J. Cent. South Univ. Technol.
(2008) 15: 324328
DOI: 10.1007/s1177100800614
Preparation of self-crosslinked acrylate emulsion with high elasticity and
its rheological properties
CHEN Li-jun(䰜ゟ)ݯ1, 2, WU Feng-qin(℺⨈)3, LI Dong-shuang(ᴢހ䳰)1, 2,
YANG Jian(ᴼ ᓎ)2, LI Rong-xian(ᴢ㤷)ܜ1, 2
(1. Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;
2. Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057, China;
3. Novel Company of Shenzhen, Shenzhen 518054, China)
Abstract: Using butyl acrylate(BA), methyl methacrylate(MMA), methacrylic acid(MAA) and mixed emulsifier as raw materials,
the self-crosslinked emulsion was prepared via pre-emulsified and semi-continuous seeded emulsion polymerization technology in
the presence of N-hydroxymethyl acrylamide and poly solidum maleate. The influence of mass ratio of BA to MMA, amount of
N-hydroxymethyl acrylamide and poly solidum maleate on the rheological properties of the self-crosslinked emulsion was studied.
Possible cross-linked mechanism of self-crosslinked monomer was investigated. And the relationship between emulsion viscosity and
shear rate was investigated. The results show that the self-crosslinked acrylate emulsion with high elasticity can be synthesized when
the mass fractions of BA is 60%, MMA is 40%, and added amount of N-hydroxymethyl acrylamide is 2.5%3.0% and added amount
of poly solidum maleate is 0.3%0.4%. The self-crosslinkage process of N-hydroxymethyl acrylamide involves two steps. One is
copolymerization of N-hydroxymethyl acrylamide and acrylate, the other is cross-linkage among polymer molecules via
condensation reaction of methylol. The emulsion is of rheological properties of pseudo-plastic fluid and belongs to non-Newtonian
fluid.
Key words: self-crosslinkage; acrylate emulsion; rheological properties; condensation reaction
cured methods of external cross-linked agent, self-
1 Introduction linkage has many merits such as high degree of
cross-linkage and convenience of use[1012]. In this work,
Emulsion paints have widespread application in self-crosslinked acrylate emulsion with high elasticity
finishing architectural wall[13]. However, conventional was prepared via pre-emulsified and semi-continuous
emulsion paints often lead to the crack of basal wall seeded emulsion polymerization technology by using N-
surface, which has an influence on the practicability and hydroxymethyl acrylamide as self-crosslinked monomer
functionality of emulsion paints. Drawbacks of and poly solidum maleate as protective colloid. Possible
conventional film can be overcome via selection of cross-linked mechanism of self-crosslinked monomer
elastic paints, but the main performance of elastic paints was put forward. In addition, the rheological properties
is dependent on the binder, i.e. polymer emulsions. of the prepared acrylate emulsion were analyzed.
Polymer emulsions with high performance are vital to
improve the properties of elastic coatings[45]. 2 Experimental
Acrylate emulsions are widely used in preparing
emulsion paints owing to their good water resistance, 2.1 Raw materials
weather resistance, ageing resistance and flexibility at Methyl methacrylate(MMA) and butyl acrylate(BA)
low temperature[67]. Self-crosslinked acrylate emulsions were from Guangdong Carpoly Coatings Corporation,
can be prepared via molecular design when some China. Monomers were distilled under reduced pressure
functional groups are introduced into molecular chain of to remove the polymerization inhibitor before use.
polymer[89]. The properties of polymer emulsion, such Potassium persulfate was recrystallized from water.
as heat resistance, water resistance and weather Polyethylene glocol mono-pnonyl phenyl ether(OP-10),
resistance, are further improved for polymer emulsions sodium dodecyl benzene sulfonate(DSBS), NaHCO3,
crosslink and cure via reaction among functional groups ammonia water, methacrylic acid(MAA),
of polymer molecules. Compared with cross-linked and N-hydroxymethyl acrylamide, poly solidum maleate and
Foundation item: Project(2003B10506) supported by Guangdong Provincial Department of Science and Technology, China
Received date: 20070829; Accepted date: 20070930
Corresponding author: CHEN Li-jun, PhD; Tel: +8675526551409; E-mail: chenlijun1975@[Link]
J. Cent. South Univ. Technol. (2008) 15: 324328 325
other reagents were all used as received. Distilled water emulsion was tested by Brookfield viscometer with No.2
was manufactured in our laboratory. rotor at 20 r/min and room temperature. The viscosity of
emulsion at different shear rates was tested by NXS-11A
2.2 Pre-emulsified and semi-continuous seeded rotary viscometer with type A rotor at room temperature.
emulsion polymerization
2.2.1 Preparation of pre-emulsified liquid 2.4 Gel rate
The pre-emulsification of parts of the monomers All the condensation products were collected after
was carried out in a four-neck glass flask equipped with a reaction and dried to constant mass. Gel rate was
stirrer, a thermometer and a dripping funnel. The calculated by
procedures are as follows[13]. m
1) Charge the distilled water, part of emulsifiers and w = 1 × 100% (1)
m2
self-crosslinked monomer into the four-neck flask under
where w is the gel rate; m1 is the mass of all the
moderate agitation.
collected dry condensation products; m2 is the mass of all
2) Set the water-bath to keep the temperature of
the monomers.
mixture at 45 ć.
3) Evenly drip part of mixed monomers of MMA,
2.5 Cross-linked degree of emulsion film
BA and MAA into the four-neck flask within 45 min
The emulsion film was formed at room temperature
under the agitation. Then the stable pre-emulsified liquid,
and then dried for 7 d. 1 g dried film was weighed and
whose appearance was milk white, was obtained for
extracted in a Soxhlet extractor with THF in 24 h. The
further use.
2.2.2 Preparation of self-crosslinked acrylate emulsion cross-linked degree of the emulsion film was calculated
Semi-continuous seeded emulsion polymerization by
was carried out in a four-neck glass flask equipped with a m1′
Dc % = × 100% (2)
stirrer, a reflux condenser and two dripping funnels. The m 2′
procedures are as follows. where Dc is the cross-linked degree of the emulsion
1) Add the distilled water, part of emulsifiers, film; m1′ is the sample mass after extraction; m ′2 is
NaHCO3 and protective colloid into the four-neck flask the sample mass before extraction.
under moderate stirring.
2) Set a water-bath to keep the temperature of
3 Results and discussion
mixture at 80 ć.
3) Drip the rest of mixed monomers of MMA, BA
3.1 Determination of mass ratio of BA to MMA
and MAA and part of initiator solution into the four-neck
Fig.1 shows that the mass ratio of BA to MMA has
flask within 15 min.
an effect on tg of the polymer emulsion. tg of the polymer
4) After reacting for 15 min the seeded emulsion,
emulsion can be preliminarily estimated from FOX
whose appearance was blue and fluorescent, was
obtained. equation[14]:
5) Drip the pre-emulsified liquid into the reactor 1 m1 m 2 m
within 4 h. After the reaction lasted for 1 h, the rest of = + +"+ i (3)
t g t g1 t g2 t gi
initiator solution was added into the reactor
simultaneously. The reaction lasted for 30 min after all
the raw materials were completely dripped into the
reactor.
6) Raise the temperature of water-bath to 90 ć and
maintain the reaction for 45 min.
7) Cool the resulted emulsion to 60 ć and adjust
pH value of the reaction mixture to 6.07.0 with
ammonia water.
Self-crosslinked acrylate emulsion was obtained
after the reaction mixture was filtered.
2.3 Characterization
MDSC 2910 was applied to analyzing glass
transition temperature (tg) of the emulsion. The raised
temperature was 50100 ć. The velocity of the raised Fig.1 Effect of mass ratio of soft monomer to hard monomer on
temperature was 20 ć/min. The viscosity of the tg of polymer emulsion