Waterborne Polyurethane Modified With Silicone Macromer and The Nylon Airbag Coated With It
Waterborne Polyurethane Modified With Silicone Macromer and The Nylon Airbag Coated With It
Waterborne Polyurethane Modified With Silicone Macromer and The Nylon Airbag Coated With It
Abstract
A waterborne polyurethane (WPU) with a double bond in the main chain was modified with a poly(dimethylsiloxane)
(PDMS) macromer having a terminal methacrylate group (PDMS methacrylate macromer) by using a radical mechanism,
and the changes in various physical properties were examined. Although the crystallinity of the soft segment domain
increased, the cohesion of the hard segments was weakened as a result of the modification with the PDMS methacrylate
macromer. The adhesion between the WPU and nylon decreased due to the hydrophobic/low polarity of the PDMS
component, and this improved the flexibility and the tear strength of the nylon-6,6 textile coated with WPU. The air
permeability of the coated textile also increased as a result of the modification.
Keywords
waterborne polyurethane, silicone macromer, nylon-6, 6, airbag
Waterborne polyurethane (WPU) is an environmen- obtain the benefits of using both types of polymers.
tally friendly material with excellent performance char- For this modification, hydroxyalkyl- or aminoalkyl-
acteristics. It has been used in a wide range of terminated difunctional silicones are normally utilized
applications, such as in flexible coatings for textiles, to introduce a silicone segment in the main chain of
hard coatings for wood and metallic surfaces, and as the WPU.6–8
an adhesive in the shoe and laminating industry,1,2 A macromer is a mono-functional monomer with a
because a wide range of monomeric materials are com- high molecular weight that has been effectively utilized
mercially available and tailor-made properties can be in industry to endow special properties both in the
obtained from well-designed combinations of the bulk and at the surface of adhesive, sealants, and coat-
monomeric materials. Polycarbonate (PC) diol is ings. A poly(dimethylsiloxane) (PDMS) macromer
superior to other polyols with respect to durability, with a terminal amine functional group has been
water resistance, and chemical resistance. m-
Tetramethylxylylene diisocyanate (TMXDI) is a diiso-
cyanate uniquely suited for WPU because processing is
1
easy due to low prepolymer viscosity, and the WPU can Department of Chemistry, Energy Harvest-Storage Research Center,
University of Ulsan, Republic of Korea
be designed to be a flexible coating with superior adhe- 2
Polyurethane Research Center, VIX Co., Ltd, Republic of Korea
sion and exceptional toughness. 3
R&D Division, Korea Dyeing & Finishing Technology Institute, Republic
In addition, the properties of WPU can be tailored of Korea
4
through hybridization with other polymers, such as Industrial Materials R&D Group, Central Research Park, Kolon
acrylics,3–5 silicones,6–8 or with nanofillers.9–11 Industries, Inc., Republic of Korea
Silicones possess unique and superior characteristics
Corresponding author:
including good flexibility, low surface energy, resistance Han Mo Jeong, Department of Chemistry, Energy Harvest-Storage
to humidity, and anti-marine fouling. Therefore, WPU Research Center, University of Ulsan, Ulsan 44610, Republic of Korea.
has been modified with silicones to simultaneously Email: hmjeong@mail.ulsan.ac.kr
2016 Textile Research Journal 86(19)
Scheme 1. The process for the preparation of air bag coated with waterborne polyurethane (WPU) modified by poly(dimethylsi-
loxane) (PDMS) methacrylate macromer.
macromer per 100 parts of solid WPU (10 parts per min–1. About 5 mg of the sample were heated to
hundred resin, 10 phr). 200 C and were then cooled down to –50 C. In the
subsequent heating scan, the glass transition tempera-
ture (Tg), melting temperature (Tm), and heat of fusion
Characterization of WPU (DHm) were measured. The dynamic mechanical prop-
The WPU films were cast from the emulsion by drying erties were determined by using a dynamic mechanical
at room temperature for 24 h and then at 60 C for 5 h thermal analyzer (DMA, Q80; TA Instruments) in the
on a Teflon plate. Differential scanning calorimetry tension mode at a heating rate of 3 C min–1 and 1 Hz.
(DSC) was carried out with a Q20 instrument (TA The tensile properties were then examined at room tem-
Instruments) at a heating and cooling rate of 10 C perature with a tensile tester (OTU-2, Oriental TM Co.,
2018 Textile Research Journal 86(19)
Table 1. Recipe for the preparation of waterborne polyurethane (WPU) modified with poly(dimethylsiloxane) methacrylate
macromer
WPU-0 1.00 68.36 0.45 1.40 0.45 1.37 0.50 2.75 0.28 0.57 0.21 0.49 3.00 25.05 0.40 0
WPU-2.5 The same with WPU-0 2.5
WPU-5.0 The same with WPU-0 5.0
WPU-10 The same with WPU-0 10.0
WPU-20 The same with WPU-0 20.0
PC diol: poly(hexamethylene carbonate) diol; BD: 1,4-butanediol; BE: 2-butene-1,4-diol; DMPA: dimethylol propionic acid; EDA: ethylenediamine;
DETA: diethylenetriamine; TMXDI: m-tetramethylxylylene diisocyanate; TEA: triethylamine.
Korea). A cast film was cut into a micro-tensile speci- Company, Inc) according to ASTM D 4032, and the
men 20 mm in length, 5 mm in width, and 0.2 mm in tear strength of the coated textile was then measured
thickness. The specimen was then elongated at a rate using a Mechanical Testing Equipment (3365 Machine,
of 100 mm min–1. InstronÕ ) according to ASTM D 2261. The air perme-
The static contact angle of the water droplet placed ability of the coated textile was measured using an Air
on the WPU film was measured using a contact angle Permeability Tester (FX3300, Textest Instruments)
measuring instrument (FM 40 EasyDrop; Kruss). In according to ISO 9237.
order to evaluate the adhesion at the WPU/nylon-6
interface, two sheets of nylon-6 films (0.025 mm thick)
were glued with WPU, and the 180 peel strength to Results and discussion
detach the two bonded nylon-6 films (20 mm in width) Properties of WPU modified with PDMS methacry-
was measured with a tensile tester (OTU-2, Oriental
late macromer
TM Co., Korea) at a peeling speed of 100 mm min–1.
A single nylon-6 film was coated with WPU (0.6 g m–2 Figure 2 shows the DSC thermograms of the WPUs.
solid) and dried for 10 min at room temperature and an The glass transition and the endothermic melting peak
additional 3 min at 90 C. Another nylon-6 film was of PC soft segments can be seen in the thermogram.
placed on this coated film and both were compressed However, the melting peak of the hard segment could
with a pressure of 9.8 MPa at 60 C for 90 s to glue the not be detected. These thermograms suggest that soft
two nylon-6 films with the WPU. and hard segment domains are phase-separated, and
the soft segment domain is crystalline while the hard
segment domain is amorphous. The DHm and the Tg of
Characterization of the textile coated with WPU the soft segment increases as the PDMS methacrylate
In order to examine the suitability of the WPU as a macromer content in the WPU increases, which proves
coating resin for an airbag, the WPU was mixed with that the crystallization of the soft segment increases in
3 phr (based on solid WPU) of thickener, TEGO the presence of the PDMS segment. This suggests that
ViscoPlus-3030, to increase the viscosity at 25 C up the phase separation between soft and hard segments
to around 10,000 cP just before coating. The thickened was enhanced by the PDMS segment. The Tm of the PC
emulsion was de-aerated by centrifuging at 3000 rpm soft segment also increases as the crystallinity of the PC
for 3 min, and then coated with a comma knife over a soft segment is increased; however, there is an exception
roll coater manufactured for laboratories by Mathis for WPU-20 because Tm is not only related to the crys-
AG. The coated textile was then dried at 90 C for tallinity but also other factors, such as crystal size or
3 min and then at 150 C for 1 min. The weight of the miscibility with other segments.
coated solid WPU was adjusted to be 30 g m–2. Figure 3(a) shows the dynamic mechanical properties
The cross-sectional morphology of the coated textile of the WPUs. The storage tensile modulus (E0 ) of the
was observed by using a field emission scanning elec- WPU-0 decreases by about 1/100th when heated in the
tron microscope (FE-SEM, JEOL JSM-6500 F). The temperature range from –50 C to 0 C, due to the glass
stiffness of the coated textile was measured using a transition of the soft segment. However, this softening
Fabric Stiffness Tester (SASD-672, J. A. King & diminishes as the PDMS methacrylate macromer
Go et al. 2019
43.8 °C
Table 3. Contact angle and adhesive strength of waterborne
-50 0 50 100
polyurethanes (WPUs)
Temperature (°C)
Contact angle Peel strength
Figure 2. Differential scanning calorimetry thermograms of Sample (degree) (N cm–1)
waterborne polyurethanes. WPU-0 73.8 1.55 0.10
WPU-2.5 83.2 0.76 0.01
WPU-5.0 88.3 0.58 0.04
WPU-10 95.7 0.46 0.02
(a) WPU-0
3 WPU-2.5
10
WPU-5.0
WPU-20 104.8 0.26 0.01
WPU-10
2 WPU-20
10
10
1 smaller as the PDMS methacrylate macromer content in
the WPU increases, which also indicates that the crystal-
E' (Pa)
0
10 linity of the soft segment has increased. However, at the
-1
10
temperature region around 50 ˚ C, E0 drops earlier on
heating at a lower temperature when the WPU is mod-
-2
10 ified with PDMS methacrylate macromer. This indicates
-3
10
that the cohesion of the hard segments is weakened in
-100 -50 0 50 the presence of the PDMS methacrylate macromer,
Temperature (°C) which suggests that a substantial amount of PDMS
(b) 10
1
WPU-0
methacrylate macromer has been grafted on the double
WPU-2.5
WPU-5.0
bond of BE in the hard segment domain and thus hin-
WPU-10
WPU-20
ders the cohesion of the hard segments.
10
0 Table 2 shows the tensile properties of the WPUs.
The 5% secant modulus and tensile strength generally
increases with only one exception: when the content of
Tan δ
-1
the PDMS methacrylate macromer increases in the
10
WPU. The main reason for this variation is the increase
in crystallinity of the soft segment, as was previously
discussed. The exceptional modulus decrease of WPU-
-2
10 20 may be due to the contribution by the soft PDMS
-100 -50 0 50
segment manifested at high content. However, the elon-
Temperature (°C)
gation at break decreases as the PDMS methacrylate
macromer content in the WPU increases. This suggests
Figure 3. Dynamic mechanical properties of waterborne that the development of a well-ordered orientation of
polyurethanes. the hard segment through an external force at high
elongation, with optimized hydrogen bonding between
content in the WPU increases due to the increased crys- hard segments, is hindered by the grafted PDMS seg-
tallinity of the soft segment, as explained in the DSC ment. Thus, a premature break occurred.15
results. In Figure 3(b), the tan peak due to the glass Table 3 shows that the static contact angle of a water
transition moves to a higher temperature and becomes droplet placed on a WPU film increases due to a
2020 Textile Research Journal 86(19)
WPU. This gentler bonding also improved the tear waterborne polysiloxane–urethane dispersion for poten-
strength of the nylon-6,6 textile coated with WPU. tial marine coatings. Polym Advan Technol 2013; 24:
The air permeability of the WPU-coated nylon-6,6 tex- 307–317.
tile increased due to the inclusion of PDMS segments 7. Rahman MM, Chun H-H and Park H. Waterborne poly-
with a high air permeability. siloxane–urethane–urea for potential marine coatings.
J Coat Technol Res 2011; 8: 389–399.
8. Lei H, Luo Y, Ge Z, et al. Preparation and properties of
Declaration of conflicting interests
waterborne siloxane-containing polyurethane for mois-
The authors declared no potential conflicts of interest with ture permeable textile coating. e-Polymers 2011; 11:
respect to the research, authorship, and/or publication of this 750–759.
article. 9. Kim BK, Seo JW and Jeong HM. Morphology and prop-
erties of waterborne polyurethane/clay nanocomposites.
Funding Eur Polym J 2003; 39: 85–91.
The authors disclosed receipt of the following financial sup- 10. Raghu AV, Lee YR, Jeong HM, et al. Preparation and
port for the research, authorship, and/or publication of this physical properties of waterborne polyurethane/functio-
article: This work was supported by the Korea Evaluation nalized graphene sheet nanocomposites. Macromol Chem
Institute of Industrial Technology (KEIT) through its Phys 2008; 209: 2487–2493.
Advanced Technology Center Program (10048772). This 11. Heck CA, dos Santos JHZ and Wolf CR. Waterborne
work was also supported by the Priority Research Centers polyurethane: the effect of the addition or in situ forma-
Program through the National Research Foundation of tion of silica on mechanical properties and adhesion. Int J
Korea (NRF) funded by the Ministry of Education (2009- Adhes Adhes 2015; 58: 13–20.
0093818). 12. Sommer S, Ekin A, Webster DC, et al. A preliminary
study on the properties and fouling-release performance
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