Hydrogen-containing silicone oil surface graft modified PET fabric water repellency

Lei Jingxin, Liao Xia, Li Qiang, Gao Jun (State Key Laboratory of Polymer Materials Engineering, Institute
of Polymer Research, Sichuan University, Chengdu 6100, China

Abstract:

Through the measurement of grafting rate, contact angle, water penetration time, tensile stress and
strain, ESCA, and water shock experiments, corona discharge induced hydrogen-containing silicone oil
grafted PET fabric and its water repellency in the presence of DCP and BP were studied. . The
experimental results show that the corona discharge can effectively initiate the graft copolymerization
of hydrogen-containing silicone oil on the surface of the PET fabric. With the extension of the corona
discharge treatment time, the grafting rate of the surface of the PET fabric increases; the water repellent
effect of the PET fabric is obvious after the grafting Reinforcement; After the graft modification caused
by corona discharge, the PET fabric is not damaged, and the mechanical properties remain basically
unchanged. Keywords: PET; corona discharge; graft modification; hydrogen-containing silicone oil;
water-repellent finishing Chinese Library Classification Number: O631 Document Identification Code: A
Article Number: 1008-9357(2000) 03-0317-04

PET fabric has high strength and low price. It is the largest variety of chemical fiber fabric materials.
However, its water repellency is poor, which limits its application range to a certain extent. A large
number of domestic and foreign research reports on the water-repellent finishing of PET fabrics[1-3] all
use the rolling-bake-baking chemical water-repellent finishing method, which uses the decomposition of
organic peroxides at high temperatures to form free radicals and initiate free energy Lower organic
monomers containing silicon or fluorine are graft-modified on the surface of PET fabrics, which have
disadvantages such as low grafting efficiency, complex process flow, high energy consumption and large
pollution.

The corona discharge treatment depth is small ( ～ 10-6mm), does not damage the properties of the
material itself, and can be operated continuously. It has been used in large-scale industrial applications
in the color printing and bonding of plastics (PP, PE, PETF). Compared with commonly used radiation
sources such as X-rays and electron beams for radiation polymerization reactions, due to the lower
energy of corona discharge, there are few reports on the use of corona discharge to initiate
polymerization reactions. We used corona discharge technology to successfully initiate the grafting of
high-hydrogen silicone oil to PET fabric, and the water repellency of the fabric was significantly
improved after grafting [4-6]. Due to the high content of chemically active tertiary hydrogen atoms, the
grafting reaction of high-hydrogen silicone oil is easy to proceed, but after the grafting reaction is
completed, a large number of tertiary hydrogen atoms still remain on the grafted product, the grafted
product is unstable and easy to occur during use Chemical changes such as oxidation reduce the water
repellency. This paper studies the use of corona discharge to initiate the grafting of PET fabric with low
hydrogen silicone oil in the presence of a compounding agent to improve the water repellency of PET
fabric. Due to the low content of tertiary hydrogen atoms in the grafting monomer, after the grafting
reaction is completed, the number of residual tertiary hydrogen atoms on the grafting unit is small, and
the product structure is stable. The low-hydrogen silicone oil grafted PET has long-term excellent water
repellency.

1 Experimental part

1.1 Raw material PET fabric: commercially available industrial products; low-hydrogen silicone oil: grade
TS-HB, produced by the Chengdu Silicone Center of the Ministry of Chemical Industry, with an H content
of 3.0 wt.%; dicumyl peroxide (DCP): Chemically pure; BP: sensitizer, chemically pure.

1.2 Preparation of grafting reaction solution Add 0.25%, 0.5%, 1.0% and 2.0% by weight of DCP and an
appropriate amount of sensitizer BP to 100 mL of hydrogen-containing silicone oil to prepare three types
of DCP. The content of the hydrogen-containing silicone oil bulk grafting reaction solution.

1.3 Preparation of grafted samples of PET fabricsWash the PET fabrics, dry them into strip samples, soak
them in the grafting reaction solution for 30 minutes, then take them out, squeeze to remove the excess
reaction solution, make the hydrogen-containing silicone oil in The adsorption capacity on the sample is
~ 20 wt %, and the GBDC-1 corona discharge processor produced by Dalian Radio No. 9 Factory is used
for corona discharge to initiate graft polymerization. Voltage: 10 000 V, hour

1.4 Test and characterization

1.4.1 Measurement of grafting rate The PET fabric after grafting is extracted with toluene to remove
unreacted monomers and monomers.

Polymer, dry, weigh until constant weight (Wt), calculate the grafting rate as follows: ε=(Wt-
W0)/W0×100% where Wt is the weight of the finished fabric and W0 is the weight of the unfinished
fabric .

1.4.2 The measurement of contact angle The contact angle between the surface of PET fabric and water
is measured by the Japanese SERIAL 20913 contact angle tester.

1.4.3 Determination of the penetration time of standing water droplets Spread the fabric sample flat on
absorbent paper, place the water droplets on the surface of the fabric sample, observe and record the
shape change of the water droplet and the time it takes to penetrate the sample.

1.4.4 The water impact test is measured according to the AATCC42-1977 standard.
1.4.5 The tensile performance test is based on the GB3923-83 standard, using the Instron 4302
electronic tensile machine to test, the tensile speed: 50 mm/min. 1.4.6 ESCA adopts Kratos XSAM 800
photoelectron spectrometer, radiation source: AlKα (hγ=1 486.6 eV), measure and record the C1s peak
and Si2p peak of the sample.

2 Results and discussion

2.1 The influencing factors of the grafting rate can be seen from Figure 1. With the extension of the
reaction time initiated by corona discharge, the grafting rate increases. The greater the content of DCP
in the grafting reaction solution, the greater the grafting rate at the initial stage of the reaction. At room
temperature, when the corona discharge grafting reaction is only 10 s, the grafting amount can reach
about 2.0%, which can meet the requirements of the water repellent finishing for the grafting amount.
According to the literature [7], in the traditional roll-bake-baking chemical water repellent finishing, the
same grafting amount needs to be baked at high temperature (~140 °C) for several minutes (~ 4 min) to
achieve. The reaction time of the grafting method in this paper is more than 20 times higher and the
temperature is more than 100 degrees higher. The decomposition temperature of DCP is 120 °C. At
room temperature, DCP cannot decompose to form free radicals to initiate the graft polymerization of
hydrogen-containing silicone oil. During the experiment, only samples immersed in the grafting reaction
solution, without corona discharge treatment, grafting rate Is 0 (Figure 1). The above analysis shows that
corona discharge plays a decisive role in the initiation of graft polymerization.

2.2 Contact angle with water

It can be seen from Figure 2 that the contact angle of the grafted PET fabric with water is greatly
increased, and the hydrophobic properties are improved. With the increase of the corona discharge
treatment time, the contact angle of the PET fabric with water appears to the maximum, and the
treatment time is further extended, and the contact angle decreases. This is because the hydrogen-
containing silicone oil monomer initiates the copolymerization to the surface of the PET fabric during the
corona discharge process, the hydrophobic performance is greatly improved, and the contact angle with
water increases. When the graft copolymerization reaction takes place for a certain period of time, the
monomer reaction is completed, further prolonging the corona Discharge time, the hydrogen-containing
silicone oil graft layer on the surface of PET fabric can be activated and oxidized by corona discharge
treatment, and the contact angle with water is reduced.

2.3 The results of the static water drop penetration experiment can be seen from Table 1.

After corona discharge treatment, the water penetration time of the PET fabric increases significantly,
and increases with the increase of the treatment time, which is similar to the grafting rate of hydrogen-
containing silicone oil shown in Figure 2. The results are consistent. The contact surface of the PET fabric
without graft modification and the water droplets continues to expand, and the water droplets
disappear The PET fabric is wet, leaving obvious traces of water. After the grafting treatment, the
contact surface of water droplets on the surface of the PET fabric will not expand. After the water
droplets disappear, the PET fabric will not be wet and there is no trace.

2.4 The water impact test results can be seen from Figure 3,

with the extension of the corona discharge graft polymerization time, the water impact permeability of
the grafted PET fabric is significantly lower than that of the ungrafted PET fabric; DCP in the grafting
reaction solution The higher the content, the lower the water impact permeability of the PET fabric
grafted by the same corona discharge time, that is, the higher the grafting rate of hydrogen-containing
silicone oil, the better the water repellency of the PET fabric. 2.5 Determination of tensile strength It can
be seen from Table 2 that the tensile strength of the PET fabric before and after grafting treatment does
not change much. After the treatment time is more than 5 minutes, the surface of the grafted sample is
very smooth. During the tensile test, the sample is easily pulled out of the grip of the tensile machine,
and the tensile test cannot be measured.
2.6 ESCA results

As shown in Figure 4, without corona discharge treatment, the surface of the PET fabric soaked in the
hydrogen-containing silicone oil grafting reaction solution did not undergo graft polymerization (the Si2p
content is 0). With the prolongation of the corona discharge treatment time, graft polymerization
occurred on the surface of the PET fabric, the area ratio of the Si2p peak to the C1s peak continued to
increase, and the amount of hydrogen-containing silicone oil grafted on the surface increased.

3 Conclusions

① In the presence of DCP and BP, corona discharge can efficiently cause hydrogen-containing silicone
oil to graft PET fabric. When the hydrogen-containing silicone oil bulk solution with a DCP content of
2.0% is used as the grafting reaction solution, when the corona discharge reaction is only 10 s at room
temperature and air atmosphere, the grafting rate of the PET fabric surface reaches 2.52%. ② The
grafting rate increases with the increase of the reaction time initiated by the corona discharge, and the
grafting rate at the initial stage of the grafting reaction increases significantly with the increase of the
DCP content in the reaction solution. ③After grafting, the contact angle of the PET fabric with water
increased significantly, the penetration time of water droplets at a standstill increased significantly, the
penetration rate of water impact decreased significantly, and the water repellency performance was
greatly improved. ④After the corona discharge initiates the grafting, the mechanical properties of the
PET fabric remain basically unchanged.
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