulsion copolymerization of the voids. Film properties are further
styrene-vinylacetate with different molar ratios improved by interdiffusion of the polymer
33:67(A1), 50:50(A2) and 67:33(A3) using a redox molecules across the area of contact of the
initiator system (K2S2O8 NaHSO3) and investigates their particles[5-7]. Thus the morphology and
film forming. Finds that the drying film characterization mechanical properties of films depend on the
took on a brittle property which is attributed to the composition and structure of the polymer
nature of styrene polymers. Explains that a molar ratio of and also on the drying conditions and envi-
67:33 from butyl acrylate and vinyl acetate in the pres- ronments[8-12]. Many of the commercial
ence of a block copolymer surfactant (pluronic F87) was latices are produced using more than one
chosen as the coemulsifier as it gives good transparent monomer to attain the desired properties
and elastic film properties but has a tacky character such as hardness and elongation, i.e. vinyl
owing to the nature of butyl acrylate polymer. Shows that acetate by itself is a relatively hard, brittle
a styrene-butylacrylate 67:33 molar ratio has high polymer, but when copolymerized with
conversion and a solid content of 51 per cent, and its film acrylics, provides a good, water-sensitive
forming gives a transparent sheet that dries within 45 polymer, and when copolymerized with
minutes. Notes that incorporation of these latices into dibutyl maleate, produces a softer, and more
interior and exterior coatings gives good characterization elastic polymer.
(hardness, ductility, adhesion and washability of 4,042 In the present work, the copolymerization
cycles) compared with the standard specifications for of styrene monomer with vinyl acetate of
evaluation of latex paint. butyl acrylate and vinyl acetate with butyl
acrylate monomer was prepared to obtain
latices with high solid content which have
good properties for use in surface coating as
interior and exterior paints.

Experiment
Materials
Vinyl acetate (VAc), butyl acrylate (BuA) and
styrene (St) monomers were distillated and
stored in a refrigerator before use; these
Pigment & Resin Technology
Volume 26 · Number 1 · 1997 · p. 6–11 monomers were supplied from Merck-
© MCB University Press · ISSN 0369-9420 Schuchardt, (Germany). Polyvinyl alcohol
6
 Emulsion copolymerization latices for interior and exterior coatings Pigment & Resin Technology
M.M.H. Ayoub Volume 26 · Number 1 · 1997 · 6–11

(PVA) (M.wt.2,500, dp.7,500) and pluronic prevent destabilization or “shocking”, may be

F87 (polyethylene oxide-propylene oxide ad- added at this point. Then the dry pigments
ducts) as emulsifiers were supplied from Poly- are slowly added, allowing time for them to
Science Inc. (USA). Potassium persulphate be thoroughly wetted. The mixer speed is
(Merch-Schuchardt, Germany) and sodium then increased to provide high shear to dis-
bisulphite (Mallin-Chardt, Germany) are used perse the pigments. This grinding is contin-
together as a redox pair initiator system.
ued until the dispersion is free of aggregates.
The emulsion paint raw materials were:
The various ingredients and conditions of the
• water;
latex formulations for exterior and interior
• dispersing agent;
paints are shown in formulae (X) and (Y)
• defoamer;
• extender/fillers pigments; Tables II and III.
• emulsion (binder); Physical and mechanical tests of dry polymer
• pH adjuster – acid/alkali, e.g. ammonium and latex paint films
hydroxide. After applying films by wire bar the physical
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and mechanical properties of dry polymer

Methods
and latex paint films were evaluated by carry-
Copolymerization of styrene, vinyl acetate and
ing out the following tests:
butyl acrylate in the presence of pluronic F78 as
(1) Whiteness test – [13].
coemulsifier
The copolymerization reaction was carried (2) Drying time – ASTM D16490-1683.
out in a 250ml, three-neck flask with a (3) Adhesion – DIN 531557.
mechanical agitator. The general make up is
given in Table I. First, water, polyvinyl alco- Table II Formula X for exterior purposes
hol (PVA) solution and potassium persulphate
with sodium bisulphite as redox initiator were Materials Weight (g)
added and stirred for 30 minutes. A mixture Water 21.34
of co-monomers of VAc-St, VAc-BuA or St- Dispex GA 40 “dispersing” 0.50
BuA with different monomer ratios in the Ajetan 217 “defoamer” 0.50
Propylene glycol 3.70
presence of pluronic F78 as coemulsifier
(Stir for ten minutes)
(which is solubilized completely in the mix-
Liquid ammonia 0.06
ture of monomers) was added gradually via a Titanium dioxide “rutile” 15.00
separating funnel at 68˚C. Sodium bicarbon- Fine calcium carbonate 20.00
ate (0.3g) was added as a buffer for the Mergal AF “preservative” 0.10
adjustment of the pH of the medium. Finally, (Stir for 20 minutes then grind)
the latices formed were filtrated and stored in Dibutyl phthalate 0.50
glass bottles for application to interior and Wood turpentine 0.50
exterior paint formulations. Texanol 0.50
Viscalex VG2 3.30
Preparation of emulsion paint Emulsion latex (51 per cent solid) 34.00
The liquid ingredients such as water and (Stir for ten minutes)
cosolvents are mixed together in the contain- Total 100.0
er which will be used to prepare the pigment Solid content “practically” (%) 60-65
dispersion. The additives necessary to pre- Pigment volume
pare the pigment dispersion, which need to concentration (PVC) (%) 31.0

Table I The polymerization conditions for the prepared copolymer of styrene, vinyl acetate and butyl acrylate

Experiment Styrene Vinyl acetate Butyl acrylate Pluronic PVC Reaction time
code (ml) (ml) (ml) F87 (g) (g) (hours)
A1 16.0 34.0 – 5.0 0.20 5.0
A2 25.5 25.5 – 5.0 0.20 9.0
A3 33.5 16.5 – 5.0 0.20 5.0
B1 – 33.5 16.5 5.0 0.20 6.0
B2 – 33.5 16.5 3.2 0.20 5.0
B3 – 33.5 16.5 3.2 0.20 5.0
C 33.5 – 16.5 5.0 0.20 5.0
7
 Emulsion copolymerization latices for interior and exterior coatings Pigment & Resin Technology
M.M.H. Ayoub Volume 26 · Number 1 · 1997 · 6–11

Table III Formula Y for interior purposes (4) Hardness – ASTM D3359-74 part 27
(1975).
Materials Weight (g)
(5) Impact resistance (deformability) –
Water 26.54
ASTM D3002-71 part 27 (1975).
Cellocize (hydroxyethyl cellulose) 0.30
Sodium hexameta phosphate 0.30 (6) Ductility – Din 5315, Bs3900 part E4
(Stir for ten minutes) (1969).
Mergal AG “preservative” 0.30 (7) Washability – ASTM D2794-69 part 27
Agetan 217 “defoamer” 0.50 (1975);
Liquid ammonia 0.06 (8) Weathering test.
(Stir for ten minutes)
Titanium dioxide “rutile” 11.0
Lithopone 16.50 Results and discussion
Fine calcium carbonate 22.50 Copolymerization of St-VAc, VAc-BuA
Propylene glycol 1.00
and ST-BuA and their film properties
(Stir for ten minutes then grind)
Seven copolymers composed from St-VAc,
Dibutyl phthalate 0.50
VAc-BuA and St-BuA at different molar
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Wood turpentine 0.50

Emulsion latex (51 per cent solid) 20.00 ratios were prepared in the presence of
(Stir for ten minutes) pluronic F78 as coemulsifier with polyvinyl
Total 100.00 alcohol, with the condition given in Table I.
Solid content “practically” (%) 50-55 These emulsion polymer latices and their
Pigment volume films’ characteristics are listed in Tables IV-
concentration (PVC) (%) 50-51 VI. Two guide formulations, one based on

Table IV Characterization of the emulsion copolymerization of styrene-vinyl acetate

Characteristics A1 A2 A3
Ratio (styrene:vinyl acetate) (33:67) (50:50) (67:33)
Conversion (percentage) 73.0 73.1 54.1
Solid content (percentage)a 33.5 33.0 20.8
pH (2 per cent dist. H20)b 3.4 3 5
Drying time
Touch Three minutes 18 minutes 30 minutes
Through 15 minutes 60 minutes 45 minutes
Whitening test:
After 30 minutes Opal white White colour Semi transparent
After two hours Opal white White colour Opal white
After 24 hours White colour White colour Opal white
Appearance of dry film Turbid, brittle White colour, brittle Semi-transparent, brittle
a b
Note: ASTM 1229; ASTM D1172, ISO4316

Table V Characterization of emulsion copolymerization of vinyl acetate-butyl acrylate latex

Characteristics B1 B2 B3 Rva
Ratio (vinyl acetate)
butyl acrylate (67:33) (67:33) (67:33) Vinyl acrylic
Conversion (percentage) 89.5 100.0 62.5 –
Solid content (percentage) 37.7 46.8 29.0 55.0
pH (2 per cent H20) 5.6 6 3.4 6
Drying time
Touch Three hours Three hours Two hours 18 minutes
Through Non dry Non dry Non dry Five minutes
Whitening test:
After 30 minutes Transparent Opal white Transparent Opal white
After two hours Opal White colour Semi-transparent White colour
After 24 hours Slightly white White colour Opal white White colour
Appearance of dry film Transparent Transparent, Transparent, Transparent,
turbid, tacky tacky, elastic tacky, elastic glossy film
Note: a Trade name Rovace 9100 from Rohom and Haas Co.
8
 Emulsion copolymerization latices for interior and exterior coatings Pigment & Resin Technology
M.M.H. Ayoub Volume 26 · Number 1 · 1997 · 6–11

Table VI Properties of the emulsion latex prepared from the in standard formulations for exterior and
copolymerization of styrene-butyl acrylate interior coating purposes (see Tables II
and III).
Characteristics C RSa
Ratio (styrene:vinyl acetate) (67:33) Styrene acrylic Physico mechanical characterization of
Conversion (percentage) 100.0 – painted films for interior and exterior
Solid content (percentage) 51.0 50.0 coatings
pH (2 per cent H20) 3.4 7.5 Tables VII and VIII show the physical and
Drying time mechanical characteristics of painted films
Touch (minutes) 15 7 for exterior and interior coatings. The films
Through (minutes) 45 30
formed were tested for adhesion on a scale
Whitening test
from 5B to 0B, where 5B indicates that no
After 30 minutes Transparent Transparent
part of the coating chipped off, and 0B
After two hours Transparent Transparent
indicates that the chipped area is 65 per cent
After 24 hours Transparent Transparent
or more. According to standard specifications
Appearance of dry film Slightly turbid, Glossy transparent
for the evaluation of latex paint formulations,
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transparent
A1, A2 and A3 show good hardness, low
Note: a Trade name Repolem 2423 from Elf Atochem Co. ductility and fail under impact and adhesion
tests compared with the references Rs and
St-Acrylic (Rs) and the other based on VAc- Rv, which appear to have high ductility, good
Acrylic (Rv) were chosen for the comparison adhesion and pass the impact test. These
purposes. results can be attributed to the nature of
From the point of view of paint storage polystyrene and polyvinyl acetate polymers.
stability, it was found that a block copoly- The latices (B1, B2 and B3) were applied to
mer surfactant of the polyethylene oxide/ exterior and interior formulations for surface
propylene oxide adducts (in this instance coatings, as in X and Y formulations, and the
pluronic F87) was extremely effective. The resulting films were found to have good
protective colloid (e.g. poly vinyl alcohol) properties such as adhesion and ductility,
increases the viscosity of the medium (water passed the impact test required for surface
phase) and reduces the pigment-settling coatings, but also had good washability char-
tendency. This improves the stability of the acteristics compared with reference Rv.
system by minimizing the tendency of the Using emulsion latex C in exterior and interi-
dispersed particles to stick together if sub- or paints in formulations X and Y respective-
jected to stresses by mechanical means such ly gave good properties such as ductility,
as freezing. hardness and passed through the impact test,
From Table IV it is clear that, by increas- and showed the noticeable advance that it
ing the styrene monomer per cent (67 per has also good washability (4,042 cycles)
cent, formula A3), the drying film character- compared with reference Rs (2,867 cycles)
istics changed to the brittle property which is and a lower value for the loss of paint than
attributed to the nature of styrene polymer. that of reference Rs.
The copolymerization of butyl acrylate and
vinyl acetate (BuA-VAc) using the molar Weathering test
ratio of 33:67, as in experiments B1, B2 and This test is conducted to assess the durability
B3 are shown in Table V. The dry films of the painted film in outdoor exposure. The
become transparent and elastic but are tacky painted panels (with dry thickness film 50-
owing to the nature of butyl acrylate poly- 70µm) was covered by aluminium foil (50
mers. Table VI shows that the copolymeriza- per cent area) and exposed to a source of UV
tion of styrene with butyl acrylate using the and IR radiation. This kind of exposure for a
molar ratio 67:33 was acceptable compared period of one hour is said to be equivalent to
with reference Rs. outdoor exposure for one year. The exterior
paints for all prepared copolymer latices were
subjected to this weathering test. The formu-
Formulation of latex paints
la X for for A1, A2, A3, B1, B2 and C
The latices obtained from the emulsion passed the weathering test compared with
copolymerization process were incorporated references Rs and Rv. The weathering test
9
 Emulsion copolymerization latices for interior and exterior coatings Pigment & Resin Technology
M.M.H. Ayoub Volume 26 · Number 1 · 1997 · 6–11

Table VII Physical and mechanical characteristics of painted film for exterior coatings

Test XA1 XA2 XA3 XB1 XB2 XB3 XC XRv XRs

Adhesion
(at 50µm) 1B 1B 0B 3B 4B 2B 1B 4B 4B
Ductility
(at 70-80µm) 1.6 1.5 2.0 3.8 4.5 5.4 7.7 7.9 7.3
Impact (1)a Deformation Deformation Deformation Deformation Pass Pass Pass Pass Pass
(2)b Deformation Deformation Deformation Pass Pass Pass Pass Pass Pass
Hardness
(at 50µm) 68.6 53.3 65.0 22.0 17.3 59.0 47.0 20.8 16.0
Effect of
ultraviolet and
infrared Pass Pass Change in Change in Pass Pass Pass Pass Pass
colour colour
Note: a The thickness of the dry film is 40µm and the height is 40 inches
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b The thickness of the dry film is 120µm and the height is 120 inches

Table VIII Physical and mechanical characteristics of painted film for interior coatings

Test YA3 YB2 YB3 VC YRv YRs

Adhesion (at 50µm) 0B 3B 2B 1B 3B 4B
Ductility (at 70-80µm) 1.8 5.6 5.2 2.5 4.7 7.2
Impact (1)a Deformation Pass Pass Pass Pass Pass
(2)b Deformation Pass Pass Deformation Pass Pass
Hardness (sec) 92.5 35.5 57.0 35.0 20.5 19.5
Washability (cycles) 235 282 55.0 4,042 6,815 2,867
Loss of paint (%) 46.1 54.0 76.0 30.5 10.0 34.0
Notes: a The thickness of the dry film is 40µm and the height is 40 inches
b The thickness of the dry film is 120µm and the height is 120 inches

for exterior formulae shows that A1, A2, A3, acrylic system with the additives such as
B1, B2 and C also passed compared with coemulsifiers and thickeners exhibited an
other references. excellent balance of mechanical properties.
The exterior exposure tests for the
prepared copolymer emulsion latices give
Conclusion
excellent performance properties compared
The objective of the work described in this with the blank. Paints based on formulae
paper is the preparation and evaluation of the A1, A2 and A3 show good hardness, low
emulsion copolymer latices of styrene-vinyl ductility and fail with respect to adhesion
acetate (St-VAc), vinyl acetate-butyl acrylate tests, these results can be attributed to
(St-BuA) and the styrene-butyl acrylate the nature of styrene and vinyl acetate
(St-BuA)using different molar ratios. It was polymers.
found that the film formed from styrene Paints based on formulae B1, B2, and B3
polymer was brittle, while that formed from show good adhesion, ductility and passed the
vinyl acetate polymer was tacky. The copoly- impact test required for surface coatings but
merization of such monomers with butyl had low washability. The paint based on
acrylate using different feeding ratios formula C in exterior and interior paint
improved the film properties. purposes gave good characteristics, especially
The incorporation of the obtained washability (4,042 cycles) compared with
copolymer latices into interior and exterior that of references Rs and Rv. We therefore
formulation paints is described and recommended these formulations for exterior
discussed. It was found that the vinyl coatings.
10
 Emulsion copolymerization latices for interior and exterior coatings Pigment & Resin Technology
M.M.H. Ayoub Volume 26 · Number 1 · 1997 · 6–11

References 6 Hvilsted, S., Prog. Org. Coatings, Vol. 13 Nos 3-4,

1983, pp. 253-71.
1 Anderson, D.G. and Vanderberg, T.J., Anal. Chem, 7 Kast, H., Makromol. Chem. Supplements, Nos 10-11,
Vol. 57 No. 5, 1985, pp. 15-29. 1985, pp. 447-61.
2 Abd El-Ghaffer, M.A., Badran, A.S. and Shendy, 8 Rutherford, A., Pigment Resin Technology, Vol. 18,
S.M.M., Journal of Elastomer and Plastic, Vol. 24 1989, pp. 13-14, 17.
No. 3, 1992, pp. 192-202. 9 Rutherford, A., Polymer Paint Colour Journal,
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3 Badran, A.S., Ayoub, M.M.H. , Ghaffar, A.A., Nasher,
H.E. and Abd El-Hikm, A.A., European Polymer 10 Schild, L.R., El-Aasser, M.S., Poehlein, G.W. and
Vanderhoff, J.W., in Becker P. (Ed.), Dekker, New York,
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NY, 1978.
4 Brown, A., Fujimara, S. and Craven, K., Journal of 11 Van-Rossum, C.A. and Van-Gerresherin, W., Polymer
Polymer Science, part A, Vol. 27 No. 10, 1961, Paint Colour Journal, Vol. 179, 1989, pp. 410-26.
pp. 3315-25. 12 Yanagihara, T., Prog. Org. Coatings., Vol. 11 No. 3,
5 Hortschansky, P., Meissner, H. and Heublein, G., Acta 1983, pp. 205-18.
Polym, Vol. 36, 1985, pp. 345-60. 13 Repolem. Ecocryl, Eif Atochem, January 1992.
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