Available online at: http://journal.ippi.ac.

ir

Synthesis of Diacetone Acrylamide Monomer and

Iranian Polymer Journal
the Film Properties of Its Copolymers
19 (10), 2010, 801-810

Nishant V. Tale and Ramanand N. Jagtap*

Department of Polymer and Surface Engineering, Institute of Chemical Technology,

N.M. Parekh Marg, Mumbai-400019, India

D
Received 22 March 2010; accepted 18 September 2010

ABSTRACT

D SI
iacetone acrylamide (DAAM) was derived from alkaline hydrolysis of 2-methyl-
4-oxo-N-[(1Z)-1(sulphooxy)prop-2-ene-1-ylidene]pentan-2-aminium as a precur-
sor which the latter was prepared by condensation of acrylonitrile and acetone
in sulphuric acid. Diacetone acrylamide was characterized by 1H NMR, FTIR and mass
spectrometry for structural conformation. The DAAM copolymer emulsions were
of
prepared by a two-stage seed batch emulsion polymerization of methyl methacrylate,
butyl acrylate and DAAM using ammonium persulphate as an initiator, sodium lauryl
sulphate and nonyl phenol as emulsifiers. Diacetone acrylamide was used as a
functional monomer. Further, the DAAM copolymer emulsions were characterized and
studied as a function of DAAM concentration by laser light scattering, viscometry and
ive

differential scanning calorimetry. The results have shown that with increased
concentration of DAAM in the emulsions there are increases in particle size, particle
size distribution and viscosity of the emulsions, whereas the glass transition
temperature (Tg) of DAAM emulsions is reduced. These emulsions comprising different
concentrations of DAAM were cross-linked with 1,3-diaminopropane and were
characterized by FTIR. The cross-linking reaction was carried out at ambient
ch

temperature resulting in formation of one-component thermoset acrylic emulsions.

These emulsions which were used as coatings were evaluated for mechanical and
chemical resistance properties. The results obtained showed that the coating
comprised of 4 wt% of DAAM in copolymer emulsion exhibited improved chemical
Key Words: resistance and mechanical properties.
Ar

diacetone acrylamide;
thermoset; INTRODUCTION
seed batch emulsion
copolymerization; Growing awareness and environ-
1,3-diaminopropane. mental legislations are imposing
restrictions on the emission of
volatile organic compounds
(VOCs). These restrictions have
forced coating manufacturer to for-
mulate coatings comprised of low
or zero content of VOCs. Emulsion
polymerization is an important
polymerization technique, as it
(*) To whom correspondence to be addressed. yields high molecular weight poly-
E-mail: rn.jagtap@ictmumbai.edu.in mers with low viscosity. Moreover,
polymers can be tailor-made in
order to exhibit desired com-
position and morphology [1-4].
Diacetone acrylamide (DAAM)
is a vinyl functional monomer hav-
ing good solubility and reactivity
ratio with most of the comonomers
and is capable of forming polymers
and copolymers with exceptional
ease [5,6]. The carbonyl groups of
DAAM can readily cross-link with
primary amines and form imines,

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Synthesis of Diacetone Acrylamide Monomer ...
whereas with secondary amines give enamines with
elimination of water molecule [7,8]. The most
striking features of this cross-link reaction is that it
proceeds rapidly at ambient temperature, therefore it
is environmentally friendly and non-hazardous,
which makes it useful in a wide variety of applica-
tions like architectural coatings [9], wood coatings
[10], water repellent coatings [11], inks [12,13] and
adhesives [14-16]. Thus, it has been emphasized in
the development of a one-component thermoset
emulsion system curable at ambient temperature
[17,18].
In some reported works [19-21], adipic acid
dihydrazide (ADH) was comprehensively utilized as
a cross-linker whereas in this contest, we used 1,3-
diaminopropane as a cross-linker instead, because of
some limitations with ADH properties, i.e., poor
solubility in water (5 g/100 mL) which coagulates the
emulsion when added directly and it is susceptible to
alkaline and acid hydrolysis due to the presence of
two amide linkages. Based on literature, DAAM was
of
prepared from acetone, acrylonitrile and sulphuric
acid by Ritter reaction [22-25].
In the present investigation, re-examination and
modification have been applied on the reaction
ive
system of acetone-acrylonitrile-sulphuric acid. We
report the formation of a water soluble intermediate,
2-methyl-4-oxo-N-[(1Z)-1(sulphooxy)prop-2-ene-1-
ylidene]pentan-2-aminium. 1,3-Diaminopropane was
used as a cross-linker to synthesize the one-com-
ch
ponent thermoset emulsions with various concentra-
tions of DAAM. The effects of DAAM concentration
on dry film thickness and mechanical and chemical
properties of coating have been studied, as well.
Ar
EXPERIMENTAL
Material
Acrylonitriles, methyl methacrylate (MMA), butyl
acrylate (BA) were purified by treating with 10% of
NaOH solution followed by washing with water to
remove inhibitor and were dried over sodium
sulphate. Acetones, sulphuric acid, ammonium
persulphate, 1,3-diaminopropane of analytical grade
were purchased from S.D. Fine Chem. Ltd. Co,
(India). Nonylphenol 10 (NP 10), sodium lauryl
802 Iranian Polymer Journal / Volume 19 Number 10 (2010)
Tale NV et al.
sulphate (SLS) were used as emulsifiers, toluene,
petroleum ether, sodium hydroxide, sodium
bicarbonate were procured from Thomas Baker
(India). De-ionized water was used throughout the
experiment.
Synthesis of Diacetone Acrylamide
A mixture of 1 mol of acrylonitrile (compound 1 in
Scheme I) and 2 mol of acetone (compound 2 in
Scheme I) were added dropwise in to 1.2 mol of
sulphuric acid 96% under constant stirring at 0°C
over a period of 2 h, after the complete addition, the
reaction mixture was heated at 45°C for 4 h. On
completion of digestion, the reaction mixture was
D
cooled to 0°C and diluted with acetone, resulting to
the formation of crystals of 2-methyl-4-oxo-N-
[(1Z)-1(sulphooxy)prop-2-ene-1-ylidene]pentan-2-
SI
aminium (compound 3 in Scheme I). The obtained
crystals were dissolved in 1/1(v/v) water/toluene
mixture, and on standing the organic and aqueous
layers separated. The monomer was extracted several
times with toluene to form an aqueous layer. By
collecting the organic layers and concentrating them
under vacuum at 50-55°C and cooling them at 0°C,
crystals of diacetone acrylamide (compound 4 in
Scheme I) were obtained. The progress of reaction
was monitored by TLC. Yield and melting point were
O
+
N
1 2
H2SO4
OSO3H O
N
3
H
Neutralization
tautomerism
O O
N
4
H
Scheme I. Synthesis of diacetone acrylamide.
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 Tale NV et al. Synthesis of Diacetone Acrylamide Monomer ...

Table 1. The recipe of seed batch emulsion polymerization of DAAM-MMA-BA.

Second stage weight (g)

Ingredient Seed

1st 2nd 3rd 4th

BA 8.25 11.85 11.85 11.85 11.85

MMA 4.25 23.85 24.85 25.85 26.85
DAAM 0.00 0.914 0.685 0.457 0.228
SLS 0.85 0.850 0.85 0.85 0.85
NP-10 0.55 0.550 0.55 0.55 0.55
APS 0.25 0.250 0.25 0.25 0.25
NaHC03 0.10 0.100 0.10 0.10 0.10
DI 27.0 27.00 27.0 27.00 27.00

their respective values of 53% and 54-56°C.
Synthesis of Copolymers of DAAM-MMA-BA
Emulsion
Sodium lauryl sulphate, NP10, and de-ionized water
were added into a three-neck flask, equipped with a
stirrer, a condenser, and thermometer. The entire
SI pre-emulsion was fed into the three-neck flask over a
of
assembly was placed in water bath connected to
temperature controller maintained at 50°C, and the
mixture was stirred at 100 rpm, followed by
introducing a ratio of 1/4 pre-emulsion of monomers
ive
D
mixture to 72°C and maintained for 20 min. A slight
blue colour appeared which indicated the formation of
seed latex particles. Now, the remaining monomer
period of 3.5 h. The remaining initiator was divided
into several equal portions and added to vessel at spe-
cific time intervals during monomer feeding, and in
the mean time a buffer solution (NaHCO3 solution)
was also added at specific intervals. Once feeding was
completed, the temperature was raised to 80°C for
another 15 min. Finally the latex was cooled and

and initiator (APS 0.1 g in 1 mL water) into the three- filtered. The recipe of seed batch emulsion poly-
neck flask, and raised the temperature of reaction merization is summarized in Table 1.

O O O O
ch

+ +
N O OC4H9

N-(2-methyl-4-oxopentan-2-yl)acrylamide Methyl methacrylate Butyl acrylate

Ar

(APS) Initiator

n n n
O O O
NHOCH3 C4H9O

O Copolymer of DAAM

Scheme II. Synthesis of DAAM copolymer.

Iranian Polymer Journal / Volume 19 Number 10 (2010) 803

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Synthesis of Diacetone Acrylamide Monomer ... Tale NV et al.

M CH2 CH M M CH2 CH M

C O O C CH3

NH H2N (CH2)3 NH2 HN C CH2 C CH3

H3C C CH3 1,3-Diaminopropane CH3 N CH2 CH2 CH2

CH2 O CH3 N

C O C HN C H2C C CH3

CH3 M H2C CH CH3

Scheme III. Cross-linking reaction between DAAM copolymer chains.

D
Preparation of an Aqueous Cross-linker Solution (Antopar, GMBH, Austria)
To make a 40% solution of 1,3-diaminopropane in the
mixture of de-ionized water, propylene glycol
monomethyl ether (PGME) and propylene glycol
monopropyl ether (PGPE) at 37/3/20 wt% ratio were
used. Propylene glycol monopropyl ether swelled the
resin and enhanced the promoter penetration of the
SI Cross-linking Procedure for the Emulsion
Emulsions were coated on the treated M.S. panel by
using a bar coater and then dried. The thickness of
dried film was about 50 μm. The coated panels were
dipped into a solution of 1,3-diaminopropane for
of
cross-linker. Phosphoric acid (3%) was added as a 10 min at room temperature and were further washed
catalyst for cross-linking reaction. with water and the remaining droplets on the surface
The polymerization of DAAM, MMA, BA and wiped out with a filter paper. The weight of the
cross-linking reaction of DAAM with 1,3-diamino- swelled panel (A) was immediately recorded and the
ive

propane is shown in Schemes II and III. panel was dried for 10 min at 110°C to obtain the
weight of dried panel (B). Swelling degree was
Monomer Characterization calculated by following equation.
FTIR analyses (Shimadzu 8400s, Japan) of DAAM
A− B
ch

and emulsion were both recorded using ATR tech- Swelling (%) = ( ) × 100
C
nique. 1H NMR spectrum of DAAM was recorded at
500 MHz using Bruker Biospin (Avance AV500WB, where
Germany) in CDCl3. For GC-MS analysis, 10 ppm A = weight of swelled panel
Ar

solution of DAAM was made in dichloromethane and
recorded the chromatogram using Shimadzu (QP
2010, Japan).
Polymer Characterization
Particle size and particle size distribution of emulsion
were measured using particle size analyzer based on
laser scattering (Cilas, 1064, France). Differential
scanning calorimetry (DSC) (Q100 V9.7 Build 291,
USA) was performed at a rate of 10°C/min. A sample
of 5-8 mg was put in an aluminium pan and used for
thermal analysis in DSC instrument. Viscosity of the
emulsion was measured using Brookfield viscometer
B = weight of the dried panel
C = weight of coating panel
Mechanical Testing on Coatings
Scrub resistance test was performed according to
ASTM 2486-79 and the film results are given as
number of cycles. Impact resistance was carried out
on both sides of coated panels and analyzed in
accordance to the standard ASTM D 2794. The
results were categorized as fair (cracking), good
(slight cracking) and best (no change).
Pencil hardness test was used to observe the hard-
ness values of the films according to ASTM D 3363.

804 Iranian Polymer Journal / Volume 19 Number 10 (2010)

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 Tale NV et al.
Figure 1. Relationships between the thickness of
cross-linked layers of DAAM copolymer and dipping time in
1,3-diaminopropane solution at room temperature.
The scratch hardness was determined by an automat-
ic scratch hardness tester as per ASTM D7027. For
adhesion testing, cross-cut adhesion tape was used to
SI mers was 50±5 μm. These films were cured by
of
assess the adhesion of film coated onto metallic
substrate according to ASTM D 3359.
Alkali resistance of panels was evaluated for film
whitening and blistering according to ASTM D 1647.
ive
Acid resistance of panels was evaluated for
peeling and corrosion of coated part according to
ch
Ar
Figure 2. FTIR Spectrum of 2-methyl-4-oxo-N-[(1Z)-1(sulfooxy) prop-2-ene-1-ylidene] pentan-2-aminium.
Iranian Polymer Journal / Volume 19 Number 10 (2010)
Synthesis of Diacetone Acrylamide Monomer ...
ASTM D 3260.
For water resistance testing, the coated panels
were immersed in water and then, the panels were
evaluated for colour change of coating, blistering,
skinning according to ASTM D 870-02. Flexibility of
the coated M.S. panel was determined by the conical
mandrel according to ASTM D 522- 93a, finally.
RESULTS AND DISCUSSION
Effect of Dipping Time on Degree of Cross-linking
Reaction
Figure 1 shows correlations between dipping time and
D
thickness of cross-linked layer of the emulsions at
four different concentrations of DAAM.
The dry film thickness (DFT) of DAAM copoly-
dipping into 1,3-diaminopropane cross-linker for
10-30 min. It was observed that with increase in
DAAM content and dipping time, the DFT value of
the cured films was increased. Diacetone acrylamide
as a polar monomer has high affinity towards water.
Therefore, when DAAM content in the copolymer is
increased from 1 wt% to 4 wt%, the swelling of the
film is also increased leading to enhanced penetration
of the 1,3-diaminopropane. This resulted into
805
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Synthesis of Diacetone Acrylamide Monomer ... Tale NV et al.

D
Figure 3. FTIR Spectrum of DAAM.

increased DFT value of the final cured film.

FTIR Analysis of 2-Methyl-4-oxo-N-[(1Z)-

SI sulphate [26]. Thus, from FTIR analysis the structure
of
1(sulphooxy)prop-2-ene-1-ylidene]pentan-2-
aminium
Figure 2 shows the peaks at 3169, 2818, 1720 and
1662 cm-1 assigned to -NH str, aliphatic C-H str,
C=O str, and amide str (C=O), respectively. The peak
ive
of 2-methyl-4-oxo-N-[(1Z)-1(sulphooxy) prop-2-
ene-1-ylidene] penta-2-aminium (compound 3 in
Scheme I) is confirmed.
FTIR Analysis of Diacetone Acrylamide
Figure 3 shows the peaks at 3280 cm-1 assigned to
N-H str, at 3088 cm-1 corresponding to =C-H str, at

at 1613 cm-1 is characteristic absorption band of
intermediate C=N str. The peak at 1531cm-1 is
assigned to C=C, and those at 1401 and 1058 cm-1
are assigned to S=O str and S-O str, respectively
ch
2899 cm-1 assigned to aliphatic C-H str, and at
1718 cm-1 and 1622 cm-1 are the characteristic
absorption bands of keto (C=O str) and amide (CONH
str) groups, respectively. Moreover, the peak at 1556

which are characteristics stretching bands of organic cm-1 is assigned to C=C str [26].
Ar

Figure 4. FTIR Specra of: (a) DAAM copolymer and (b and c) cross-linking DAAM copolymers.

806 Iranian Polymer Journal / Volume 19 Number 10 (2010)

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 Tale NV et al.
Figure 5. 1H NMR Spectrum of DAAM.
Confirmation of Cross-linking Reaction of DAAM
Copolymer with 1, 3-Diaminopropane by FTIR
Figure 4 shows FTIR spectrum of DAAM copolymer
(spectrum a) and cross-linking DAAM copolymers
(spectra b and c). Carbonyl groups of DAAM readily
react with 1,3-diaminopropane to form imines (C=N)
and shows the characteristic IR absorption at 1623
cm-1 and indication of the cross-linking reaction
of
taken place between the carbonyl group and 1,3-
diaminopropane. It is also evident from the emulsion
spectra that the absence of the carbonyl group (C=O)
peak at 1713 cm-1 and amide peak at 1681 cm-1 and
ive
NH groups peak at 3325 cm-1 [26] confirm the cross-
linking reaction.
1H NMR Analysis of Diacetone Acrylamide
ch
Figure 5 shows the arrangement of proton of
diacetone acrylamide. 1H NMR (500 MHz, CDCl3) δ
: 1.4 (3H, s), 1.7 (3H, s), 2.1 (3H, s), 2.9 (2H, s), 5.5
(1H, d), 6.0 (2H, d), 7.2 (1H, s, -NH) ppm [26].
Ar
Mass Spectrometry of Diacetone Acrylamide
Figure 6 shows molecular-ion peak of DAAM at
M/Z = 169 which indicates the formation of DAAM
Table 2. Particle size of DAAM copolymers at various DAAM contents.
Sample DAAM in emulsion
No. (wt%)
1 1
2 2
3 3
4 4
Iranian Polymer Journal / Volume 19 Number 10 (2010)
Synthesis of Diacetone Acrylamide Monomer ...
Figure 6. Mass spectrometry of DAAM.
having molecular weight 169, the base peak (100%
intensity) at M/Z = 58, and other fragments having
M/Z = 154, 126, 112, 100, 84, 72, 55, 41, and 27,
D
respectively [26].
SIEffect of DAAM Concentration on Particle Size
and Particle Size Distribution of DAAM
Copolymers
The particle size of DAAM copolymer emulsions
increased with DAAM concentration, as DAAM has
high affinity towards water, thus it migrates towards
the aqueous phase bringing on this the size of
micelles increases which lead to increase in particle
size, and also it may stabilize latex like surfactants
[21]. The bimodal particle size and particle size
distribution of DAAM copolymer emulsions were
observed with increased concentration of DAAM
which resulted in diminished stability of the
emulsions. The results of particle size and particle
size distribution of DAAM copolymers at various
concentrations of DAAM are summarized in Tables 2
and 3, respectively.
Effect of DAAM Concentration on Glass
Transition Temperature of DAAM Copolymers
The DSC thermograms of the copolymers are shown
Particle size Stability at room
(μm) temperature (day)
10.41 312
10.65 312
11.60 377
15.42 232
807
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Synthesis of Diacetone Acrylamide Monomer ...
Table 3. Particle size distribution of DAAM copolymers with varying DAAM contents.
Sample Particle size
No. distribution 1 2
(wt%)
1 D10% 1.35 μm
2 D50% 7.28 μm
3 D90% 25.14 μm
in Figure 7. In copolymers, DAAM is polymerized
with MMA and BA, wherein part of MMA is replaced
with DAAM at 1 to 4 wt%. The glass transition
temperature of MMA and DAAM are 100°C and
77°C, respectively. As the weight fraction of the soft
monomer DAAM is increased, due to the decrease in
the weight fraction of hard MMA monomer, this
resulted in decrease in the glass transition temperature
of the final copolymers from 27.06°C to 13.65°C.
Effect of DAAM Concentration on Viscosity of
SI Dramatic improvement was observed in chemical and
of
DAAM-MMA-BA Emulsion
Figure 8 shows the relation between concentrations of
DAAM on viscosity of the emulsion. Hydrophilic
DAAM contains carbonyl group which can form
ive
inter- and intramolecular hydrogen bonds with water
molecules. The hydrogen bond formation of carbonyl
groups of DAAM is enhanced in a manner which is
proportional to DAAM concentration. In this way,
ch
molecular chains are compelled to overcome the
strong hindrance when emulsion flows. Therefore,
Ar
Figure 7. DSC Thermogram of DAAM copolymer with
varying amounts of DAAM concentrations.
808 Iranian Polymer Journal / Volume 19 Number 10 (2010)
Tale NV et al.
DAAM concentration
3 4
(wt%) (wt%) (wt%)
1.11 μm 1.87 μm 1.51 μm
7.31 μm 8.20 μm 10.57 μm
26.29 μm 27.90 μm 37.79 μm
viscosity is increased with concentration of DAAM,
and the viscosity increases to the highest values when
the DAAM concentration is 4 wt%.
D
Effect of DAAM Concentration on Film Properties
of Its Cross-linked Copolymer Emulsion
water resistance of DAAM copolymer sample
containing 4 wt% of DAAM to cross-link with 1,3-
diaminopropane, because 1,3-diaminopropane has
hydrocarbon chain and two amino groups, and after
cross-linking there are no such functionalities left to
be susceptible to acid, alkali and water. Also, the
cross-linked reaction of carbonyl group of DAAM
and 1,3-diaminopropane increases the molecular
weight and provides denser polymer network on the
substrate.
This is a unique monomer, which with increased
DAAM weight percentage, two extreme properties
viz; hardness and flexibility are also enhanced.
Therefore, this monomer constitutes an important part
in commercial thermosetting emulsions for wider
Figure 8. Effect of DAAM concentration on viscosity of
DAAM copolymer emulsions.
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 Tale NV et al. Synthesis of Diacetone Acrylamide Monomer ...

Table 4. The film properties of cross-linked DAAM copolymers.

DAAM concentration in emulsion

Properties of cross-linked
DAAM copolymer 1 2 3 4
(wt%) (wt%) (wt%) (wt%)

Scrub resistance (cycles) Wet 2700 >4800 >5600 >6500

Dry 3300 >5700 >6300 >7300

Impact resistance fair good good best

Pencil hardness 2H 3H 4H 4H
Scratch hardness (Kg) 1.25 1.35 1.5 1.8
Flexibility pass pass pass pass
Adhesion Fair good good best

D
Chemical resistance NaOH good good better excellent
48 h immersion H2SO4 good good good excellent
Water good good better excellent

applications on a variety of substrates. The results of

different film properties are summarized in Table 4.
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