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Waterborne Polyurethane Modified With Silicone Macromer and The Nylon Airbag Coated With It

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Original article

Textile Research Journal


2016, Vol. 86(19) 2015–2021

Waterborne polyurethane modified ! The Author(s) 2015


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with silicone macromer and DOI: 10.1177/0040517515619352
trj.sagepub.com
the nylon airbag coated with it

Cheol Wan Go1, Jeong Han Yang2, Dong-sup Kwak3,


Gi-Woong Kim4 and Han Mo Jeong1

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)

used to modify a polyurethane coating to provide an


antifouling capability.12 The PDMS macromer with a
terminal methacrylate group (PDMS methacrylate
macromer) can be copolymerized with vinyl mono-
mers to make a contact lens that has a high oxygen
permeability.13,14 The terminal acrylic group can also
be grafted on the WPU by using a radical mechan- Figure 1. Chemical structure of poly(dimethylsiloxane)
ism.15 However, to the best of our knowledge, no methacrylate macromer.
paper has yet investigated the modification of WPU
with PDMS methacrylate macromer, and in this
study, a WPU with double bond in the main chain
Preparation of WPU
was grafted with PDMS methacrylate macromer
through a radical mechanism, and the changes in var- The reactor consisted of a 500 mL round-bottomed,
ious physical properties were examined. four-necked separable flask with a mechanical stirrer,
The textile of airbags can be coated with silicone a thermometer, and a condenser that attached a drying
rubber to prevent unwanted permeation of the inflating tube at the outlet. The reaction was carried out in a
gas through the textile and to protect the textile from heating mantle with a temperature controller.
damage due to the exposure to the hot gas that is used The isocyanate(NCO)-terminated prepolymer was
to inflate the airbag. WPU is considered to be a good prepared by reacting TMXDI and PC diol at 90 C
candidate as a coating resin for newer airbag designs, for 6 h in the presence of DBT (0.03 parts per 100
particularly for side curtain airbags. An airbag that is part of solid WPU) (Scheme 1). Then, DMPA was
coated with WPU has a longer gas pressure retention fed into the reactor to carry out an additional reaction
time at a lower coating level because the WPU effec- at 100 C for 20 h. Then, the BD and BE mixture was
tively seals the gas leakage, particularly along the fed into the reactor to react at 90 C for 6 h. Some
seams. However, the strong adhesion between the amount of acetone was added into the reactor when
WPU and the textile reduces the flexibility of the textile the viscosity became too high, and it was then cooled
and makes the coated textile become stiff. Therefore, down to room temperature. TEA was then fed into the
this study investigates the suitability of a WPU mod- reactor and was agitated for 1 h to neutralize the
ified with PDMS methacrylate macromer for use as an DMPA unit in the NCO-terminated prepolymer. The
airbag coating resin by assessing the properties of neutralized NCO-terminated prepolymer was emulsi-
nylon-6,6 textiles coated with the WPUs, including fied by feeding water at room temperature slowly for
their stiffness, tear strength, and air permeability. 40 min into the reactor under agitation. EDA and
DETA were dissolved in water (10 wt%) and were
then fed into the emulsion at 40 C, and the chain exten-
Experimental details sion by these amines was carried out for 2 h. The result-
ing WPU was a stable emulsion with a solid content of
Materials
about 35 wt%.
Poly(hexamethylene carbonate) diol (PC diol; Asahi- In order to modify the WPU, the PDMS methacry-
Kasei, Duranol T6002, 2000 g/mol), was dried and late macromer was fed and thoroughly mixed at 60 C
degassed at 95 C under a vacuum for 48 h. for 1 h. The PDMS methacrylate macromers can not
Dimethylol propionic acid (DMPA; Aldrich) was only polymerize by themselves but also graft on WPU
dried at 60 C for 48 h in a vacuum oven. 1,4- by a radical mechanism with a radical initiator. We
Butanediol (BD; Aldrich), 2-butene-1,4-diol (BE; used BE together with BD as chain extenders because
Aldrich), TMXDI (Allnex), dibutyltin dilaurate the double bond of the BE unit can improve the graft-
(DBT; Aldrich), potassium persulfate (KPS; Aldrich), ing efficiency on WPU. The radical initiator, KPS (0.5
acetone, PDMS methacrylate macromer (800–1000 g/ parts per 100 parts of macromer) was dissolved in water
mol; Gelest, see Figure 1), and a thickener (TEGO (10 wt%) and fed drop-wise into the emulsion for 1 h to
ViscoPlus-3030, Evonik Industries) were used as graft or polymerize the PDMS methacrylate macromer
received. Ethylenediamine (EDA; Aldrich), diethylene- through a radical mechanism at 60 C for 2 h. The recipe
triamine (DETA; Aldrich), and triethylamine (TEA; that was used to prepare the WPU modified with
Aldrich) were dried with 4 Å molecular sieve before PDMS methacrylate macromer is shown in Table 1.
use. Nylon-6,6 textile, woven to have 180  180 threads The sample designation codes provide information on
dm–1 with a yarn of 470 dtex/136 f, was coated with the amount of PDMS methacrylate macromer that was
WPU to examine the suitability of the WPU as a coat- used to modify the WPU. For example, WPU-10 was
ing resin for an airbag. modified with 10 parts of PDMS methacrylate
Go et al. 2017

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

Soft segment Hard segment

PC diol BD BE DMPA EDA DETA TMXDI


TEA Macromer
Sample mol wt% mol wt% mol wt% mol wt% mol wt% mol wt% mol wt% mol phr

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

Table 2. Tensile properties of waterborne polyurethanes


-34.9 °C
(WPUs)
-34.8 °C 5.2 J/g WPU-0
43.2 °C
5% Secant Tensile Elongation
Sample modulus (MPa) strength (MPa) at break (%)
-34.6 °C 5.7 J/g WPU-2.5
43.9 °C WPU-0 16.6  0.3 32.2  0.9 986  12
Exotherm

6.0 J/g WPU-5.0 WPU-2.5 16.8  0.6 32.8  1.4 968  18


-33.5 °C
44.1 °C
WPU-5.0 18.5  0.2 33.3  0.8 908  10
6.9 J/g WPU-10
WPU-10 20.3  0.3 36.5  1.0 852  11
-32.9 °C
44.6 °C WPU-20 18.7  0.4 38.3  1.1 807  14
7.8 J/g WPU-20

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)

Table 4. Physical properties of nylon-6,6 textile coated with


waterborne polyurethane (WPU)

Tear Air permeability


Sample Stiffness (N) strength (N) (L dm–2 min–1)

WPU-0 21.7  1.3 135  4.9 0.52


WPU-2.5 15.7  2.0 138  5.2 0.79
WPU-5.0 15.6  1.4 151  5.8 1.11
WPU-10 13.3  1.2 184  5.7 1.44
WPU-20 9.5  1.0 255  6.9 1.62

each fiber by an external force becomes more free when


gently bonded. Therefore, the decrease in stiffness, that
is, the increase in flexibility with an increased content of
PDMS segments in WPU, is mainly due to the reduced
adhesion and consequent alleviated solidarity of the
fibers.
Table 4 also shows that the tear strength of the tex-
tile coated with WPU increases as the content of PDMS
segments in WPU increased. The focus of the external
force at the tearing point will decrease when the
number of cases of independent deformation of the
fibers due to the external force increases as a result of
gentle bonding. Therefore, the increase in tear strength
is mainly due to the gentler bonding of the fibers with
the WPU modified with a PDMS methacrylate
Figure 4. Cross-sectional morphology of nylon-6,6 textile macromer.
coated with (a) WPU-0 and (b) WPU-10. The air permeability of the textile coated with WPU
increased as the content of PDMS segments in WPU
modification with the PDMS methacrylate macromer increased, as shown in Table 4. This increase is mainly
because it is a hydrophobic material.16 Table 3 also due to the presence of the PDMS segment because the
shows that the peel strength to detach the nylon-6 air permeability of PDMS is higher than that of
films glued by WPU decreases as the PDMS methacry- polyurethane.18
late macromer content in the WPU increases. This The guidelines suggested for a commercial airbag are
shows that the interactions at the interface between as follows: stiffness  15 N, tear strength  250 N, and
WPU and nylon-6 decrease due to the reduction in air permeability  2.0 L dm–2 min–1. The data shown in
the polarity of the WPU by the PDMS segment.17 Table 4 show that the nylon-6,6 textile coated with
WPU-20 satisfies all three of these guidelines.
Properties of nylon-6,6 textile coated with WPU
Figure 4 shows the cross-sectional morphology of the
Conclusions
textile coated with WPU, which demonstrates that the WPU was modified with PDMS methacrylate macro-
penetration of WPUs into the textile is limited, and mer by using a radical mechanism, and the thermal
the penetration degrees into the textile of WPU-0 properties measured by DSC and mechanical properties
(Figure 4[a]) and WPU-10 (Figure 4[b]) are similar. measured by a DMA and a tensile tester indicated that
This shows that the penetration of WPU into the textile the crystallinity of the soft segment increased but that
was effectively limited by thickening, and the effect of the cohesion of the hard segments was weakened by the
the modification by PDMS methacrylate macromer on modification.
penetration is insignificant. The hydrophobic PDMS segment hybridized with
Table 4 shows that the stiffness of the textile coated WPU increased the contact angle of water on WPU
with WPU decreased as the content of PDMS segments and reduced the adhesion between the WPU and
in WPU increased. The textile fibers should deform nylon. This improved the flexibility of the nylon-6,6
monolithically in response to external forces when textile coated with WPU because the solidarity of the
adhered by glue. However, the independent motion of fibers was alleviated by gentler bonding of the modified
Go et al. 2021

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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