Progress in Organic Coatings 105 (2017) 9–17

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Preparation and assistant-film-forming performance of aqueous

polyurethane dispersions
Lei Wang a , Yanan Zhu b , Jinqing Qu a,∗
a
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
b
Carpoly Chemical Group Co. Ltd., Jiangmen 529085, Guangdong, China

a r t i c l e i n f o a b s t r a c t

Article history: A series of novel trimethylol propane monoesters were synthesized to prepare aqueous polyurethane
Received 13 October 2016 dispersions (PUD), which were used as a polymer coalescent to assist the film forming of high Tg poly-
Received in revised form acrylate latexes (PA). The effects of trimethylol propane monoester categories, NCO/OH molar ratios, soft
19 November 2016
segment contents, dimethylolpropionic acid (DMPA) contents, and diamine chain extenders on assistant-
Accepted 7 December 2016
film-forming performance of PUD were investigated. The surface microstructures of PA/PUD blend latexes
were also characterized with scanning electron microscopy (SEM) and transmission electron microscope
Keywords:
(TEM). The results showed that the PUD prepared from trimethylol propane monolaurare (TMPLA) with
Trimethylol propane monoester
Aqueous polyurethane dispersion
long-chain alkyl groups displayed excellent assistant-film-forming ability. The assistant-film-forming
Assistant-film-forming ability of PUD was increased with decreasing of NCO/OH molar ratios and hard segment proportions. The
Waterborne wood paints optimum preparation process of better assistant-film-forming PUD was that isophorone diisocyanate
(IPDI), polyether 220 (N220), trimethylol propane monoester (TMPLA) and adipic acid dihydrazide (ADH)
as reactants, 1.5 of the NCO/OH molar ratios, 55/45 of the soft/hard segment mass ratio and 5% of ␻
(DMPA). The high Tg polyacrylate latexes with PUD could form a continuous transparent film at 5 ◦ C with
30 g L−1 of the volatile organic compounds (VOC) contents and display good film performance.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction a methacrylic dicyclopenadiene-oxygen-ethyl ester (DPOMA) car-

Nowadays, with ever-increasing environmental protection and
health awareness, the ultralow or even zero volatile organic
compounds (VOC) waterborne coating has become an important
developing trend of coating industry [1–4]. For waterborne coat-
ing industry, polyacrylate (PA) coatings are widely used in coating
industry due to possessing good performance including weather-
resistance and physical and chemical properties.
However, waterborne coatings industry owning high film hard-
ness and good chemical resistance need polyacrylate latexes
with high glass transition temperature (Tg ), amount of organic
small molecule solvents are necessarily used as coalescents to
assistant PA formation the excellent film at low temperature
(below 5 ◦ C), thus increased the VOCs contents in the waterborne
coatings [5,6]. During the past several decades, some meth-
ods have been discussed to low or eliminate organic coalescent
including using reaction active coalescent, core-shell polymer
emulsions and hard/soft latex blends [7–9]. Emmons found that
∗ Corresponding author.
E-mail address: cejqqu@scut.edu.cn (J. Qu).
rying vinyl groups as a coalescent could both assist film-forming
of PA and also react with oxygen catalyst with an organic cobalt
salt, while it tremendously decreased the storage times of latexes
[7]. The core-shell polymer latexes are intensively studied because
these exhibit low minimum film forming temperature (MFFT) and
are promising candidates for low VOC coatings [10–12]. Hughes and
Michael demonstrated that the polyacrylate latexes with core/shell
structures could significantly decrease the MFFT and VOC contents
of latexes and coatings [10,11]. Cui found that there was no obvi-
ous boundary between core and shell part in polymer latexes and
possibly existed more complex structures including interpenetrat-
ing network, grafted and ionic bonding [12]. However, it was very
difficult to coordinate the balance of MFFT and Tg of polyacry-
late latexes. As a result, the small molecular organic coalescent
were also added to improve the film properties during film-forming
process of waterborne industry coatings. Hard/soft latex blending
methods which were explained that the high glass transition tem-
perature (Tg ) (i.e., hard latex) blended with a suitable amount of
low-Tg latex (i.e., soft latex) could form a good continuous film at
low temperature (below 5 ◦ C) [13]. It has already become the most
potential methods to prepare the ultralow and zero VOC contents
waterborne wood coatings [14]. Jensen and Colombini reported

http://dx.doi.org/10.1016/j.porgcoat.2016.12.005
0300-9440/© 2016 Elsevier B.V. All rights reserved.
10 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17
Table 1
The appearance, yields of mono-ester, di-esters and tri-esters of the trimethylol propane monoester.
monoester appearance
TMPOA Deep yellow
TMPBA yellow
TMP-tBA yellow
that the ratios of particle size between hard and soft latexes and
the hard/soft blending composition had not only a great effect on
MFFT and film properties, but also an obvious influence on blend-
ing morphology and viscoelastic [15,16]. Although the hard/soft
latex blends could form a continuous and transparent film under
low temperature, the proportion of soft latexes (low Tg ) in blend
systems often exceed that of hard latex (high Tg ) and obviously
decrease chemical resistance and hardness. We have previously
synthesized a soft low Tg polyacrylate latexes (Tg = –20 ◦ C) and pre-
pared hard/soft latex blends with a 65/35 of the mass ratio, and
discovered that it could form a continuous and transparent film
with good performance without addition of any small molecules
organic coalescent [17].
On the other hand, aqueous polyurethane dispersions (PUD)
have attracted an increasing attention in a broad range of appli-
cations due to their perfect properties including flexibility and
excellent physical and mechanical properties [18–20]. Moreover,
polyurethane as a type of block copolymer display excellent film-
forming properties owning to the soft segment Tg low up to −60 ◦ C
[21]. Meanwhile, it is able to significantly change the film-forming
ability and compatibility with other polymers by adjusting the
ratios and structure between hydrophobic and hydrophilic groups
[22]. Polyurethane-acrylic hybrid latexes (PUA) which introduced
polyacrylate moieties in polyurethane may lead to form the syner-
gistic effect of polyacrylate and PU, many literatures reported the
preparation methods and relationships of structures and proper-
ties [23–25]. However, few studies reported PUD replaced the small
molecular organic coalescent to assistant polyacrylate latexes film
formation. In this paper, we first synthesized a series of trimethy-
lol propane monoesters as a novel diol chain-extender (Scheme 1),
and prepared aqueous polyurethane dispersions (Scheme 2), which
were used as a polymer coalescent to assist the film forming of
high Tg polyacrylate latex. The effects of its basic building blocks on
the assistant-film-forming performance of PUD were investigated,
we also demonstrate the relationship of the structure of PUD and
its assistant-film-forming ability, and prepare good performance
waterborne wood coatings with ultralow VOCs contents.
2. Experimental section
2.1. Materials
Polyacrylate latex (PA) (solid content = 47%, MFT = 50 ◦ C,
␩ = 2370 mPa·s, average particle size = 129 nm) was obtained from
Carpoly Chemical Group Co., Ltd. Polypropylene glycol (N220,
Mw = 2000), Polytetra-methylene-ether-glycol (PTMG, Mw = 2000),
Polycaprolactone (PCL, Mw = 2000), Castor oil (C. O.) and dimethylol
propionic acid (DMPA) were purchased from Perstorp Indus-
trial Surfaces Co., Ltd. (Sweden). Toluene diisocyanate (TDI),
isophorone diisocyanate (IPDI), Hexamethylene diisocyanate (HDI)
were offered by Degussa and bio-based aliphatic isocyanate
polymer (FLO100) was offered by Vencorex. p-Toluenesulfonic
acid was purchased from Adamas. Triethylamine (TEA, Aldrich).
1,4-Butyleneglycol (BDO, Perstorp), trimethylol propane (TMP),
Lauric acid (LA), Oleic acid (OA), Benzoic acid (BA), and 4-tert-
Butylbenzoic acid (tBA) were supplied by Aladdin. Ethylenediamine
(EDA), diethylenetriamine (DETA), adipic acid dihydrazide (ADH)
and 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA) were
Yield,% di-ester yield,% Tri-ester yield,%
85.7 7.3 7.0
84.6 10.5 1.1
87.8 11.1 1.1
purchased from Acros. Unless otherwise stated, reagents were pur-
chased and used without purification.
2.2. Synthesis of trimethylol propane monolaurare (TMPLA)
A 500 mL three-necked flask was equipped with a three-way
stopcock and a magnetic stirring bar, and flushed with dry nitro-
gen. Trimethylol propane (134 g, 1 mol), Lauric acid (200 g, 1 mol),
xylene (30 mL) and p-toluenesulfonic acid (0.3 g) were fed in
the flask. The mixture was stirred at 180 ◦ C until the acid value
upto 5 mg KOH/g. Then, the solvent was removed under reduced
pressure and the partly crude product was purified by silica gel
column chromatography using dichloromethane/methanol (20:1,
v/v) as an eluent to afford the product of monoester. A light
yellow liquid was obtained with a yield of 88.3%. Di-ester and Tri-
ester were obtained with a yield of 9.8% and 1.9%, respectively.
Trimethylol propane monooleic (TMPOA), trimethylol propane
monobenzoic (TMPBA), and trimethylol propane mono-4-tert-
butylbenzoic (TMP-tBA) were synthesized in a manner similar to
TMPLA. The appearance, yields of mono-ester, di-esters and tri-
esters of the trimethylol propane monoester were listed in Table 1.
The spectrum data and elemental analysis were given as follow.
2.2.1. TMPLA
IR (−1 , KBr): 3428, 2943, 2873, 1490, 1382, 1256, 1175, 1089,
1033, 1005, 890, 837, 792, 747.
1 H NMR (400 MHz, ı in ppm, DMSO-d ): 4.39 (s, OH), 3.82 (s,
6
CH2 ), 3.38 (m, CH2 ), 2.25 (m, CH2 ), 1.51 (m, CH2 ), 1.27 (m,
CH2 ), 0.87 (m, CH3 ).
13 C NMR (100 MHz, ı in ppm, DMSO-d ): 176.03, 62.44, 60.21,
6
41.47, 32.89, 31.31, 29.76, 28.88, 22.76, 21.19, 13.67, 8.83.
Elemental analysis: calculated C, 68.31; H, 11.47; Founded C,
68.47; H, 11.29;
2.2.2. TMPOA
IR (−1 , KBr): 3419, 2977, 2895, 1607, 1403, 1270, 1161, 1107,
1029, 995, 903, 821, 785, 716.
1 H NMR (400 MHz, ı in ppm, DMSO-d ): 5.48 (d, CH CH-), 4.01
6
(m, OH), 3.65 (s, CH2 ), 3.45 (m, CH2 ), 2.32 (d, CH2 CH), 2.17
(m, CH2 CH), 1.64 (m, CH2 ), 1.30 (m, CH2 ), 0.84 (m, CH3 ).
13 C NMR (100 MHz, ı in ppm, DMSO-d ): 173.01, 129.79, 65.53,
6
62.68, 43.47, 34.03, 33.31, 31.55, 29.63, 29.28, 29.12, 29.07, 25.29,
22.88, 21.19, 13.67, 8.83.
Elemental analysis: calculated C, 72.31; H, 11.63; Founded C,
72.16; H, 11.90;
2.2.3. TMPBA
IR (−1 , KBr): 3420, 2988, 2930, 2871, 1805, 1600, 1010, 911,
827, 734.
1 H NMR (400 MHz, ı in ppm, DMSO-d ): 8.05 (m, −ArH), 7.66
6
(t, −ArH), 7.56 (m, −ArH), 4.17 (s, OH), 3.64 (s, CH2 ), 3.45 (m,
−CH2 ), 1.69 (s, CH2 ), 0.91 (m, CH3 ).
13 C NMR (400 MHz, ı in ppm, DMSO-d ): 166.73, 133.45, 131.27,
6
129.88, 128.61, 67.32, 64.09, 43.04, 22.92, 7.78.
Elemental analysis: calculated C, 65.53; H, 7.61; Founded C,
65.33; H, 7.50;
 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17
Scheme 1. Synthesize of trimethylol propane monoesters.
2.2.4. TMP-tBA
IR (−1 , KBr): 3438, 2991, 2976, 2879, 2857, 1793, 1609, 1023,
931, 849, 745.
1 H NMR (400 MHz, ı in ppm, DMSO-d ): 7.94 (m, −ArH), 7.40
6 ω (DPM) % =
(m, −ArH), 4.17 (s, −OH), 3.64 (s, CH2 ), 3.45 (s, CH2 ), 1.69 (s,
CH2 ), 1.35 (m, CH3 ), 0.91 (m, CH3 ).
13 C NMR (400 MHz, ı in ppm, DMSO-d ): 165.47, 156.29, 129.04,
6 was tested according to ASTM D2354using a house-built MFFT
127.07, 125.35, 64.67, 60.95, 44.09, 34.66, 30.77, 21.69, 7.43.
Elemental analysis: calculated C, 69.36; H, 8.90; Founded C,
69.28; H, 9.02;
2.3. Synthesis of novel aqueous polyurethane dispersion (PUD)
PUDs were synthesized in round bottom glass reactor equipped
with a mechanical stirrer, a thermometer, a reflux condenser, a
temperature controller, and a nitrogen inlet using prepolymer pro-
cess as described in literature [26]. The isocyanate terminated
prepolymer (runs 1 for example) was prepared by reacting IPDI
(5.73 g, 25.78 mmol), N220 (11.11 g, 5.56 mmol), TMPLA (2.28 g,
6.60 mmol) and DMPA (1.00 g, 0.75 mmol) at 80 ◦ C using acetone as
solvent until the NCO content determined by the di-n-butylamine
back-titration method reached to the theoretical value [27]. The
isocyanate terminated prepolymer was then neutralized by TEA
to 100% neutralization at 50 ◦ C and then cooled to 40 ◦ C followed
by dispersion in water and chain extension by EDA as the reported
process [28]. The aqueous polyurethane dispersions with solid con-
tent of about 40 wt% were obtained after the acetone was removed.
The schematic illustration of the preparation of the PUD is given in
Scheme 2. The molar ration of NCO and OH groups was defined as
n(NCO)/n(OH), the mass percentage of soft segment and DMPA in
PU prepolymer was defined as ␻(soft) and ␻(DMPA), respectively.
2.4. Characterization
The IR spectrum of PUDs was analyzed with a Perkin-Elmer 2200
Fourier transform infrared spectrophotometer (FTIR, USA) and 1 H
(400 MHz) and 13 C (100 MHz) NMR spectra were recorded on a
Bruker AC 300 spectrometer using DMSO-d6 as deuterated solvent.
The average particle size and distributions of WPU dispersions
were measured with a Malvern Nano-ZS laser particle sizer (UK)
which size test range was from 6 to 6000 nm. Approximately 0.1 mL
of the polyurethane dispersion was diluted with 3 mL distilled
water and measured at 25 ◦ C.
Morphologies of films were investigated by a field emission
scanning electron microscope (Hitachi S-3700N, Japan) and trans-
mission Electron Microscope (JEM-1010, Japan). For the SEM
studies the extrudates were cleaved along the transverse direc-
tions, and the cleaved surfaces were gold-coated. For TEM, samples
were microtomed and mounted on carbon-coated copper grids. 8%
11
Dipropylene glycol methyl ether (DPM) were added into the PA as
a film-forming coalescent, the [␻ (DPM)] = 8% according to Eq. (1).
weight of DPM
× 100% (1)
total weight of the composite emulsions
Minimum Film Forming Temperature (MFFT) of polymer latexes
instrument.
2.5. Assistant-film-forming ability of PUD
Polyacrylate latexes with high glass transition temperature (Tg )
also exhibit high MTTF, means the film formation is very difficult in
r.t or 5 ◦ C, and need added amount of organic coalescent to assistant
PA film formation, The stronger the Assistant-film-forming ability,
the less the amount of coalescent. PUD substituted a small molecule
coalescent to assistant PA film formation, the PUD assistant-film-
forming ability was defined as the minimum mass percentage of
PUD in blend latexes [␻(PUD)] to make the PA form a continuous
transparent film at 5 ◦ C without other coalescent. PA, glass plate
and paint brushes were placed at 5 ◦ C for about 16 h, the films were
prepared with PUD and PA mixtures and placed at 5 ◦ C for 24 h,
then observed the film appearance. [␻(PUD)] as the PUD assistant-
film-forming ability was calculated as Eq. (2).
weight of PUD
ω (PUD) % = × 100% (2)
total weight of the composite emulsions
2.6. Preparation of composite emulsions films
The films were prepared by casting polymer latexes onto polyte-
trafluoroethene (PTFE,Ф = 7 mm) plate, drying at room temperature
for 48 h, and annealing at 80 ◦ C for 12 h. The PTFE plate was washed
by ethanol before use, and the thickness of dried film was about
1 mm.
2.7. Chemical resistance of films
The water- and solvent-resistance of the film were characterized
by water/solvent absorption. Film samples (weight W0 , dimen-
sions 25mm × 25mm × 1 mm) were immersed in water/ethanol at
room temperature for 8 days, removed from the water/ethanol, and
weighed (W1 ). Then the film samples were dried to constant weight
(W2 ) at room temperature. The percentage of the water absorption
(WA , %), the ethanol absorption (WE , %), the weight loss of poly-
mer films in water (Wx, %) and ethanol (Wy, %)were calculated
according to the following formula.
W1 -W2
WA/E % = × 100% (3)
W2
12 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17

CH3 NCO R NCO

HO OH HOH2C C CH2OH
polymeric polyols COOH polyisocyanates

Prepolymerization

O O CH3 O O
OCN O C HN R HN C OH2C C CH2O C NH R NH C O NCO
COOH

HO R' OH

O O O CH3 O O O
OCN O C HN R' O C HN R HN C OH2C C CH2O C NH R NH C O R' NH C O NCO
COOH
N Water

O O O CH3 O O O
OCN O C HN R' O C HN R HN C OH2C C CH2O C NH R NH C O R' NH C O NCO
COON(C2H5)3

H2N R'' NH2

O O O CH3 O O O
HN R'' NHC NHR' O C NHR NHC OH2C C CH2O C NH R NH C O R' NH C NH R'' NH
COON(C2H5)3

n-PUD

Scheme 2. Synthesis process of aqueous polyurethane dispersions.

W0 -W2
WX/Y % = × 100%
W0
2.8. Drying time of films
Surface-drying time of the coatings was determined according
to the standard EN ISO 9117-3 [29] by assessing the adhesion of
small 0.5 g transparent glass beads (diameter 75–150 ␮m) to the
coated wood surface. Actual drying time of the films was tested
according to Chinese Standard GB/T 1728–1979(1989).
3. Results and discussion
3.1. Structure of trimethylol propane monoesters and PUDs
It was illustrated in Scheme 2 that the synthetic routes for
trimethylol propane monoesters TMPLA, TMPOA, TMPBA and TMP-
tBA. They were synthesized by the esterification of TMP and LA,
OA, BA and tBA in 85–88% yields, respectively. Fig. 1 shows the
NMR spectrum of trimethylol propane monolaurare. In the 13 C NMR
spectra of the TMPLA, it can be found that the chemical shift of C9
and C11 connected with the quaternary carbon atom had become
different. In addition, a signal around 173 ppm assigned to ester car-
bonyl is observed. All these results clearly indicate that the TMPLA
was successfully synthesized form esterfication of TMP and LA.
Table 2 summarized the conditions and results of PUD syn-
thesized by using prepolymer process from trimethylol propane
monoesters, PUDs from TMPLA and TMPOA in runs 1 and 2 exhib-
ited big viscosities and particle sizes owing to the long hydrophobic
aliphatic chains, they also displayed better assistant-film-forming
abilities with low MFFT and ␻ (PUD) than that of BDO-based PUD.
The possible reasons was that PUDs with the long alkyl chain in
run 1 and 2 display good flexibility and more easily fill into the
gap among PA particles and benefit for the film formation of high
(4)
Tg PA to decrease the MFFT of PA from 29.2 ◦ C to 24.1 ◦ C. Com-
pared with TMPLA, PUDs from TMPBA and TMP-tBA in runs 3 and
4 exhibited slightly low assistant-film-forming ability and higher
film hardness than that of BDO-based PUD due to the rigid struc-
ture of benzene groups. However, TMPOA-based PUD possessed
deep color lead to form deep yellow film and could not prepare
white paints; the TMPLA-based PUD was used in following studies.
The TMPLA-based PUD and TMPLA structures were also exam-
ined by IR spectroscopes (Fig. 2). The peaks at 3428 cm−1 and
1713 cm−1 attributed to the stretching vibration of OH and C O
bonds were observed in the IR spectra of TMPLA. No absorption
peaks around 3428 cm−1 attributable to the stretching vibration of
OH bonds were observed in the IR spectra of TMPLA-based PUD,
and the new peak at 3348 cm−1 and 1548 cm−1 were attributed to
NH characteristic peaks. All these results clearly indicated that
TMPLA-based PUD was successfully prepared from TMPLA.
3.2. Investigation assistant-film-forming performance of PUD
influenced by its structure
3.2.1. Molar ratios of NCO/OH
Table 3 summarized the conditions and results of the effects
of molar ratios of NCO/OH on the assistant-film-forming ability of
the PUDs. The viscosities of PU prepolymer became too large to
emulsify and obtain a larger particle sizes PUD when the molar
ratios of NCO/OH was less than 1.1 in runs 6. With an increasing
of the NCO/OH molar ratios, residual NCO% of the PU prepolymer
increased, the PU prepolymer viscosities decreased and were easily
to be dispersed to small particle sizes of PUDs. While the molar ratio
of NCO/OH exceeded 1.7, it was difficult to disperse the PU prepoly-
mer and provided big particle sizes PUDs with a poor appearance
due to increasing crosslinked structures of PUD by excess NCO
 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17 13

Table 2
Influences of trimethylol propane monoesters on the assistant-film-forming ability of PUDsa .

runs diol chain extenders viscosities/mPa s particle sizes/nm MFFT/ ◦ C ␻(PUD)/%

1 TMPLA 355 140 24.1 25

2 TMPOA 410 190 24.3 25
3 TMPBA 120 75 34.5 40
4 TMP-tBA 247 84 36.3 35
5 BDO 115 60 29.2 30
a
IPDI, N220 and ADH as reactants, n(NCO)/n(OH) = 1.5, ␻(soft) = 55%, ␻(DMPA) = 5%.

Table 3
Effects of NCO/OH molar ratios on the assistant-film-forming ability of PUDsa .

runs n(NCO) /n(OH) viscosities/mPa s particle sizes/nm MFFT/ ◦ C ␻(PUD)/%

6 1.1 674 102 32.9 35

7 1.3 533 122 29.1 30
1 1.5 335 140 24.1 25
8 1.7 270 176 34.0 35
9 1.9 188 218 39.3 40
a
IPDI, N220, TMPLA and ADH as reactants; ␻ (soft) = 55% and ␻(DMPA) = 5%.

Fig. 2. FT-IR spectra of TMPLA and PUD.

1
Fig. 1. H NMR and 13 C NMR spectra of TMPLA. Fig. 3. Effects of NCO/OH molar ratios on the assistant-film-forming ability of PUDs.

and diffusion, weakening the assistant-film-forming ability of PUD.

groups reacted with water and ethylene diamine. The MFFT of com-
posite emulsions first decreases and then increases sharply. The
MFFT of composite emulsions was the minimum value with 1.5 of
the NCO/OH molar ratio. Fig. 3 also showed the MFFT from 35.8 ◦ C
to 31.2 ◦ C with the NCO/OH molar ratios increased from 1.5 to 1.9,
resulting in rapidly decreasing of assistant-film-forming ability.
The large amount of residual NCO reacted with water and diamine
chain extender to form the rigid urea structures and corsslinking
networks, to resist the polymer latex molecular chain movement
Thus, 1.3–1.5 of the NCO/OH molar ratios is perfect.
3.2.2. Proportion of soft segment
Table 4 exhibited the influence of the soft segment contents on
the assistant-film-forming ability of PUD. In general, the average
particle sizes of PUDs decreased and the viscosities increased with
increasing of the soft segment mass percentage. The assistant-film-
forming ability of PUD increased with the increasing of the soft
segment contents in the range of 45–65%, the MFFT of blend latex
14 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17

Table 4
Influences of proportions of soft/hard segment on the assistant-film-forming ability of PUDsa .

runs (soft)/% viscosities/mPa s particle sizes/nm MFFT/ ◦ C ␻(PUD)/%

10 45 156 237 32.7 40

11 50 220 174 30.9 35
1 55 335 140 24.1 25
13 60 487 101 29.4 30
14 65 636 92 29.3 30
a
IPDI, N220, TMPLA and ADH as reactants; n(NCO)/n(OH) = 1.5 and ␻(DMPA) = 5%.

Fig. 4. Influences of proportions of soft/hard segment on the assistant-film-forming Fig. 5. Influences of ␻ (DMPA) on the assistant-film-forming ability of the PUDs.
ability of PUDs.

in Fig. 4 decreased from 32.7 ◦ C to 29.8 ◦ C and the MFFT of com-

posite emulsions decreased to 24.1 ◦ C with 55% of the soft mass
proportions. It was possible that high contents soft segment were
benefit from the free diffusion of the polymer chain and the defor-
mation of latex particles, which attributed to the very low Tg and
good compatibility of the soft segments. However, high contents
soft segments would induce poor film hardness and properties.
Hence, the 55% of soft segment was good.

3.2.3. Polymeric polyols

Table 5 revealed the influence of polymeric polyols categories
on the assistant-film-forming ability of PUDs. It was obvious
that polyether polyol N220 exhibited much better assistant-film-
forming performance with more lower MFFT and ␻(PUD) than that
of other polymeric polyols. PUDs from N220 possessed small aver-
age particle sizes and low viscosities, and displayed low polarity
and good compatibility with PA leading to easily filled in the gap of
PA latex particles.
3.2.4. Influences of dimethylolpropionic acid concentration [␻
(DMPA)]
Table 6 displayed the effects of ␻ (DMPA) on the assistant-film-
forming ability of the PUDs. It was distinct that the average particle
sizes of PUD and blend latex MFFTs decreased with the increas-
ing the content of DMPA due to the smaller average particle sizes
PUDs was good for filling in the gap of PA latexes to benefit the
film formation of blend latex system. However, it can be seen from
Fig. 5 that the assistant-film-forming ability hardly changed with
enhancement of the ␻ (DMPA) in the range of 5.0–8.0%, attribut-
ing to the polarity of PUD increased with the increasing of the ␻
(DMPA) and lead to bad compatibility with PA, on the other hand,
the water-resistance of PUD films with high contents DMPA would
change bad, and thus the ␻ (DMPA) below 5% was better.
3.2.5. Diisocyanates
The effects of diisocyanate categories on the assistant-film-
forming ability of the PUDs were listed in Table 7. It was clearly
found that the PUD from FLO100 displayed excellent assistant-
Fig. 6. Effects of assistant-film-forming PUD in runs 1 on MFFT of composite latexes.
film-forming ability with low the blend latex MFFT and ␻(PUD),
while the PUD from TDI exhibited bad assistant-film-forming per-
formance. The order of the PUD assistant-film-forming ability was
FLO100 > IPDI >HDI > TDI. The reason may be high Tg of PUD hard
segments from TDI weaken the diffusion ability of the polymer
chain and led to difficult in the deformation of latex particles.
In contrast, the PUD from FLO100 and HDI possessed wonderful
flexibility aliphatic chains and low hard segments Tg to display
excellent assistant-film-forming performance. However, the PUD
from FLO100 exhibited high viscosities and extremely expensive,
and was not suitable for practical application, so IPDI and HDI were
satisfied diisocyanates.
3.2.6. Diamine chain extender
The influence of the diamine chain extender on the assistant-
film-forming ability of PUDs was discussed in Table 8. It was
known that diamine chain extender was usually used as post-chain
extender in PUDs and played a significant role for the assistant-
film-forming performance of PUDs. It could be found that PUD
prepared from ADH has lowest the MFFT of blend latex with min-
 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17 15

Table 5
Effects of polymeric polyols on the assistant-film-forming ability of PUDsa .

runs polymeric polyols viscosities/mPa s particle sizes/nm MFFT/ ◦ C ␻(PUD)/%

1 N220 335 140 24.1 25

15 PTMG 230 114 30.9 35
16 PCL 165 100 31.2 35
17 C.O. 1380 103 34.5 40
a
IPDI, TMPLA and ADH as reactants; n(NCO)/n(OH) = 1.5, ␻(soft) = 55 and ␻(DMPA) = 5%.

Table 6
Influences of the effects of ␻ (DMPA) on the assistant-film-forming ability of the PUDsa .

runs ω(DMPA)/% viscosities/mPa s particle sizes/nm MFFT/ ◦ C ␻(PUD)/%

18 4.0 256 192 31.3 35

1 5.0 335 140 24.1 25
19 6.0 445 128 29.3 30
20 7.0 570 119 29.0 30
21 8.0 656 104 28.8 25
a
IPDI, N220, TMPLA and ADH as reactants; n(NCO)/n(OH) = 1.5 and ␻(soft) = 55%.

Table 7
Effects of diisocyanate categories on the assistant-film-forming ability of the PUDsa .

runs diisocyanates viscosities/mPa s particle sizes/nm MFFT/ ◦ C ␻(PUD)/%

22 TDI 217 115 34.7 40

1 IPDI 335 140 24.1 25
23 HDI 460 46 28.4 30
24 FLO100 1240 26 23.5 25
a
TMPLA, N220 and ADH as reactants, n(NCO)/n(OH) = 1.5, ␻(soft) = 55% and ␻(DMPA) = 5%.

Table 8
Influences of diamine chain extenders on the assistant-film-forming ability of PUDsa .

runs diamine-chain extender viscosities/mPa s particle sizes/nm MFFT/ ◦ C ␻(PUD)/%

25 EDA 128 76 29.7 30

26 DETA 137 107 29.9 30
1 ADH 335 140 24.1 25
27 IPDA 440 256 32.5 35
a
IPDI, N220 and TMPLA as reactants, n(NCO)/n(OH) = 1.5, ␻(soft) = 55% and ␻(DMPA) = 5%.

Fig. 7. Particle sizes and distributions of blend latex PA and PUD.

imum ␻(PUD), and displayed the excellent assistant-film-forming

ability. This may be attributed to the crosslinking reaction of car-
bonyl groups from PA and hydrazide group from ADH at ambient
Fig. 8. TEM images magnification of composite latex with 25% of ␻ (PUD).
temperature [30,31].

3.3. Investigation effects of ␻ (PUD) on MFFT of the blend latexes

Fig. 6 presented the effects of ␻ (PUD) in runs 1 on the MFFT form a continuous transparent film at 5 ◦ C without any organic
of blend latexes. It was demonstrated that the MFFT of blend latex small molecular coalescents. However, the blend latex film exhib-
decreased from 66 ◦ C to 4.5 ◦ C with increasing of ␻(PUD) in the ited slight low hardness and poor film properties when the content
range of 0–25%, the blend latex with 25% ␻(PUD) in runs 1 could of ␻ (PUD) in runs 1 exceeded 25%.
16 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17

Fig. 9. SEM images of pure PA films (a) and composite films (b).

3.4. Particle size and distributions Table 9

Properties of blend latex with 25% of ␻ (PUD)a .

Fig. 7 illustrated the particle sizes and distributions of PUD in Properties PA Blend latex
runs 1, PA and blend relaxes with 25% of ␻ (PUD) in runs 1. It ␻(PUD)/% 0 25
could be seen from Fig. 7., the average particle sizes of PA, PUD ␻(DPM)/% 8 0
in runs 1 and blend latexes were all unimodal distributions, the Tack free time/min 12 13
Actual drying time/h <
= 24 h 24 h
average particle sizes of the blend latex was between PU and PA
Water absorption/% 7.8 7.1
while the particle size distribution became bigger indicating the
Alcohol absorption/% 16.5 20.0
PUD in runs 1 had excellent compatibility with PA to generate the Pencil hardness H-HB B
uniform system. Gloss(60◦ ) 72 84
VOC/g L−1 120 30
a
3.5. TEM results PUD in runs 1.

Fig. 8 illustrated the TEM images of particle morphology of blend 4. Conclusions

latex with 25% of ␻ (PUD). It was found that the particle of blend
latex was well distributed and had no aggregations with the small
particles of PUD in runs 1 distributed among big particles of PA
latexes, which indicating the blend latex could be stable in an uni-
form system.
3.6. SEM results
Fig. 9 exhibited the SEM images of pure PA1 film and blend latex
film with 25% of ␻ (PUD). It is found that the blend latex with 25%
of ␻ (PUD) in runs 1 as a coalescent could form a homogeneous
film, and the film appearance is more flat than that of PA (adding 8%
dipropylene glycol methyl ether (DPM) as film-forming coalescent).
This indicates the PUDs is able to totally substitute small molecular
organic coalescent.
3.7. Film properties
The film properties of PA latex (adding dipropylene glycol
methyl ether (DPM) as film-forming coalescent) and the blend latex
with 25% of ␻ (PUD) in runs 1 were presented in Table 9. The results
show the blend latex film displayed higher gloss and slight low
harness than those of PA latex while the drying times and water-
/alcohol-resistance were similar to that of PA latex. Especially, the
VOCs contents of paint from blend latex was low to 30 g/L, much
lower than that of PA latex, indicating that this novel PUDs could
be used as a polymer coalescent replace small molecular organic
coalescent to assist the film forming of high Tg polyacrylate latexes.
A series of trimethylol propane monoesters were synthesized
and used a diol chain-extender to prepare novel PUDs, which were
used as a polymer coalescent to assist the film forming of high Tg
polyacrylate latexes. PUD from TMPLA or TMPOA exhibited more
excellent compatibility and assistant-film-forming performance
due to the long flexibility aliphatic chain structures. In addition,
the block structure of PUD including soft segment and its con-
tents, diisocyanate and diamine extend categories, molar ratios of
NCO and OH groups, and DMPA contents all affect the assistant-
film-forming performance of PUD. The composite latex with 25%
of ␻ (PUD) exhibited a uniform coating system with 30 g L−1 of the
volatile organic compounds (VOC) and form a continuous transpar-
ent film at 5 ◦ C. The TEM and SEM analysis results of composite films
displayed good film appearance and properties, which indicated
the PUD in runs 1 could be used as a polymer coalescent substituted
small molecule counterparts to prepare high performance and low
VOC contents waterborne industry paints.
Acknowledgments
This work was financially supported by the Natural Sci-
ence Foundation of Guangdong, China (No. 2015A030313205),
the Science and Technology Program of Guangdong Province
(No. 2015A010105010), and Special Project on the Integration
of Industry, Education and Research of Guangdong Province
(Nos. 2012A090300004, 2014B090903010, 2015B0909250062,
2016B030302004 and 2016B090930005).
 L. Wang et al. / Progress in Organic Coatings 105 (2017) 9–17
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