Synthesis and Characterization of nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion

Accepted Manuscript Title: Synthesis and Characterization of Nano-SiO2 Modified Fluorine-containing Polyacrylate Emulsifier-free Emulsion Author: Jianhua Zhou Xin Chen Hao Duan JianZhong Ma Yurong Ma PII: DOI: Reference:

S0169-4332(15)00123-3 http://dx.doi.org/doi:10.1016/j.apsusc.2015.01.098 APSUSC 29535

To appear in:

APSUSC

Received date: Accepted date:

6-12-2014 14-1-2015

Please cite this article as: J. Zhou, X. Chen, H. Duan, J.Z. Ma, Y. Ma, Synthesis and Characterization of Nano-SiO2 Modified Fluorine-containing Polyacrylate Emulsifier-free Emulsion, Applied Surface Science (2015), http://dx.doi.org/10.1016/j.apsusc.2015.01.098 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Graphical Abstract (for review)

Nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion was synthesized by emulsifier-free emulsion polymerization and sol-gel process using

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ed

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ethyl silicate as precursor for nano-SiO2.

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Synthesis and Characterization of Nano-SiO2 Modified Fluorine-containing Polyacrylate Emulsifier-free Emulsion

a

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Jianhua Zhou a,b∗, Xin Chena, Hao Duana, JianZhong Maa, Yurong Ma a, College of Resource and Environment, Shaanxi University of Science and

b

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Technology, Xi’an 710021, China

Shaanxi Research Institute of Agricultural Products Processing Technology, Xi’an

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710021, China. Corresponding Author

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*Corresponding author. Tel.: +86-029-86132559-609; Fax: +86-029-86132559-603.

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E-mail address: [email protected](J. H. Zhou)

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ABSTRACT Nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion,

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consisting of methyl methacrylate, butyl acrylate, dodecafluoroheptyl methacrylate and ethyl silicate, was successfully synthesized by emulsion polymerization using

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surfmer and sol-gel process. When increasing ethyl silicate content, the latex

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centrifugal stability decreased, and the latex particle size increased. The contact angle results showed that the finished fabric had an excellent water and oil repellency. compared

with

fluorine-containing

polyacrylate

emulsifier-free

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Furthermore,

emulsion, the obtained nano-SiO2 modified fluorine-containing polyacrylate

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emulsifier-free emulsion proved to be highly solvent-resistant and water-resistant. In addition, the transmission electron microscopy(TEM) indicated that the nano-SiO2

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presented on the surface of latex particles. The atomic force microscope(AFM) and energy dispersive X-ray spectrometer(EDX) confirmed that the hybrid film had a

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rough surface and the organic fluorine segment could migrate onto the film-air interface.

Key words: nano-silica; organic fluorine; polyacrylate soap-free emulsion;

water

and oil proof agent

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INTRODUCTION Polyacrylate has many excellent properties such as good film-forming, gloss,

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transparency, adhesion, and mechanical properties etc. It has been widely used in many fields of leather[1], paper making[2], textile industry[3-4] and coating industry[5-7]

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etc. However, some drawbacks such as poor water resistance, poor solvent resistance,

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poor stain resistance, limit its application. Fluorinated polymers, with many attractive properties including low surface energy, high resistance to thermal, chemical and

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weather attack, render high thermal, chemical resistance, and oil and water repellency to fluorine-containing polyacrylate [8-13]. Due to the small size effect, surface effect,

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volume effect and macroscopic quantum tunneling effect of nano-silica, nano-silica in

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polyacrylate can improve the strength, abrasion resistance, age resistance, solvent

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resistance and weather resistance of polyacrylate[14].

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In recent years, to meet the requirements of environment and resource protection, emulsion polymerization has been widely studied as it is of no pollution, fast polymerization, and higher molecular weights. However, the residual emulsifier in conventional fluorine-containing polyacrylate emulsion could easily migrate to the film surface during the film formation process, resulting in the deleterious effects on the films properties[15], On the other hand, it can induce the environmental pollution. To avoid the drawbacks resulted from emulsifier, the emulsifier-free emulsion polymerization[16-25] is applied as it endows latexes with the following advantages: no emulsifier migration during film formation, excellent shear stability and monodisperse particle size distribution[26-29]. Therefore, emulsifier-free emulsion polymerization is a

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very promising method in preparing environmentally friendly nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion with excellent properties.

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In the present study, the nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion was synthesized by the combination of emulsifier-free

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emulsion polymerization with sol-gel process with ethyl silicate (TEOS) as precursor

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for nano-SiO2. The influences of amount of ethyl silicate (TEOS) and dodecafluoroheptyl methacrylate (DFMA) on the properties of the copolymer were

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analyzed. The structure and properties of hybrid emulsion were assessed by atomic

and solvent resistance tests, ect. 2. EXPERIMENTAL SECTION

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2.1. Materials

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force microscope(AFM), energy dispersive X-ray spectrometer(EDX) analysis, water

Methyl methacrylate (MMA), butyl acrylate (BA), ammonium persulfate (APS),

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ethyl silicate (TEOS) were purchased from Tianjin Kemiou Chemical Co. Ltd, antlytically pure and used as received. γ -methacryloxypropyltrimethoxysilane (KH-570) was purchased from Nanjing Shuguang Chemical Company, and used as received. Alkyl vinyl sulfonate (AVS) was produced by Hanerche Chemical Company, and used as received. Dodecafluoroheptyl methacrylate (DFMA) was obtained from Harbin Xuejia Fluorin Silicon Chemical Co., Ltd. Stearyl acrylate(SA) was purchased from Tianjin Tianjiao Chemical Co., Ltd. and used as received. 2.2

Synthesis

of

nano-SiO2

modified

fluorine-containing

polyacrylate

emulsifier-free emulsion

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The

recipes

for

nano-SiO2

modified

fluorine-containing

polyacrylate

emulsifier-free emulsion were described in Table1. For a typical experiment, 12.32g

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of BA, 3.28g of MMA, 0.38g of AVS, and 15g of deionized water were mixed in the beaker and stirred vigorously to form the pre-emulsion I. 5.28g of BA, 3.96g of MMA,

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4g of DFMA, 1g of SA, 0.38g of AVS, and 15g of deionized water were mixed in the

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beaker and then intensively homogenized to form the pre-emulsionⅡ.

A 250-mL three-neck round-bottomed flask equipped with a reflux condenser, a

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thermometer and a mechanical stirrer was filled with 0.38g of AVS, 1/3 APS aqueous solution(0.44g of APS was solved in 30g water), and 1/4 pre-emulsionⅠ and 15mL

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of deionized water with a stirring rate of 250rpm at 70℃ and kept still for 20min. Then, both the 1/3 APS aqueous solution and remnant pre-emulsionⅠwere added

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dropwise into the reacting mixture for 90min. After that, the reaction was carried out continuously for another 2h.

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Then, the polymerization continued with slow addition of the pre-emulsionⅡ and

remnant APS aqueous solution during 120min. 2.8g of KH-570 was added to the flask. The reaction mixture was kept at 80~85℃ for 2h, then cooled down to 50℃. Then 1.6g of TEOS was added to emulsion under magnetic, and contents of the flask were stirred at 50℃ for 12h.

2.3 Preparation of the latex film The hybrid emulsion was cast onto a pyrex glass plate and became film at room temperature. Then the film was dried at 80℃ for 3h to remove water from inside the film. At last, the film was annealed at 120℃ for 30min.

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2.4 Fabric treatment The cotton fabrics were padded with two dips and nips (70-80% wet pick up) in a

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solution containing nano-SiO2 modified fluorine-containing polyacrylate soap-free emulsion of 70g/L. After treatment, the cotton fabrics were dried at 80℃ for 3min

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and cured at 160℃ for 3min.

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2.5 Characterizations

Centrifugal ratio: sample emulsion was first filtered with filter screen (mesh

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number: 200) and put into TG 16-WS desktop centrifuge(3000r/min) for 30min. The precipitation was dried and weighted. Centrifugal ratio was calculated as the formula:

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wc=mc/ms, in which mc was the quantity of precipitation solid and ms was the quantity of sample. The particle size of the synthesized emulsion was measured with Malvern

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Nano-ZS instrument (Malvern Instruments, UK) at a fixed acattering angle of 90°at room temperature. Transmission electron microscopy (TEM) micrographs of the

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nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion

particles was performed on a Hitachi H-600 electron microscope (Hitachi Ltd., Tokyo, Japan) at a voltage of 75 kV. The sample was stained with 1 % phosphotungstic acid solution. The solvent resistance of the film was determined as follows. The film specimen (weight=W0, dimensions=20 mm×20 mm) was immersed in toluene for 24

h at room temperature to attain swelling and dissolution equilibrium. The remaining film specimen was removed from the solvent, and the weight of the film (W1) was measured. The film was dried to a constant weight (W2) at room temperature. The gel content (wt %) was calculated from W2/W0×100, the swelling ratio was calculated

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from W1/W2. The film specimen (weight=Wa, dimensions=20 mm×20 mm) was immersed in water for 24h at room temperature. The remaining water of film

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specimen was removed from the surface, and the weight of the film (Wb) was measured. The water absorption ratio was calculated from (Wb- Wa)/Ws × 100. angles(CA)

measurements

were

performed

on

a

contact

angle

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Contact

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goniometer(OCA 20, Dataphysics Company, Germany) by the sessile drop method with a microsyringe at room temperature. Static contact angles were obtained from

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the injection volume of 5µL water or diiodomethane droplets on the surface of finished fabric. The average of nine readings of contact angle at different locations of

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one sample was used as the final value of each sample. The surface energy between finished fabric and an ordinary liquid was as follows:

)γ

liquid

d

liquid

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(1 + cosθ

p d  γ liquid γd γ liquid γp    =4 d + p p  d γ γ γ γ + + liquid liquid  

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d p in which γ=γd+γp, γliquid= γ liquid + γ liquid , γ was surface tension, γd was dispersion

component and γp was polar component, θliquid was contact angle of the finished fabric

with water or diiodomethane. The numberical values used were γ Hd 2O =21.8mJ/m2,

γ Hp O 2

=51.0mJ/m2,

d γ CH I

2 2

=49.5mJ/m2,

p γ CH I

2 2

=1.3mJ/m2.

Atomic

force

microscope(AFM) was performed using a SPA-400 AFM(Seiko Instruments Inc. Japan). Images were acquired under ambient conditions in tapping mode using a nanoprobe cantilever. For AFM measurements, the corresponding nano-SiO2 modified

fluorine-containing polyacrylate emulsifier-free emulsion(1wt% solid content) were cast onto the prepared silicon wafers and then dried at room temperature. The energy

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elemental analysis of the hybrid films was carried out by a Field emission scanning electron microacopy(FE-SEM) equipped with an energy dispersive X-ray(EDX)

3. RESULTS AND DISSCUSSION Synthesis

of

nano-SiO2

modified

fluorine-containing

polyacrylate

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3.1

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spectrometer(Hitachi JEOL-JSM-6700F system, Japan).

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emulsifier-free emulsion

Nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion was

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synthesized by emulsion polymerization using surfmer and sol-gel process, as shown in Scheme 1. Nano-SiO2 as an inorganic nanomaterials was introduced into

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fluorine-containing polyacrylate emulsifier-free emulsion system, and it often formed precipitate because agglomeration affected the stability of emulsion system. In this

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work, nano-SiO2 was formed by the hydrolysis of ethyl silicate (TEOS). A silane coupling agent containing double bond, KH-570 was expected to increase the

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miscibility of the fluorine-containing polyacrylate and the silica component, improving the stability of the hybrid emulsion. The study demonstrates that the emulsion appearance, acid-alkali stability and

caicium ion stability have been improved. However, the centrifugal stability was slightly affected by the dosage of TEOS. Fig.1 shows the influence of dosage of TEOS on centrifugal stability of latex. As shown in Fig.1, the rate of centrifugal sedimetation increases with the increase of TEOS content. Silane coupling agent KH-570 enhances the compatibility of organic and inorganic phases. It contains silyloxymethyl and unsaturated double bond,

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thus the silyloxymethyl can combine with the silanol groups on the nano-SiO2, and the double bond can copolymerize with acrylate monomers. Consequently, nano-SiO2

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and fluorine-containing polyacrylate become covalently bound to increase the miscibility of both the components and prevent the agglomeration of silica particles

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due to phase separation. TEOS can form the nano-SiO2 by the hydrolysis, the free

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nano-SiO2 content increases with the increasing of TEOS amount, however, the excessive nano-SiO2 will result in agglomeration under the centrifugation, and the

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hybrid emulsion stability has a decline trend. 3.2 Micromorphology of the latex particles

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Fig.2 displays the TEM images of the latex particles(P4 in Table1) . It is apparent

d

that the latex particles are well-shaped as regular sphere of which the diameter is

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approximately 90nm with a narrow size distribution. Xue et al[30] demonstrated that

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the silica shell can be characterized by the non-stained TEM. Cui et al[31] reported that the fluorinated polyacrylate latex particles were uniform spheres by the 2% phosphotungstic acid solution stain. In the present experiment, the sample in Fig.2a was stained with 1% phosphotungstic acid solution, and the sample in Fig. 2b wasn’t stained. In the synthesis of hybrid emulsion( see experimental section 2.2), TEOS was added to the reaction system at the last step. According to the TEM images(Fig. 2) and TEOS feeding method, it can be confirmed that the nano-SiO2 particles present on the outer layer of latex particles. 3.3 Particle size of latex particles

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Effect of the TEOS amount on the average particle size is shown in Fig.3. Obviously, the average particle size of hybrid emulsion is bigger than that of

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fluorine-containing polyacrylate emulsifier-free emulsion. Moreover, the average particle size of hybrid emulsion increases from 114.6nm to 126.7nm when the TEOS

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amount increases from 2% to 8%. This results from the fact that the silica sol is

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formed by the hydrolysis and polycondensation of TEOS on the surface of latex particles, which is consistent with the result of the TEM. Compared with the average

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particle size of latex particles prepared with the DLS and TEM, the average particle size of latex particles prepared by DLS is a little larger, owing to the fact that the

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hydrodynamic diameter is measured by the particle size analyzer based on the dynamic light scattering. Consequently, the average particle diameters of emulsion

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d

particles increase along with the increase of TEOS content. 3.4 Water resistance and solvent resistance of hybrid film

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Nano-SiO2 formed by the TEOS hydrolysis can function as a crosslinking point to

enhance the crosslinking degree of hybrid film. Thus, the resulted hybrid films will have good solvent-resistant, water-resistant and mechanical properties. The water resistance of the film was characterized by water absorption rate

measurement, as shown in Fig.4. Obviously, the water absorption rate of the films decreases with the increasing TEOS. It is so because the water resistance is resulted from the three-dimensional crosslinking network of hybrid film containing the silica component as a crosslinking point. As the nano-silica particles are distributed in the polyacrylate component evenly, the crosslinking densities of the hybrid films increase

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along with the increase of nano-silica content, which is considered to strengthen the resistance of hybrid film to water.

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Solvent resistance has been known as one of the relevant properties when nano-sized silica particles are applied as the filler for polymers[1]. The solvent

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resistance of the film was characterized by solvent extraction and swelling

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measurements[32], as demonstrated in Fig.5. It’s obvious that the hybrid film obtained from the hybrid emulsion has higher gel contents and smaller swelling ratios than that

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of the film obtained from the fluorine-containing polyacrylate emulsion. Meanwhile, the gel content increases from 73.4% to 95.9%, and the swelling rate decreases from

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7.34% to 2.15% with the increment of the amount of TEOS from 0% to 8%. This

d

indicates that the hybrid film has a good solvent resistance. Moreover, the solvent

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resistance of hybrid film increases when increasing dosage of TEOS. It can be

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attributed to the crosslinking densities of the hybrid films increase along with the increase of TEOS doasge, which is considered to increase the resistance of hybrid film to organic solvent.

3.5 Water and oil repellency of hybrid emulsion

Nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion is

used as a fabric finishing agent. In the finishing process, the composite latex can form the film on the fabric surface. In the curing process, the fluorinated groups have storng tendency to migrate and accumulate on the surface of finished fabric to decrease the surface energy of fabric, rendering excellent water and oil repellency to

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the finished fabric. In the present study, we evaluated the effect of fluorine-containing monomer

content

on

water

and

oil

repellency

Nano-SiO2

modified

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fluorine-containing polyacrylate emulsifier-free emulsion. The water contact angle is commonly used as a criterion for the evaluation of

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hydrophobic of a solid surface[33]. It is well-known that the chemical composition and

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surface roughness of the films can affect the contact angles[33–34]. The influence of different DFMA content on water/oil (diiodomethane) contact angle of finished fabric

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was investigated by varying the amount of flourinated monomer ranging from 5% to 25%, as shown in Fig.6. It can be observed from Fig.6 that the water/oil contact

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angles of the finished fabric increase along with the increase of DFMA content. On

d

the contrary, in Fig.7 the surface energy declines with the increase of DFMA dosage.

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The increase in the water and oil contact angle of the finished fabrics, and the

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reduction of the surface energy of latex film with increasing the amount of DFMA, may be ascribed to the extremely low surface energy and high hydrophobicity of the fluorinated groups, which can accumulate on the surface of finished fabrics during the latex film formation.

3.6 Microstructure morphology of composite film

Fig. 8 AFM images of sample films prapared from polyacrylate soap-free emulsion(a, b), fluorine-containing polyacrylate soap-free emulsion(c, d) and nano-SiO2 modified fluorine-containing polyacrylate soap-free emulsion(e, f). Atomic force microscopy （ AFM ） was used to examine the microstructure

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morphologies of polyacrylate film, fluorine-containing polyacrylate film, and nano-SiO2 modified fluorine-containing polyacrylate film, as shown in Fig.8.

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Simulation experiment study of hybrid emulsion on the monocrystalline silicon wafer. The monocrystalline silicon wafer surface is very smooth and it is an inorganic silicon

cr

material. The monocrystalline silicon wafer can generate a lot of silanol group by the

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concentrated sulfuric acid treatment, rendering the similar struature with the cotton fiber. Comparing the difference of surface morphology between polyacrylate film(see

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panel a and b) (P0 in Table1) and fluorine-containing polyacrylate film(see panel c and d)(P1 in Table1), samples (a) and (c), the surface of the latter is much rougher

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than that of the former. The surface roughness of polyacrylate film and fluorine-containing polyacrylate film was 0.060nm and 1.201nm, respectively,

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d

indicating that the organic fluorine have migrated toward the surface and resulted in aggregation. This phenomenon can be explained by the fact that the organic fluorine

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segment migrates toward the film surface during the heat treatment[35], and phase

separation between fluorinated and nonfluorinated components occurs for fluorine-containing polyacrylate film, improving the roughness of the latex film[36]. The surface roughness of nano-SiO2 modified fluorine-containing polyacrylate film(P3 in Table 1) was 1.442nm，indicating that nano-SiO2 further improves the

roughness of latex film. As a fabric finishing agent, the low surface energy and rough surface of composite film endow the finished fabric with an excellent water and oil repellency. 3.7 EDX analysis of composite film

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The surface property of materials is associated compactly with surface chemical composition, so energy dispersive X-ray spectrometer(EDX) was used in this work to

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analyze surface element of nano-SiO2 modified fluorine-containing polyacrylate film(P2 in Table 1) and results are presented in Fig.9 and Table 2. It can be found that

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the fluorine element content of nano-SiO2 modified fluorine-containing polyacrylate

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film is 6.68%, 8.68% and 10.66% in the film-glass interface, film section and film-air interface, respectively. It can be attributed to tendency of organic fluorine segment to

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migrate onto the film-air interface and occupy it during the formation of the latex film, which can effectively derease the surface free energy of the latex film. Therefore, the

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4. CONCLUSIONS

d

interface, consistent with Fig.8.

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EDX results indicate a remarkable enrichment of the fluorine atoms on the film-air

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Nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion was successfully synthesized with emulsifier-free emulsion polymerization and the sol-gel process. The latex centrifugal stability decreased with the increase of ethyl silicate content. The DLS analysis confirmed that the latex particle size increased with the increase of TEOS content. The solvent extraction and swelling measurements indicated that the obtained hybrid latex film exhibited better solvent resistance than pure fluorine-containing polyacrylate emulsifier-free emulsion film. In addition, the water and oil contact angle of the finished fabrics increased along with the increase of DFMA. Furthermore, the TEM indicated that the nano-SiO2 presented on the surface of latex particles, and the AFM results proved that the hybrid film had a rough

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structure. At last, the EDX and CA analysis revealed that the fluorine atoms had a tendency to migrate to the film surface during film formation, leading to low surface

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te

d

M

an

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cr

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energy, and high water and oil repellency of the hybrid film.

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Acknowledgments

This work was supported by the Start-up Foundation of Scientific Research of

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Shaanxi University of Science and Technology (NO. BJ11-16), the National Natural Science Fund of China (NO. 21206088), Postdoctoral Science Foundation

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of Shaanxi Province, the Academic Backbone Cultivation Program of Shaanxi

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University of Science and Technology(NO. XSGP201205), Key Scientific Research Group of Shaanxi province (No: 2013KCT-08), and Scientific Research

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M

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Group of Shaanxi University of Science and Technology(NO. TD12-03).

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24. G.L. Xu, L.L. Deng, X.F. Wen, P.H. Pi, D.F. Zheng, J. Cheng, Z.R. Yang, Synthesis and characterization of fluorine-containing poly-styrene-acrylate latex

Ac ce p

with core–shell structure using a reactive surfactant, Journal of coatings technology and research 8.3 (2011) 401-407.

25. X.Y. Xiao, Y. Wang, Emulsion copolymerization of fluorinated acrylate in the presence of a polymerizable emulsifier, Colloids and Surfaces A: Physicochemical and Engineering Aspects 348.1 (2009) 151-156.

26. M. Save, M. Manguian, C. Chassenieux, B. Charleux, Synthesis by RAFT of amphiphilic block and comblike cationic copolymers and their use in emulsion polymerization for the electrosteric stabilization of latexes, Macromolecules 38.2(2005) 280-289.

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27. J. Rieger, F. Stoffelbach, C. Bui, D. Alaimo, C. Jérôme, B. Charleux, Amphiphilic poly (ethylene oxide) macromolecular RAFT agent as a stabilizer and control

ip t

agent in ab initio batch emulsion polymerization, Macromolecules 41.12(2008) 4065-4068.

cr

28. D. E. Ganeva, E. Sprong, H. de Bruyn, G. G.Warr, C.H. Such, B. S. Hawkett,

us

Particle formation in ab initio RAFT mediated emulsion polymerization systems, Macromolecules 40.17(2007) 6181-6189.

an

29. S. Garnier, A. Laschewsky, New amphiphilic diblock copolymers: surfactant properties and solubilization in their micelles, Langmuir 22.9(2006) 4044-4053.

M

30. C. H. Xue, Z. D. Zhang, J. Zhang, S. T. Jia, Lasting and self-healing superhydrophobic surfaces by coating of polystyrene/SiO2 nanoparticles and

te

d

polydimethylsiloxane, Journal of Materials Chemistry A 2.36 (2014)15001-15007. 31. X. J. Cui, S. L. Zhang, G. Yan, H. Y. Wang, Preparation and characterization of core–shell

Ac ce p

emulsifier-free

interpenetrating

polymer

network-fluorinated

polyacrylate latex particles, Colloids and Surfaces A: Physicochemical and Engineering Aspects 324.1 (2008) 14-21.

32. Tamai, Toshiyuki, and Mitsuru Watanabe, Acrylic polymer/silica hybrids prepared by emulsifier free emulsion polymerization and the sol–gel process, Journal of Polymer Science Part A: Polymer Chemistry 44.1 (2006) 273-280. 33. J. W. Ha, I. J. Park, S. B. Lee, Hydrophobicity and sliding behavior of liquid droplets on the fluorinated latex films, Macromolecules383(2006) 736-744. 34. R. R. Thomas, K. G. Lloyd, K. M. Stika, L. E. Stephans, G. S. Magallanes, V. L.

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Dimonie, acrylic

M. S. El-Aasser, Low free energy surfaces using blends of fluorinated copolymer

and

hydrocarbon

acrylic

copolymer

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latexes, Macromolecules 33.23(2000) 8828-8841. 35. W. Xu, Q.F. An, L.F. Hao, D. Zhang, M. Zhang, Synthesis and characterization of

us

structure, Applied Surface Science 268 (2013) 373-380.

cr

self-crosslinking fluorinated polyacrylate soap-free latices with core-shell

36. X.Y. Xiao, J.F. Liu, Synthesis and characterization of fluorine-containing

Ac ce p

te

d

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Engineering 16.4 (2008) 626-630.

an

polyacrylate emulsion with core-shell structure, Chinese Journal of Chemical

Scheme. 1 Schematic illustration of synthetical mechanism for the hybrid emulsion.

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Table. 1 Recipes for nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion P0

P1

P2

P3

P4

P5

F1

F2

F3

F4

MMA/g

7.24

7.24

7.24

7.24

7.24

7.24

7.24

7.24

7.24

7.24

BA/g

17.60

17.60

17.60

17.60

17.60

17.60

17.60

17.60

17.60

17.60

APS/g

0.44

0.44

0.44

0.44

0.44

0.44

0.44

0.44

0.44

0.44

AVS/g

1.14

1.14

1.14

1.14

1.14

1.14

1.14

1.14

1.14

1.14

KH-570/g

2.80

2.80

2.80

2.80

2.80

2.80

2.80

2.80

2.80

2.80

SA/g

1.00

1.00

1.00

1.00

1.00

1.00

1.00

1.00

1.00

TEOS/g

0.00

0.00

0.80

1.60

2.40

3.20

1.60

1.60

1.60

1.60

DFMA/g

0.00

4.00

4.00

4.00

4.00

DI water/g

75.00

75.00

75.00

75.00

75.00

1.00

4.00

2.00

6.00

8.00

10.00

75.00

75.00

75.00

75.00

75.00

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cr

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Sample

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Table. 2 Element content of the hybrid film C(wt%) O(wt%) F(wt%) Si(wt%)

Sample

21.78

6.68

1.48

film section

58.11

30.88

8.68

2.32

67.53

18.16

10.66

3.66

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te

film-glass interface 70.06

film-air interface

Page 24 of 30

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Ac ce p

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d

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Fig. 1 Effect of dosage of TEOS on centrifugal stability of latex.

Fig. 2 TEM images of the latex particles stained with (a) and without (b) 1% phosphotungstic acid solution.

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Ac ce p

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d

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Fig. 3 Effect of dosage of TEOS on latex particle size.

Fig. 4 Effect of dosage of TEOS on water absorption of the hybrid film.

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Ac ce p

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d

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Fig. 5 Effect of of dosage of TEOS on solvent resistance of the hybrid film.

Fig. 6 Effect of of dosage of DFMA on water and oil repellency of finished fabrics.

Page 27 of 30

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Ac ce p

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Fig. 7 Effect of of dosage of DFMA on surface energy of finished fabrics.

Page 28 of 30

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Fig. 8 AFM images of sample films prapared from polyacrylate soap-free emulsion(a,

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b), fluorine-containing polyacrylate soap-free emulsion(c, d) and nano-SiO2 modified

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fluorine-containing polyacrylate soap-free emulsion(e, f).

Page 29 of 30

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Fig. 9 EDX spectra of film-glass interface(a), film section(b) and film-glass interface(c) of

Ac ce p

te

d

M

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nano-SiO2 modified fluorine-containing polyacrylate film.

Page 30 of 30