Synthesis and Application of a Novel Modified
Polysiloxane Polymer with High Reaction Activity as
Water Repellent Agent for Cotton Fabrics
Chaohong Dong1,2, Zhou Lu2, Ping Zhu1,2, Lei Wang2, Fengjun Zhang2
1
College of Textile & Clothing, Jiangnan University, Wuxi CHINA
2
Laboratory of Fiber Materials and Modern Textile, Qingdao University, Qingdao CHINA
Correspondence to:
Chaohong Dong email: [email protected]
ABSTRACT
A novel poly(4-iodobutoxylmethylsiloxane) (PIBMS)
water repellent with high reaction activity was
synthesized
using
poly(hydromethylsiloxane)
(PHMS), methyl iodide (MeI) and tetrahydrofuran
(THF) in the presence of a catalytic amount of PdCl2.
The new chemical active group of PIBMS could
covalently bond to the cotton fabric. It is conducive
to improve the washability of treated cotton fabric.
The structure of PIBMS was confirmed by the FT-IR
and 1H NMR spectra. The PIBMS was applied onto
cotton fabric by a pad-dry-cure process. PIBMS was
applied to cotton fabrics and the effect of the process
parameters on water repellent performance was
studied. The morphology of PIBMS polymer film on
the cotton fabric was investigated by SEM. The water
repellency of treated cotton fabrics before and after
vigorous washes was compared. The results show
that the water repellent grade of cotton fabric treated
with PIBMS was 90. The contact angle of the treated
cotton fabric was 136.94°, which was higher than that
of the untreated cotton fabric. The water repellent
grade of treated cotton fabric was still as high as 80
after 20 times washing. The tear strength and the
tensile strength of cotton fabric significantly
increased after PIBMS treatment. The air
permeability and the water vapor permeability of
treated cotton fabric were slightly lower than those of
untreated cotton fabrics.
INTRODUCTION
Cotton fabric is an important textile product applied
in daily life and industry. This is because cotton
fabric’s many characteristics, such as softness, make
it desirable to the consumer. But at the same time,
cotton fabric has poor water repellency which
restricts its application in some areas. Finishing
with water repellents is a good way to impart water
repellency to cotton fabric.
Fluorine containing chemicals are known to have
low surface free energy which make them the most
important water and oil repellents [1-2]. Fluorine
containing chemicals are widely used in cotton
fabric finishing. However, certain fluorochemicals
were found to have potential risk to humans and the
environment [3-6]. People have made great efforts
to develop environment-friendly water repellents.
Polysiloxanes are known as reasonable water
repellents in a wide range of textile application
because of their useful properties [7-8], such as
good hydrophobicity, breathability, and high
thermal stability which is attributed to the high
flexibility of the Si–O bond [9]. The polysiloxane
modification using functional polymers or
compounds gradually becomes an important way to
broaden the application of polysiloxane. Xie K. et al.
[10] investigated the system of siloxane and acrylic
monomers. An Q. F. et al. [11] synthesized a novel
polysiloxane (RCAS) bearing dodecyl and carboxyl
side groups by reaction of a dodecyl/amino
functionalized polysiloxane with maleic anhydride.
Keywords: Reaction activity; Polysiloxanes
modification; Cotton fabric; Water repellency;
Washability
Journal of Engineered Fibers and Fabrics
Volume 10, Issue 2 – 2015
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Because of the excellent hydrophobicity of
polysiloxanes, many efforts have been done to
develop high-performance polysiloxanes water
repellents [12-13]. Hou A. Q. et al. [14] synthesized
a novel polysiloxane material modified with
fluorocarbon
group
through
ring-opening
polymerization, the result showed that the sample
treated with the modified polysiloxane emulsion got
excellent repellency to water.
EXPERIMENTAL
Materials
Poly(hydromethylsiloxane) (PHMS) was obtained
from Jinxinli Fine Chemical Plant of Qingdao;
Tetrahydrofuran (THF) was obtained from Bodi
Chemical Co., Ltd. of Tianjin; Methyl iodide (MeI)
was obtained from Shanpu Chemical Co., Ltd. of
Shanghai; Palladium chloride (PdCl2) was obtained
from Zhongxing Chemical Co., Ltd. of Tianjin;
Toluene was obtained from Laiyang Economic and
Technological Development Zone Fine Chemical
Plant; Zirconium oxychloride was obtained from
Aladdin Reagent Co., Ltd.
Poly(hydromethylsiloxane) (PHMS) is one of the
most important components of water repellency
[15-17]. The Si-OH group coming from hydrolysis
of Si-H bond could dehydrate, condensate, and
crosslink to form film on the surface of the material
[18-19]. Thus the water repellency of cotton fabric
can be obtained by PHMS treatement. But the fabric
handle and washability are unsatisfactory, because
of the brittle film formed on the fiber [20]. To solve
this problem, a new chemical active group can be
introduced onto PHMS, which can combine to
cotton fabric with a covalent bond [21-22].
Consequently, this new water repellent agent not
only has the traditional advantages of polysiloxane,
but also improves the durability of finishing.
Therefore, it can provide a long-lasting water
repellency effect.
Preparation and Characterization of PIBMS
A mixture of PHMS (10.3 g, 22.9 mmol Si-H 45.8
mmol), MeI (7.2 g, 51 mmol), THF (9.9 g, 137
mmol), and PdCl2 (0.125 g, 0.71 mmol) was stirred
at 50 ºC until the Si-H absorption band of the FT-IR
spectrum was almost disappeared. The reaction
progress could also be monitored by the 1H NMR
spectrometry. After the resulting black precipitates
were filtered, the volatile substances including
excess THF and MeI were evaporated under
reduced process to give PIBMS in 79.8% yield
(29.5 g, 35 mmol). PIBMS was colorless viscous oil
and was soluble in common organic solvents. The
structure of PIBMS was verified by 1H NMR
spectrum (JEOL LA500, Japan).
We recently reported PdCl2-catalyzed reactions of
α,ω-dihydropoly(dimethylsiloxane) with methyl
iodide (MeI) and tetrahydrofuran (THF), which
afforded
4-iodobutoxy-terminated
poly(dimethylsiloxane) [23]. Based on these results
and application to engineering textiles, we design a
synthesis process to introduce an activity group
onto PHMS which can improve its reaction activity
with cotton fabric.
FT-IR spectra of the PIBMS were recorded on a
Nicolet 5700 FT-IR apparatus. The spectra were
recorded over the range of 4000-400 cm-1. The
resolution was 4 cm-1 and the number of scans was
64 for each spectrum.
Treatment of Cotton Fabric with PIBMS
The desized, scoured, bleached cotton fabrics
(14.75 tex × 14.75 tex，133 ends per inch × 72 picks
per inch) samples were immersed in an aqueous
solution containing PIBMS and zirconium oxide
chloride at room temperature for 4 min under proper
pH condition. Then the cotton fabrics were padded
through two dips and two nips with a wet pick-up of
70%. Finally, the samples were dried at 100 °C for 3
min and cured at 150 °C for 4 min.
In this work, a new water repellent with high
reaction activity was firstly synthesized by
poly(hydromethylsiloxane) (PHMS), methyl iodide
and tetrahydrofuran (THF) in the presence of PdCl2
as
catalyst.
The
structure
of
poly(4-iodobutoxylmethylsiloxane) (PIBMS) thus
obtained was characterized by FT-IR and 1H NMR
spectra. The water repellency, tearing strength,
tensile strength, air permeability and water vapor
permeability of the cotton fabric treated with
PIBMS were investigated. PIBMS can combine to
cotton fabric with covalent bond due to the activity
group; therefore, the durability of the treated cotton
fabric with PIBMS is improved.
Journal of Engineered Fibers and Fabrics
Volume 10, Issue 2 – 2015
Evaluation of Water Resistance Properties
The water repellent properties of the fabrics were
evaluated in accordance with AATCC Test Method
22: Water Repellency. Fasten the test specimen
securely in the hoop, and let the surface of the
fabric specimen be exposed to the water spray. The
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surface of the specimen should be smooth and
without wrinkles. 250 mL of distilled water at 27 ±
1 °C (80 ± 2 °F) was poured into the funnel of the
tester and sprayed onto the test specimen for 25 - 30
s. Took the hoop by the bottom edge and tapped the
opposite edge firmly once against a solid object
with the fabric facing the object, then rotated the
hoop 180° and tapped once more on the point
previously held. Rated as follows: 100 - no sticking
or wetting of the specimen face; 90 - slight random
sticking or wetting of the specimen face; 80 wetting of specimen face at spray points; 70 partial wetting of the specimen face beyond the
spray points; 50 - complete wetting of the entire
specimen face beyond the spray points; 0 - complete
wetting of the entire face of the specimen.
cN/g, Five specimens (100 mm × 63 mm) with
specific shape were die-cut from the sample fabric.
The specimens were mounted between two clamps,
precut by a knife then torn through a fixed distance
by the swinging pendulum to generate the average
tearing force in Newton for weft directions.
Tensile Strength
The tensile strengths of the samples were measured
according to EN ISO test method 13934-1 using a
JAMES.H.HEAL tester. Samples with the size of 30
cm × 5 cm were subjected to test.
Comfortable Properties
Air permeability tests were made with TEXTTEST
FX 3300 air permeability test equipment. According
to ISO 9237 test standards, the test pressure for the
normal fabrics is 100 Pa, the applied test area is 20
cm2 and the measuring unit is mm/s.
Hydrophobic properties were also characterized by
an Easy Drop video optical contact angle meter. The
contact angle was calculated using the formula θ =
2 tan-1 (2h/d), where h is the height of the water
droplet and d is the width of the droplet touching
the film.
Water vapor permeability tests were made with
YG601 water vapor permeability test equipment.
The test was made in accordance with
GB/T12704.1-2009 test standards. The measuring
unit is g/(m2·h).
Washability of Treated Cotton Fabric
According to GB/T 8629-2001 (National Standards
of the People’s Republic of China for textile,
Experiment with the family washing and drying
procedures), the treated cotton fabric was washed
with 2 g/L neutral detergent solution 5 times for 5
minutes each time. Then it was dried at room
temperature and its water repellency was tested.
According to the operational processes mentioned
above, the cotton fabric was washed 20 times and
its water repellency was tested for 4 times.
RESULTS AND DISCUSSION
Synthesis and Characterization of PIBMS
The reaction schematic plot is shown in Scheme 1.
Scanning Electron Microscope (SEM)
Scanning electron microscope (SEM) was conducted
on a JSM-6010LA instrument (Japan Electron Optics
Laboratory Co.Ltd.) to investigate the surface
morphology of cotton fabric. A sputter coater was
used to pre-coat conductive gold onto the surface
before observing the microstructure at 5.0 kv.
Tear Strength of the Treated Cotton Fabric
The tear strength of the treated fabrics was
measured using James H. Heal digital tear strength
tester in accordance with ISO 13937-1:2000.
Scheme 1. Preparation of PIBMS.
The fabric was conditioned in a standard
environment of 21 ± 1°C and 65 ± 2% relative
humidity for at least 4 hours. Equipped with a group
of heavy hammer to adapt to the whole range: 3200
Journal of Engineered Fibers and Fabrics
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173
FT-IR spectra of PHMS and PIBMS are shown in
Figure 1. In the FT-IR spectra, the transmissivity of
Si-H bond at PIBMS was higher than that at PHMS.
The data showed that Si-H bond stretching vibration
reduced, which was the powerful demonstration of
the activity of Si-H bond.
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FIGURE 2. 1H NMR spectrum of PHMS in CDCl3.
FIGURE 1. FT-IR spectra of PHMS and PIBMS
For comparison, the FT-IR spectra of PHMS and
PIBMS were recorded as shown in Figure 1. The
absorption peak at 2950 cm-1 was attributed to the
symmetric and asymmetric telescopic vibration of
the –CH3[24-25]; the absorption peak located at
2160 cm-1 was assigned to stretching vibration of
the Si-H bonds[24, 26]; the absorption peak located
at 1280 cm-1 was assigned to –CH3 deformation
vibrations of the siloxane components[26]. It can be
seen from Figure 1 that the peak intensity at 2160
cm-1 of PHMS is much stronger than that of PIBMS,
indicating that the Si-H bond stretching vibration is
greatly reduced after modification. So it can be
verified that the modification reaction occurred at
Si-H bond. So the change of the peak intensity at
2160 cm-1 was the characterization of the reaction
which occurred at the Si-H group.
FIGURE 3. 1H NMR spectrum of PIBMS in CDCl3.
As shown in Figure 3, the Si-H bonds were entirely
converted to 4-iodobutoxy units and no unidentified
signals were detected in the 1H NMR spectrum. 1H
NMR (δ in CDCl3) 0.09-0.14 (br s, SiMe), 1.64 (qui,
4H, OCH2CH2, J = 7.5 Hz), 1.91 (qui, 4H, CH2CH2I,
J = 7.5 Hz), 3.22 (t, 4H, CH2I, J = 7.0 Hz), 3.70 (t,
4H, CH2O, J = 6.0 Hz) [27].
In order to verify the existence of iodide ion in
PIBMS, the conversions between C-I bonds and
C-N bonds were examined (Scheme 3 and Figure S1,
See supporting information).
1
H NMR spectra of PHMS and PIBMS are shown
in Figure 2 and Figure 3, respectively. 1H NMR
spectrum of PHMS shows that the signal for Si-H
appeared at 4.7 ppm. 1H NMR spectrum of PIBMS
shows that the signal for O-CH2 appeared at 3.7
ppm, the signal for I-CH2 appeared at 3.22 ppm.
Based on the above analysis, it was come to the
conclusion that the modification reaction had
occurred.
Journal of Engineered Fibers and Fabrics
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Treatment of Cotton Fabric with PIBMS
Effect of Content of PIBMS on Water Repellency
TABLE I. Effect of different content of PIBMS on the grade of
water repellency.
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The surface energy depends on the chemical
composition of the material. Silicon and oxygen
atoms arranged on the surface of fabric have played
an important role in lowering the surface energy.
The content of PIBMS has a significant impact on
water repellency of treated cotton fabric. As
expected, Table I shows that the water repellency
grade of treated cotton fabric is improved with the
increment of the content of PIBMS until to 50 g/L.
When the content of PIBMS reached to 50 g/L, the
water repellency grade of treated cotton fabric was
90, and only slight wetting was observed on the
surface. This phenomenon also was observed when
the content of PIBMS reached to 60 g/L. As a result,
the optimum content of PIBMS was 50 g/L.
Effect of Ph Value on Water Repellency
TABLE III. Effect of pH value on the grade of water repellency.
PIBMS (g/L) Catalyst (g/L)
TABLE II. Effect of different content of catalyst on the grade of
water repellency.
pH
Water
Repellent
grade
50
5
9
80
50
10
9
90
50
15
9
90
50
20
9
90
Water
Repellent
grade
50
10
7
70
50
10
8
80
50
10
9
90
50
10
10
90
Table III shows that pH value has a great impact on
the water repellency of treated cotton fabric. The
water repellency of treated cotton fabric was
improved with the increase of pH value until to 9.
In alkaline condition, NaO-Cell is formed due to the
reaction between cellulose and alkaline [29];
O-Cell which acts as nucleophilic reagent can
promote the departure of I- of PIBMS and react with
PIBMS. We can conclude that alkaline condition
contributes to better combine between cotton fabric
and PIBMS. But when the pH value was over 9, the
water repellency grade of treated cotton fabric
didn’t improve with the increase of pH value
anymore. Therefore, the optimum pH value was 9.
Effect of Content of Catalyst on Water Repellency
PIBMS (g/L) Catalyst (g/L)
pH
Effect of Curing Temperature on Water Repellency
Proper directional alignment of silicone polymer on
the fiber surface is a necessary factor to impart
water repellency to treated cotton fabric with
silicone polymer. To improve directional alignment
of silicone polymer on the fiber surface, additives
are needed to add. Generally, the additive applied in
silicone polymer treatment is Zirconium
oxychloride. Zirconium oxychloride is used as
catalyst in the water repellency finishing [28].
Zirconium oxychloride could promote the
directional alignment of the PIBMS on the cotton
fiber surface by the coordination of Zr and oxygen
atoms of PIBMS. Table II shows that: when the
content of catalyst was 10 g/L, the water repellency
grade of treated cotton fabric was 90 which meant
the catalyst had worked effectively at this
concentration. When the concentration of catalyst
was over 10 g/L, the water repellency grade of
treated cotton fabric didn’t improve with the
increase of catalyst concentration anymore. As a
result, the optimum content of catalyst was 10 g/L.
Journal of Engineered Fibers and Fabrics
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TABLE IV. Effect of curing temperature on the grade of water
repellency.
PIBMS (g/L) Catalyst (g/L)
pH
Curing
Temperature
and Time
/ o C， min
Water
Repellent
grade
50
10
9
140 × 4
80
50
10
9
150 × 4
90
50
10
9
160 × 4
90
50
10
9
170 × 4
90
Table IV shows that curing temperature has an
impact on the water repellency of treated cotton
fabric. When the curing temperature reached to 150
o
C, the water repellency grade of treated cotton
fabric was 90. This was ascribed to the favorable
effect of the temperature to form covalent bond
between PIBMS and cotton fabric giving rise to the
formation of PIMBS film that deposited on the
fabric [30]. Increasing curing temperature to 170oC
is accompanied by a slight yellowness of cotton
fabric and a slight stiff handle [30].
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As discussed above, the optimum condition of
treatment was the content of PIBMS was 50g / L,
the content of catalyst was 10g/L, the pH value was
9, and the curing condition was 150 oC for 4
minutes. The water repellency grade of treated
cotton fabric was 90 at the optimum condition.
Figure 4 shows that there was slight random
sticking or wetting on the treated fabric after
sprayed, so the water repellent grade is 90. Dripped
a drop of water on the surface of treated cotton
fabric, the spreading condition of water droplet was
observed, Figure 5 shows that water droplet slightly
wet the surface of treated cotton fabric. It indicates
that the water repellency of treated cotton fabric is
excellent.
Evaluation of Water Resistance Properties
The surface condition of the cotton fabric after
being sprayed is shown in Figure 4. The spreading
condition of water droplet on the surface of treated
cotton fabric is shown in Figure 5.
(a) Untreated cotton fabric (θ = 88.37 o)
FIGURE 4. Surface condition of the fabric after sprayed.
(b) Cotton fabric treated with PIBMS (θ = 136.94 o)
FIGURE 6. Contact angle of water drop on the cotton fabrics.
(a) Vertical direction
The contact angle of the untreated cotton fabric and
treated cotton fabric were measured as shown in
Figure 6. As can be seen, the contact angle of
untreated cotton fabric was only 88.37o, while the
contact angle of cotton fabric treated with PIBMS
was 136.94 o. The treated cotton fabrics with PIBMS
showed excellent water repellency.
(b) Horizontal direction
FIGURE 5. The spreading condition of water droplet on the
surface of cotton fabric.
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Surface Properties
the gap between fibers was clear. As for the treated
fabric, PIBMS was evenly distributed on the surface
of cotton fibers and formed a uniform film. The film
can weaken capillary effect of cotton fabric. Then
water wetting ability of treated cotton fabric was
reduced. It played a certain role in water repellency.
When the curing temperature was more than 140 °C,
PIBMS molecules were directionally arranged on
fabric, while hydrophobic groups (-CH3) of PIBMS
were toward gaseous phase. Therefore, the
fabric/water interfacial tension was reduced.
Ultimately, the cotton fabric treated with PIBMS
had excellent water repellency.
(a)
Washing Durability
The water repellent grade and contact angle of
treated cotton fabrics after wishing are shown in
Table V. We can know that the water repellency
grade of treated cotton fabric was still as high as 80
after 20 times washing. The washability of treated
cotton fabric was increased due to the finishing
agent combined to cotton fabric with covalent bond.
The reaction schematic is listed as the Scheme 2.
TABLE V. The Water Repellent grade and Contact angle of
treated cotton fabrics after wishing.
(b)
FIGURE 7. SEM images of untreated (a) and treated cotton
fabric with PIBMS (b).
Washing times
The SEM images of untreated and treated cotton
fabrics are shown in Figure 7. The surface of
untreated cotton fabric (Figure 7a) was smooth and
0
5
10
15
20
Water
Repellent
grade
90
90
90
80
80
Contact angle
136.94
134.31
131.24
128.16
123.06
(Figure 8)
(a)
(b)
(c)
(d)
(e)
FIGURE 8. Contact angle of water drop on the cotton fabrics
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CH3
CH3
H3C
Si
O
Si
be due to the film formed on the fiber surface
distributes stress uniformly and reduces the
concentration of stress leading to the enhancement
of fiber strength.
CH3
O
CH3
Si
PIBMS
n
CH3
O
CH2
CH3
CH2
TABLE VI. Tensile strength of untreated and treated cotton
fabrics.
CH2
CH2
O
O
O
Item
O
Tensile strength
Tensile strength
(N)
(N)
in warp direction
in weft direction
Untreated fabric
523
348
Treated fabric
601
404
O
O
PIBMS
SCHEME 2. Reaction between PIBMS and cotton fabric.
Tear Strength
According to ISO13937-1: 2000, all the samples
were treated under the optimum finishing conditions,
then were cut into 100 mm × 75 mm strips. A drop
hammer tear strength machine was used to measure
tear strength of the treated cotton fabric. The results
show that the tear strength of untreated cotton fabric
was 14.1 N and the tear strength of treated cotton
fabric was improved to 15.8 N. This definitely was
an improvement (about 12 %) of tear strength for
the PIBMS treated cotton fabric compared with the
untreated cotton fabric. The reason may be that the
film formed on the surface of fibers due to
GPPDMS reduces the coefficient of friction
between fibers and yarns contributing to better
removability of fibers and yarns, therefore, more
yarns are available to bear the force when the fabric
is tore.
Comfortable Properties
Table VII shows that the air permeability of treated
cotton fabric was decreased. The reason may be that
the film formed on the fiber surface reduces gaps
between fibers and leading to less amount of air can
pass through the treated cotton fabrics. Comparing
to the untreated fabric, the water vapor permeability
of treated fabric also decreased as shown in Table
VII. The number of pores on the fabric determines
the water vapor permeability of fabric. During the
finishing, some pores were filled with chemical
agents via bonding leading to lower water vapor
permeability. In addition, the PIBMS treated cotton
fabric formed a water repellent film on its surface
which decreased the water vapor permeability of
fabric.
TABLE VII. Comfortable properties of untreated and treated
cotton fabric.
Tensile Strength
Tensile properties of untreated and treated cotton
fabrics were tested and the data are presented in
Table VI. Tensile strengths of untreated cotton
fabrics in warp and weft direction are 523 N and
348 N respectively. The tensile strengths of treated
fabrics in warp and weft direction are 601N and 404
respectively, which is higher than those of untreated
cotton fabrics. The rupture of cotton fiber is
possibly due to the structure flaws and weak links in
its aggregation structure. When the cotton fiber is
stretched, these flaws and weak links are firstly
damaged and then leading to a concentration of
stress in the main chain of partly orientated
macromolecules, finally, these molecule chains are
broken and leading to the rupture of cotton fiber.
The enhancement of tensile strength of the treated
cotton fabric in both warp and weft directions may
Journal of Engineered Fibers and Fabrics
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Air
permeability
(mm/s)
Water vapor
permeability
Untreated
fabric
343
510.8
Treated fabric
250
458.7
Item
(g/(m2 ·h))
CONCLUSION
Poly(4-iodobutoxylmethylsiloxane) (PIBMS) was
prepared by poly(hydromethylsiloxane) (PHMS),
methyl iodide and tetrahydrofuran with the catalyst
of palladium chloride added. The results of FT-IR
and 1H NMR demonstrate that the product of
PIBMS
was
successfully
prepared.
The
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contact angle of cotton fabric finished by PIBMS
was 136.94o which proved that the cotton fabric
treated with PIBMS had good water repellency. The
SEM results show that the PIBMS evenly
distributed on the surface of finished cotton fabric
and formed a uniform film. The water repellency of
cotton fabric treated with PIBMS was better than
that of untreated cotton fabric. In addition, the tear
strength and tensile strength of cotton fabric treated
with PIBMS also increased. The air permeability
and the water vapor permeability of treated cotton
fabric were slightly lower than those of untreated
cotton fabrics. The cotton fabric treated with
PIBMS had satisfactory water repellency and
washability.
[6]
[7]
[8]
[9]
ACKNOWLEDGMENTS
The financial support by National Natural Science
Foundation of China (NO: 50773032) and doctoral
fund by the ministry of education of Higher
Education Institutions are greatly appreciated.
[10]
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AUTHORS’ ADDRESSES
Chaohong Dong
Ping Zhu
College of Textile & Clothing
Jiangnan University
Wuxi 214064
CHINA
Chaohong Dong
Zhou Lu
Ping Zhu
Lei Wang
Fengjun Zhang
Laboratory of Fiber Materials and Modern Textile
Growing Base for State Key Laboratory
Qingdao University
Qingdao 266071
CHINA
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