Progress in Organic Coatings 86 (2015) 1–10

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Progress in Organic Coatings

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

A new method to synthesize high solid content waterborne

polyurethanes by strict control of bimodal particle size distribution
Shao-Jun Peng a,b , Yong Jin c,d,∗ , Xin-Feng Cheng a,b , Tong-Bing Sun a,b ,
Rui Qi a,b , Bao-Zhu Fan a,b
a
Chengdu Institute of Organic Chemistry, Chinese Academy of Science, Center of Polymer Science and Technology, Chengdu 610041,
People’s Republic of China
b
University of Chinese Academy of Sciences, No. 19A Yuquan Road, Beijing 100049, People’s Republic of China
c
National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065, People’s Republic of China
d
Key Laboratory of Leather Chemistry and Engineering (Sichuan University), Ministry of Education, Chengdu 610065, People’s Republic of China

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

Article history: A new method named two-step emulsification process was developed to synthesize high solid content
Received 3 July 2014 waterborne polyurethanes by strict control of the bimodal particle size distribution. In the first step, a
Received in revised form 10 March 2015 series of 40% solid content polyester-based (WPU-1) with low content of hydrophilic group and large
Accepted 17 March 2015
particle size were firstly synthesized. In the second step, polyether-based prepolymers (WPU-2 prepoly-
Available online 5 April 2015
mers) with high content of hydrophilic group were firstly prepared and WPU-1 emulsions were used to
emulsify WPU-2 prepolymers to obtain the final emulsions with high solid content (WPU-3). The parti-
Keywords:
cle size of WPU-3 present bimodal distribution and the diameter ratio and volume percentage of large
Waterborne polyurethanes
High solid content
particles to small particles in WPU-3 were able to be strictly controlled by this method. The viscosity of
Particle size distribution WPU-3 with 55% solid content was only 489.1 mPa s−1 when the diameter ratio of large particles to small
particles was 9.2 and the volume percentage of large particles was 74%.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
The coatings industry sees the rapid development of aqueous
dispersions to meet the requirement of environmental legisla-
tions and human health in the past several decades [1–4]. Among
these aqueous dispersions, waterborne polyurethanes (WPUs)
have received increasing attention due to their excellent chemi-
cal and mechanical properties since the noteworthy work made by
Dieterich and his colleagues who developed the field in 1970s [5,6].
WPUs have a wide range of applications in adhesives and coatings
for wood, automobiles, plastics, leather, textiles and so on [7–14].
High solid content (HSC) WPUs have been a research hotpot
because they increase the space-time yield of the reactor and
reduce the film-forming time [15]. However, high solid content
WPUs always bring high viscosity which increases the burden of the
production and product handling equipment. Generally speaking,
the viscosity of the WPUs grows slowly with the increment of solid
∗ Corresponding author at: National Engineering Laboratory for Clean Technology
of Leather Manufacture, Sichuan University, Chengdu 610065, People’s Republic of
China. Tel.: +86 13658027079; fax: +86 028 85223978.
E-mail address: jinyong@cioc.com (Y. Jin).
content until near the up limit of solid content. Above the up limit
of solid content, the viscosity increases extremely rapidly with the
augment of solid content since the particles are so crowded that the
interactions between neighboring particles are strong [16]. To solve
the contradictory between solid content and viscosity, the research
was mainly focused on the preparation of WPUs with multimodal
particle size distribution [17,18].
Particle size distribution (PSD) is an important parameter in
determining the relationship between solid content and viscosity
[19,20]. WPUs with multimodal PSD usually increase the up limit
of solid content for small particles are able to fit into the interstices
between large particles. Furthermore, if the difference on particle
diameters and volume percentage is in a reasonable range, small
particles will efficiently pack into the voids among the large parti-
cles, thus increasing the maximum packing factor of particles [21].
Therefore, preparation of high solid content WPUs needs to synthe-
size particles with multimodal PSD, including the precise control of
the diameter ratio and volume percentage of large particles to small
particles [22].
Although lots of literatures on HSC aqueous dispersions made
by emulsion polymerization have been published, there are only
several scientific articles focused on the preparation of HSC WPUs
with bimodal or multimodal PSD [23–25]. In fact, the synthetic

http://dx.doi.org/10.1016/j.porgcoat.2015.03.013
0300-9440/© 2015 Elsevier B.V. All rights reserved.
2 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10
process of WPUs is totally different from aqueous dispersions
prepared by emulsion polymerization, leading to the different
structure of particles. Most of the WPUs are synthesized by
self-emulsification process and self-emulsifiers are used to mod-
ify hydrophobic PU backbones with built-in hydrophilic groups
including carboxylate, sulfonate, or quaternary ammonium salt or
non-ionic groups [26]. As a result, WPUs particles usually consist
of hydrophobic core, water swelling layer and electric double layer
[27]. The existence of water swelling layer makes the synthesis of
HSC WPUs very difficult for large amounts of water are absorbed
by the water swelling layer of WPUs particles.
In the published scientific articles concentrated on HSC WPUs,
He and Sun synthesized 50% solid content WPUs using polyether
diol containing sulfonate as the hydrophilic monomer and found
that the PSD was very broad even bimodal when the weight ratio of
hydrophilic monomer was low [23]. Zhang et al. also prepared 50%
solid content WPUs with multimodal PSD using polyol consisting of
trifunctional siloxane (PES) and propylene oxide glycol (PPG) as the
mixed soft segments [24]. Lee et al. reported the high solid (45%)
and high stability WPUs via ionic groups in the chain termini. The
authors found that the dispersions containing ionic groups at the
chain termini gave the smallest dispersion size and the highest vis-
cosity, owing to the high mobility and low free energy of the chain
ends [25]. Although some HSC WPUs with broad or multimodal PSD
were synthesized, there was not systematic and detailed research
on the preparation of HSC WPUs with bimodal PSD in a reproducible
manner and a method focused on the precise control of the diame-
ter ratio and volume ratio of particles in WPUs has never been seen.
In this work, a new method named two-step emulsifica-
tion process was applied to synthesize high solid content WPUs
with bimodal PSD by taking advantage of the difference in the
hydrophilicity of polyurethane backbones. The diameter ratio and
volume percentage of large particles to small particles were strictly
controlled to achieve the optimal bimodal PSD and obtain the most
reasonable packing efficiency of particles. We hope this work would
offer the theoretical guidance to prepare HSC WPUs with low vis-
cosity by strictly controlling the bimodal PSD.
2. Experimental
2.1. Materials
Isophorone diisocyanate (IPDI, analytical grade), Isophorone
diamine (IPDA, analytical grade) 2,2-dimethylol propionic acid
(DMPA, 98% purity) and di-n-butylamine (DNBA) were pur-
chased from Aladdin Reagent (Shanghai, China). Poly propylene
glycol (PPG, Mw = 1000), Poly-1,4-butylene adipate glycol (PBA,
Mw = 1000), 1,4-butanediol (BDO), ethanol and triethylamine
(TEA) were supplied by Shanghai Chemical Reagent Corpora-
tion (Shanghai, China). Acetone, N-methyl pyrrolidone (NMP) and
dibutyltin dilaurate (DBTDL) were purchased from J&K China
Chemical Ltd.
PPG, PBA and DMPA were dried in vacuum at 100 ◦ C for 8 h
before use. The solvents and chemicals were used as received unless
stated.
Fig. 1. A general process for producing WPU-3 with bimodal PSD.
2.2. Synthetic strategy
Generally speaking, the size of WPU particles was strongly influ-
enced by the self-emulsifier content in its backbones. Therefore, we
firstly synthesized two series of WPUs with different particle sizes
by adjusting the DMPA content, namely WPU-1 and WPU-2. WPU-1
series was based on polyester soft segment with low DMPA con-
tent while WPU-2 series was based on polyether soft segment with
high DMPA content. Step-wise charging sequence of raw materials
was applied to make sure that WPU-1 and WPU-2 were unimodal
PSD with low PDI. In the experiment, WPU-1 and WPU-2 samples
were regarded as parallel samples to compare with HSC WPUs with
bimodal PSD, namely WPU-3.
In the preparation of WPU-3, a new method named two-step
emulsification process was used. In the first step, WPU-1 with low
DMPA content was firstly synthesized by step-wise reaction. Di-n-
butylamine titration method and FTIR were applied to make sure
that no NCO groups existed in WPU-1 emulsions. The solid content
of WPU-1 emulsions was set as 40%. After that, WPU-1 emulsion
was used to emulsify WPU-2 prepolymer with high DMPA content
and WPU-3 series were obtained after the removal of acetone, the
producing process as shown in Fig. 1. Two parameters were set in
the synthesis of WPU-3, namely diameter ratio and volume ratio
of large particles to small particles. The influence of diameter ratio
on viscosity in WPU-3 at fixed solid content was firstly discussed,
and the most reasonable diameter ratio was selected. At the most
reasonable diameter ratio, the influence of volume ratio on viscosity
in WPU-3 was analyzed.
2.3. Preparation of polyester-based waterborne polyurethane
(WPU-1)
IPDI and PBA were firstly charged in the reactor, catalyzed by
DBTDL in the presence of N2 atmosphere. The reaction was reacted
at 80 ◦ C until the theoretical NCO content of the prepolymers was
reached, as determined by the di-n-butylamine titration method.
Then, DMPA was added to react for 2 h to bring the backbone
hydrophilicity. After that, BDO was added to react for 2 h. The mix-
ture was cooled to 30 ◦ C and TEA was added. Acetone (20 wt%) was
added at the same time to reduce the viscosity. The neutralization
reaction proceeded at the same temperature for 30 min. Then, dis-
tilled water was added to the reactor and the stirring rate was kept
at 600 rpm for 30 min and 300 rpm for another 30 min. IPDA was
added to extend the final backbones. Finally, WPU-1 was obtained
after the removal of acetone at 50 ◦ C and the vacuum degree of
0.09 MPa for 30 min by the rotary evaporation instrument. The
compositions of the WPU-1 were listed in Table 1, and the reaction
process was illustrated in Scheme 1.
2.4. Preparation of polyether-based waterborne polyurethane
(WPU-2)
IPDI, PPG and DBTDL were charged in the reactor, in the presence
of N2 atmosphere. The reaction was reacted at 80 ◦ C until the the-
oretical NCO content of the prepolymer was reached. Then, DMPA
S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10 3

Scheme 1. Preparation process of WPU-1.

Scheme 2. Preparation process of WPU-2.

4 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10

Table 1
The prepolymer composition of WPU-1.

Samples designation Prepolymer composition (molar ratio) DMPA content mmol/g (×10)

IPDI PBA DMPA BDO TEA IPDA

WPU-1-a 2.0 1.30 0.175 0.325 0.175 0.20 0.97

WPU-1-b 2.0 1.30 0.20 0.30 0.20 0.20 1.11
WPU-1-c 2.0 1.30 0.225 0.275 0.225 0.20 1.25
WPU-1-d 2.0 1.30 0.25 0.25 0.25 0.20 1.39

Table 2
The prepolymer composition of WPU-2.

Samples designation Prepolymer composition (molar ratio) DMPA content mmol/g (×10)

IPDI PPG DMPA BDO TEA IPDA

WPU-2-a 2.0 1.30 0.45 0.05 0.45 0.20 2.50

WPU-2-b 2.0 1.30 0.40 0.10 0.40 0.20 2.22
WPU-2-c 2.0 1.30 0.35 0.15 0.35 0.20 1.94
WPU-2-d 2.0 1.30 0.30 0.20 0.30 0.20 1.67

was added to react for 2 h to bring the backbone hydrophilicity. 3. Characterizations

After that, BDO was added to react for 2 h. The mixture was cooled
to 30 ◦ C. Next, TEA and acetone (20 wt%) was added. The neutral- The FTIR spectra of the dispersions were recorded with a Thermo
ization reaction proceeded at the same temperature for 30 min. Fisher Nicolet 6700 type FTIR spectrophotometer. Each sample was
Then, distilled water was added to the reactor and the stirring rate scanned 64 times at a resolution of 4 cm−1 . All of the spectra were
was kept at 600 rpm for 30 min and 300 rpm for another 30 min. scanned within the range 400–4000 cm−1 . To ensure the repro-
IPDA was added to extend the final backbones. Finally, WPU-2 ducibility of the results, each sample was scanned at three different
was obtained after removing the acetone at 50 ◦ C and the vacuum locations.
degree of 0.09 MPa for 30 min by the rotary evaporation instru- The viscosity of the WPU dispersions was measured in a Brook-
ment. The compositions of the WPU-2 were listed in Table 2, and field digital viscometer (Modal DV-III). Measurement was carried
the reaction process was showed in Scheme 2. out at 25 ◦ C, by using the spindle NO. 18 at 10 rpm.
The particle size and its distribution of the dispersions were
analyzed by dynamic light scattering (Malvern Zetasizer Nano-ZS),
2.5. Preparation of HSC waterborne polyurethane (WPU-3) by using a monochromatic coherent He–Ne laser (633 nm) as the light
two-step emulsification process source and a detector that detected the scattered light at an angle
of 90. The sample was first diluted in deionized water to a con-
IPDI and PPG were firstly charged in the reactor, catalyzed by centration of 0.1 wt%, followed by ultrasonic wave treatment to
DBTDL in the presence of N2 atmosphere. The reaction was reacted homogenize the dispersion.
at 80 ◦ C until the theoretical NCO content of the prepolymer was Transmission electron microscopy (TEM) images were obtained
reached. Then, DMPA was added to react for 2 h. After that, BDO was from a HITACHI-H7650 Microscope with an accelerating voltage of
added to react for 2 h. The mixture was cooled to 30 ◦ C and TEA was 80 kV and the samples were stained by 0.2 wt% phosphotungstic
added. Acetone (20 wt%) was added at the same time to reduce the acid hydrate before observation.
viscosity. The neutralization reaction proceeded at the same tem- The solid content of the dispersion was detected by drying it at
perature for 30 min. Then, WPU-1 was added to the reactor and the 80 ◦ C for 3 days and calculating the weight ratio of residue to the
stirring rate was kept at 600 rpm for 30 min and 300 rpm for another dispersion.
30 min. IPDA was added to extend the final backbones. The vigorous
stirring was continued for an hour. Finally, high solid content WPU- 4. Results and discussion
3 (above 50%) was obtained after removing the acetone at 50 ◦ C and
the vacuum degree of 0.09 MPa for 30 min by the rotary evaporation 4.1. FTIR spectra of WPUs
instrument. The compositions of the WPU-3 were listed in Table 3,
and the reaction process as shown in Scheme 3. Fig. 2 showed the FTIR spectra of WPU-2-a, WPU-3-e, WPU-
3-f and WPU-1-a. The disappearance of bands at 2270 cm−1 and
the appearance of bands around 3350 cm−1 in all samples indi-
cated that all the NCO groups have reacted completely. From
Table 3
The prepolymer composition of WPU-3. a–d, the bands around 2900 cm−1 changed from multimodal bands
to slightly shoulder bands, which was attributed to the plenty of
Sample WPU-1 WPU-2 Prepolymer mass ratio
methyl groups and methine groups contained in polyether seg-
designation prepolymer prepolymer (WPU-1/WPU-2)
ments and methylene groups contained in polyester segments
WPU-3-a WPU-1-a WPU-2-a 1:1 [26]. The bands of a and b around 1110 cm−1 were ascribed to
WPU-3-b WPU-1-b WPU-2-b 1:1
WPU-3-c WPU-1-c WPU-2-c 1:1
the stretching vibration of the C O of polyether, and the band of
WPU-3-d WPU-1-d WPU-2-d 1:1 d around 1210 cm−1 were the stretching vibration of the C O of
WPU-3-e WPU-1-b WPU-2-b 1:2 polyester while the peaks of c from 1110 to 1250 cm−1 did not
WPU-3-f WPU-1-b WPU-2-b 2:1 exhibit obvious characteristic [27]. The bands around 1750 cm−1
WPU-3-g WPU-1-b WPU-2-b 1:3
were very sharp, mainly owning to the presence of C O in the
WPU-3-h WPU-1-b WPU-2-b 3:1
urethane and urea segments or polyester segments.
 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10 5

Scheme 3. Preparation process of WPU-3.

To distinguish the different carbonyl groups in the urethane and
urea segments, the FTIR spectra from 1500 cm−1 to 1800 cm−1 were
amplified in Fig. 3. According to the previous literatures [28], the
bands of free urethane groups are usually around 1740 cm−1 and
the bands of associated urethane groups are around 1702 cm−1 .
Meanwhile, the bands of free urea groups range from 1670 to
1689 cm−1 and the bands of associated urea groups are from 1630 to
1649 cm−1 . From Fig. 3, it can be identified that all the WPUs show
single band from 1700 cm−1 to 1750 cm−1 which can be attributed
to the C O in urethane groups or ester groups. More precisely, the
band of a is around 1720 cm−1 which can be ascribed to the combi-
nation of urethane groups and associated urethane groups whereas
the bands of b, c and d are around 1735 cm−1 by the combined
effect from urethane groups and ester groups. As for bands from
1600 to 1700 cm−1 , owing to the low content of urea groups in
polyurethanes, the bands around 1635 cm−1 which can be ascribed
to the associated urea groups in a, b and c are slight. Furthermore,
the band of d in this area is even negligible for there was no ether
groups in polyester-based WPU, leading to fewer associated urea
groups compared with a, b and c.
4.2. Particle size, PSD, viscosity, solid content and stability of
WPU-1
Fig. 4 showed that all polyester-based WPU-1 samples exhibited
unimodal PSD. Table 4 listed the particle size, PSD, viscosity, solid

Fig. 2. FTIR analysis of WPUs ((a) WPU-2-a; (b) WPU-3-e; (c) WPU-3-f; (d) WPU-1- Fig. 3. FTIR analysis of WPUs from 1500 cm−1 to 1800 cm−1 ((a) WPU-2-a; (b) WPU-
a). 3-e; (c) WPU-3-f; (d) WPU-1-a).
6 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10
Fig. 4. The particle size distribution of WPU-1.
content and stability of WPU-1. Table 4 revealed that the average
particle size of WPU-1 samples tended to be smaller with the incre-
ment of DMPA content. At the meantime, the viscosity was getting
higher which can be attributed to the augment of water swelling
layer induced by the increment of total surface area of particles
[29,30]. The samples from WPU-1-b to WPU-1-d showed good sta-
bility while the stability of the WPU-1-d was poor due to the large
particle size of WPU-1-a.
4.3. Particle size, PSD, viscosity, solid content and stability of
WPU-2
Similar as Fig. 4, all polyether-based WPUs in Fig. 5 also
presented unimodal PSD. From Table 5, it can be found that WPU-
2 samples exhibited smaller particle size and higher viscosity
compared with WPU-1 owing to the higher carboxyl content in
polyurethane chains.
4.4. Particle size, PSD, viscosity, solid content and stability of
WPU-3 (a–d)
From Fig. 6 it was interesting to find that WPU-3-a, WPU-3-
b and WPU-3-c exhibited bimodal particle size distribution while
WPU-3-d showed unimodal particle size distribution. From WPU-
3-a to WPU-3-c, two peaks of the samples tended to be close and
finally emerged into one peak in WPU-3-d. This phenomenon can
be explained by the different hydrophilicity between WPU-1 and
Table 4
Particle size, PSD, viscosity, solid content and stability of WPU-1.
Sample designation Particle size (nm)
WPU-1-a 1789.1
WPU-1-b 1106.9
WPU-1-c 558.7
WPU-1-d 372.4
a
Stability after six months.
WPU-2 prepolymers in the preparation of WPU-3. From WPU-3-a
to WPU-3-d, the difference of DMPA content between WPU-1 and
WPU-2 prepolymers diminished gradually and the average particle
size between WPU-1 and WPU-2 tended to be close. As a mat-
ter of fact, the DMPA contents between WPU-1-d and WPU-2-d
prepolymers were so close that the average particle size between
WPU-1-d and WPU-2-d were similar, resulting in the unimodal PSD
of WPU-3-d. This indicated that the difference of the hydrophilicity
in polyurethane chains between the first-step prepolymers and the
second-step prepolymers ought to be obvious enough to synthesize
WPUs with bimodal PSD.
Fig. 6 revealed that the sizes of large particles in WPU-3 (exclud-
ing WPU-3-d) were close to the particle size of the corresponding
WPU-1 samples and the sizes of small particles in WPU-3 were
similar to the particle size of corresponding WPU-2-b samples.
Moreover, the intensity ratio of large particles to small particles in
WPU-3 (excluding WPU-3-d) was nearly 1:1 which was in accor-
dance with the mass ratio of WPU-1 to WPU-2 well. This indicated
that most of WPU-2 prepolymers were emulsified at the outside of
WPU-1 particles rather than inside of these particles.
From Table 6, it was found that the particle polydispersity index
(PDI) was getting smaller and the viscosity increased from WPU-3-a
to WPU-3-d. WPU-3-d showed extremely high viscosity and nearly
cannot flow because of its unimodal particle size distribution.
According to the research on traditional emulsions by Greenwood,
small particles were able to fit into the packs among large parti-
cles when the diameter ratio of large particles to small particles
PDI Viscosity (mPa s−1 /25 ◦ C) Solid content (%) Stabilitya
0.267 45.2 40.6 Unstable
0.226 67.6 39.9 Stable
0.210 98.5 40.3 Stable
0.162 138.1 39.7 Stable
 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10 7

Fig. 5. The particle size distribution of WPU-2.

Table 5
Particle size, PSD, viscosity, solid content and stability of WPU-2.

Sample designation Particle size (nm) PDI Viscosity (mPa s−1 /25 ◦ C) Solid content (%) Stabilitya

WPU-2-a 76.3 0.067 577.4 40.5 Stable

WPU-2-b 102.6 0.130 487.9 39.8 Stable
WPU-2-c 136.8 0.210 319.3 40.3 Stable
WPU-2-d 192.1 0.274 267.2 39.9 Stable
a
Stability after six months.

Fig. 6. The particle size distribution of WPU-3 (diameter ratio variation).

8 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10
Fig. 7. The particle size distribution of WPU-3 (volume ratio variation).
Table 6
Particle size, PDI, viscosity, solid content and stability of WPU-3 (diameter ratio variation).
Sample designation Particle size (nm) PDI
WPU-3-a 312.5 0.71
WPU-3-b 373.1 0.63
WPU-3-c 306.7 0.45
WPU-3-d 287.4 0.31
L/S: large particles to small particles.
a
Stability after six months.
was more than 5.67 [21]. As shown in Table 6, WPU-3-c presented
relatively high viscosity with the diameter ratio of 4.7. It can be
attributed to the factor that many small particles were too large
to fit into the interstices among large particles in WPU-3-c with
the diameter ratio of 4.7, thus decreasing the packing efficiency. It
was very interesting to find that the viscosity of WPU-3-a with the
diameter ratio of 16.7 was higher than WPU-3-b with the diame-
ter ratio of 9.2, which indicated that the packing density decreased
when the diameter ratio of large particles to small particles was too
large. Therefore, we fixed the diameter ratio as 9.2 and changed the
mass ratio between WPU-1-b and WPU-2-b to study the influence
of volume percentage of large particles to the viscosity and solid
content of WPUs.
4.5. Particle size, PSD, viscosity, solid content and stability of
WPU-3 (e–h)
Fig. 7 showed that all samples presented bimodal PSD with the
nearly fixed diameters of large particles and small particles, which
was attributed to the fixed compositions of WPU-1-b and WPU-
2-b. From WPU-3-e to WPU-3-h, the volume percentage of large
particles changed gradually. Furthermore, the volume percentage
of large particles of WPU-3 showed direct correlation with the mass
ratio of WPU-1-b to WPU-2-b. This proved that the volume percent-
age of large particles of WPU-3 with bimodal PSD can be strictly
controlled by adjusting the mass ratio of WPU-1 and WPU-2.
Viscosity (mPa s−1 /25 ◦ C) Solid content (%) Diameter ratio (L/S) Stabilitya
722.8 55.1 16.7 Unstable
619.0 55.3 9.2 Stable
960.4 54.8 4.7 Stable
6267.2 54.6 – Stable
From Table 7, it can be seen that WPU-3-e and WPU-3-g showed
relatively higher viscosity while WPU-3-f and WPU-3-h presented
lower viscosity. According to the research by Chu and Guyot, the
emulsion exhibited lower viscosity and higher packing density
when the volume percentage of large particles was in the range
of 70–80% [31]. As Table 7 listed, the volume percentage of large
particles in WPU-3-e and WPU-3-g were 34% and 24% and the
whole volume of small particles were much larger than the inter-
stices among large particles, leading to the low packing density
and high viscosity. As for WPU-3-f and WPU-3-h, the volume per-
centage of large particles were 66% and 74% respectively and the
packing density increased with the decrement of the whole vol-
ume of small particles, resulting in lower viscosity. Compared with
WPU-3-e, WPU-3-h presented lower viscosity which indicated that
the volume percentage of large particles of WPU-3-h might be more
advantageous to increase the packing density.
4.6. Particle morphology of WPUs
Fig. 8 showed the TEM photographs of WPU-1-b, WPU-2-b
and WPU-3-h. As can be seen in the TEM photographs, WPU-1-b
and WPU-2-b exhibited unimodal PSD and the particle sizes were
around 1000 nm and 100 nm respectively. On the contrary, WPU-
3-h presented bimodal PSD and large particles were in the range of
800–1200 nm while small particles were around 100 nm. The TEM
photographs agreed with the DLS data well, proving the successful
synthesis of WPUs with bimodal PSD.
 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10 9

Table 7
Particle size, PDI, viscosity, solid content and stability of WPU-3 (volume ratio variation).

Sample designation Particle size (nm) PDI Viscosity (mPa s−1 /25 ◦ C) Solid content (%) Volume percentage (L) Stabilitya

WPU-3-e 206.8 0.65 942.7 55.1 34% Stable

WPU-3-f 836.2 0.64 572.0 54.9 66% Stable
WPU-3-g 144.7 0.46 1032.6 54.7 24% Stable
WPU-3-h 921.9 0.48 489.1 55.3 74% Stable

L: large particles.
a
Stability after six months.

Fig. 8. TEM photographs of WPUs; (a) WPU-1-b, (b) WPU-2-b, (c) WPU-3-h.

WPUs with reasonable bimodal PSD could raise the up limit of

solid content for small particles were able to fit into the interstices
among large particles, which increased the packing density.

5. Conclusion

A series of high solid content waterborne polyurethanes (WPU-

Fig. 9. The relationship between solid content and viscosity of WPUs.
4.7. Up limit of solid content of WPUs
Fig. 9 revealed the relationship between solid content and
viscosity. It was found that the viscosity of WPU-1-b and WPU-2-b
grew slowly with the increment of solid content under 46% solid
content and the viscosity increased rapidly above this point. As for
WPU-3-h, the viscosity remained low growth rate with the solid
content until 55% solid content. Therefore, the up limit of solid
content of WPU-1-b and WPU-2-b was regarded as 46% and the up
limit of solid content of WPU-3-h was 55%. Generally speaking, the
interaction between WPUs particles was mainly induced by Brow-
nian movement at low solid content. With the increment of solid
content, the average distance between particles shortened and the
collisions between particles added, resulting in the slow augment of
viscosity. When the solid content was near the up limit of solid
content, the average distance between particles was near the
hydrodynamic diameters of WPUs particles, leading to the strong
interaction among particles and rapid increment of viscosity.
3) were synthesized by two-step emulsification process. In the first
step, polyester-based WPU-1 with relatively large particle size was
firstly synthesized. In the second step, polyether-based prepoly-
mers based on WPU-2 with high DMPA content were prepared
firstly and WPU-1 emulsions were applied to emulsify WPU-2 pre-
polymers to get WPU-3.
It was found that WPU-1 and WPU-2 exhibited unimodal PSD
while WPU-3 showed bimodal PSD. Moreover, the diameter ratio of
large particles to small particles of WPU-3 can be controlled by the
difference of hydrophilicity between WPU-1 and WPU-2 prepoly-
mers and the volume percentage of large particles was controlled
by the mass ratio between WPU-1 and WPU-2 prepolymers. WPU-3
showed low viscosity (under 1000 mPa s−1 ) with 55% solid content
while WPU-1 and WPU-2 nearly cannot flow at the same solid con-
tent, which was attributed to the ratio of small to large particles of
WPU-3 with bimodal PSD since bimodal PSD of WPU-3 effectively
increased the packing efficiency of particles.
WPU-3 showed the lowest viscosity (489.1 mPa s−1 ) when the
diameter ratio of large particles to small particles was 9.2 and the
volume percentage of large particles was 74% and the up limit of
solid contents of WPU-1 and WPU-2 were limited to 46% while the
up limit of solid content of WPU-3 was as high as 55%.
Acknowledgments
This work was financially supported by the National High-
tech Research and Development Projects (863) (2013AA06A306),
National Natural Science Foundation of China (20874102), Sichuan
Province Science and Technology Support Projects (2010FZ0093)
10 S.-J. Peng et al. / Progress in Organic Coatings 86 (2015) 1–10

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