Fluorine-containing Polyacrylate Research Articles

Influence of Fluorine-Containing Monomer Content on the Hydrophobic and Transparent Properties of Nanohybrid Silica Polyacrylate Coating Materials.

Nanosilica-modified, fluorine-containing polyacrylate hybrid coating materials, consisting of dodecafluoroheptyl methacrylate (DFMA), methyl methacrylate (MMA), 2-ethyl hexyl acrylate (2-EHA), 3-(trimethoxysilyl) propyl methacrylate (KH-570), and tetraethylorthosilicate (TEOS), are synthesized successfully by free radical polymerization and the sol–gel process. It is revealed that the content of the fluorine-containing polyacrylate hybrid coating materials from DFMA monomers significantly improves the properties of the films. The polyacrylate coating film prepared with a weight ratio of DFMA/MMA at 1:5 exhibits the largest water contact angle of 105.4°, which demonstrates that DFMA can effectively improve the hydrophobicity of the coating film. Moreover, the silicon coupling agent (KH-570) is used to graft silica with acrylate. Spherical in shape, the surface morphology of the nanohybrid film exhibits a core–shell structure, which increases the surface roughness and enhances the hydrophobic properties. The as-prepared fluorine-containing nanohybrid silica polyacrylate film possesses a high transmittance of 89–97% in the visible light region, indicating its potential as a very attractive solution in many practical areas.

Preparation of an amphiphilic Janus SiO2/fluorinated polyacrylate latex film and its application as a hydrophobic fabric agent

Amphiphilic Janus particles are characterized by their anisotropic morphology and unique physical and chemical properties. In the present research, amphiphilic Janus particles were used as stabilizing agents to prepare a fluorine-containing polyacrylate composite emulsion. The influences of the structure and dosage of amphiphilic Janus SiO2 particles and the amount of fluorine-containing monomer hexafluorobutyl methacrylate on the stability of the composite emulsion were investigated. It was noticed that when the hydrophilic and hydrophobic groups of Janus SiO2 particles were polyacrylamide and polymethyl methacrylate, respectively, the stabilization of the polyacrylate emulsion with Janus SiO2 particles was achieved. When 0.3 wt% of polyacrylamide/polymethyl methacrylate amphiphilic Janus SiO2 particles and 8 wt% of hexafluorobutyl methacrylate were used, a stable composite emulsion was obtained. The conversion rate reached 98.7% with an average particle size of 500 nm. The composite emulsion was applied for fabric finishing. The water contact angle of the fabric increased from 21.4° to 140.2°, demonstrating its greatly improved hydrophobicity. Therefore, it could be inferred that the synergistic effect of amphiphilic Janus SiO2 nanoparticles and hexafluorobutyl methacrylate improved the water resistance of the latex film.

Synthesis of Ag/fluorine-containing polyacrylate latex stabilized by Ag nanoparticle hybrid amphiphilic random copolymer micelles via Pickering emulsion polymerization and its application on fabric finishing

Ag/fluorine-containing polyacrylate latex was successfully synthesized via Pickering emulsion polymerization using Ag/poly(2-dimethylaminoethyl methacrylate-co-hexafluorobutyl acrylate) (Ag/P(DMAEMA-co-HFBA)) hybrid micelles as particle emulsifiers. The influences of introducing the Ag nanoparticles (NPs) component and the concentration of Ag/P(DMAEMA-co-HFBA) hybrid micelles on emulsion polymerization and finished cotton fabric properties were studied. The results showed that the Ag/fluorine-containing polyacrylate latex had a higher conversion, smaller particle size than the fluorine-containing polyacrylate latex using P(DMAEMA-co-HFBA) micelles as emulsifiers, indicating the positive effect of Ag NPs on emulsion polymerization. And thermogravimetric analysis (TGA) proved that Ag NPs improved the thermal stability of the latex film. Moreover, the surface of the cotton fabric finished by Ag/fluorine-containing polyacrylate latex showed more rough morphology, better hydrophobicity and excellent antibacterial activity owing to the synergistic effect of the cationic fluorine-containing polyacrylate compounds and Ag nanoparticles. Meanwhile, the presence of Ag NPs also improved the tensile strength of the finished cotton fabric, but reduced slightly the whiteness. When the concentration of Ag/P(DMAEMA-co-HFBA) hybrid micelle emulsifier was 8 mg/mL, the Ag/fluorine-containing polyacrylate latex particles presented regular raspberry-shaped with an average diameter of 120 nm, and the water/oil contact angles of finished cotton fabric attained 145° and 90°, respectively. In addition, the finished cotton fabric exhibited excellent antibacterial properties against both S. aureus and E. coli as the concentration of Ag/P(DMAEMA-co-HFBA) hybrid micelles was 12 mg/mL. The mechanism for the formation of Ag/fluorine-containing polyacrylate latex was proposed.

Solution Blowing of Polyacrylonitrile Nanofiber Mats Containing Fluoropolymer for Protective Applications

A new type of hydrophobic polyacrylonitrile (PAN) nanofiber is fabricated by solution blowing of a blend solution of fluorine-containing polyacrylate (FPA) and PAN. The nanofibers’ surface composition, hydrophobicity, and protection ability were evaluated to clarify the effects of FPA addition. Results revealed that FPA addition increased the nanofiber diameter, as well as enhanced the hydrophobicity and transport properties of the nanofiber mats. The mats had average water contact angles of 123.44°, 132.11°, and 137.11° for FPA contents of 0.66 wt%, 1.98 wt%, and 3.30 wt%, respectively. All these results suggested the potential of the solution blowing nanofiber mats as protection materials.

Water sensitivity of fluorine-containing polyacrylate latex coatings: Effects of crosslinking and ambient drying conditions

In this study, fluorine-containing polyacrylate latexes comprising different levels of copolymerized perfluorethyl groups were prepared by the two-stage emulsion polymerization of 2,2,2-trifluoroethyl methacrylate, methyl methacrylate, butyl acrylate and methacrylic acid as main monomers, where the fluorine-containing monomer was copolymerized only into the second stage polymer. The effects of keto-hydrazide self-crosslinking and its combination with pre-coalescence and ionomeric crosslinking, respectively, on coating wettability, water absorption and water whitening were investigated. For the keto-hydrazide self-crosslinking, diacetone acrylamide was copolymerized into the second stage polymer to provide sites for the subsequent reaction with adipic acid dihydrazide. The pre-coalescence crosslinking of latex particles was introduced by copolymerizing allylmethacrylate during the synthesis and the ionomeric crosslinking was provided by the addition of a commercial zinc complexing agent. The influences of ambient conditions during the film-forming process in terms of temperature and relative humidity differences on coating wettability were evaluated. Further, changes of coating wettability as a function of water exposure duration were tested. The results showed that the highest level of hydrophobicity at the same amount of copolymerized 2,2,2-trifluoroethyl methacrylate could be achieved in the case of non-crosslinked latex films dried at elevated temperatures, whereas the highly crosslinked latexes combining pre-coalescence crosslinking and keto-hydrazide self-crosslinking provided the most water whitening-resistant coating films.

Synthesis and Characterization of Novel Fluorine-Containing Water-Based Antirust Coating

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which styrene(St) and butyl acrylate (BA) were used as main monomers and dodecafluoroheptyl methacrylate(DFMA) as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum (FT-IR), scanning electron microscopy (SEM), particle size analysis, differential scanning calorimetry (DSC). The FTIR results showed that DFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a narrow particle size distribution. From the results salt spray test presented, it seems when the content of DFMA was 5wt% anti-rust performance of emulsion is relatively better. DSC and TGA also showed that their film exhibited higher thermal stability than that of fluorine-free emulsion.

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

Nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion, consisting of methyl methacrylate, butyl acrylate, dodecafluoroheptyl methacrylate and ethyl silicate, was successfully synthesized by emulsion polymerization using surfmer and sol–gel process. When increasing ethyl silicate content, the latex 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. Furthermore, compared with fluorine-containing polyacrylate emulsifier-free emulsion, the obtained nano-SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion proved to be highly solvent-resistant and water-resistant. In addition, the transmission electron microscopy (TEM) indicated that the nano-SiO2 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 rough surface and the organic fluorine segment could migrate onto the film–air interface.

Synthesis and Properties of Nano-TiO<sub>2</sub> Modified Fluorine-Containing Polyacrylate Soap-Free Emulsion

Nano-TiO2Modified Fluorine-Containing Polyacrylate Soap-Free Emulsion was Successfully Synthesized via Soap-Free Emulsion Polymerization Technique, in which the Polymerization Monomers Consisted of Methyl Methacrylate (MMA), Butyl Acrylate (BA) and Dodecafluoroheptyl Methacrylate (DFMA). the Influence of Amount of Initiator, Emulsifier, Containing Fluorine Monomer and nano-TiO2on the Performance of Emulsion was Investigated. the Results Showed that the Good Polymerization Stability, and High Monomer Conversion were Obtained when the Amount of Ammonium Initiator was 1.2%, the Amount of Reactive Emulsifier was 3.5%. with Increasing Amount of DFMA, the Monomer Conversion Decreased and the Gel Rate Increased Gradually with the Increase of DFMA Amount. UV-Blocking Ability of the Cotton Fabric Treated with the Hybrid Emulsion Containing Nano-Tio2increased with Increasing Amount of Nano-TiO2. IR Spectrum Results Showed that Nano-TiO2and Fluorine-Containing Monomer were Successfully Introduced in the Segmental Structure of the Polymer. SEM Revealed that Nano-TiO2was Loaded on the Surface of the Treated Cotton Fabric which had Good Hydrophobicity.

Synthesis of self-crosslinking fluorinated polyacrylate soap-free latex and its waterproofing application on cotton fabrics

Fluorinated polyacrylate latexes are preferably candidates for the textile water repellent finishes as a result of their special surface property and especially economical, low-toxic characteristics compared to fluorinated polyacrylate solutions. The benefits of soap-free latex prepared from reactive surfactants are now well known. We herein used a reactive emulsifier, ammonium allyloxtmethylate nonylphenol ethoxylates sulfate (DNS-86), to prepare novel self-crosslinking fluorinecontaining polyacrylate soap-free latex (FMBN) with core-shell structure by co-polymerization of dodecafluoroheptyl methacrylate (DFMA), methyl methacrylate (MMA), butyl acrylate (BA), and N-methylolamide (NMA), and then treated the cotton fabric with FMBN. Results showed that the as-prepared latex particles had the uniform spherical core-shell structure with an average diameter of 116 nm. FMBN could form a smooth resin film on the treated fabric/fiber surface under Field emission scanning electron microscopy (FESEM) observation, but some protuberances appeared on that surface from Atomic force microscopy (AFM) image. X-ray photoelectron spectroscopy (XPS) analysis indicated the fluoroalkyl groups tended to enrich at the film-air interface. Hydrophobicity of the FMBN treated fabric was superior to that of the fabrics treated by general emulsion and the non-crosslinking one. In addition, the above three latexes didn’t influence whiteness of the treated fabrics at all. However, they all, and in especial two self-crosslinking latexes would make the treated fabrics stiffer compared to non-crosslinking one.

Synthesis of cationic core-shell fluorine-containing polyacrylate soap-free latex and its application on cotton substrate

Fluorinated polyacrylate latexes are preferably potential materials for use in the textile finishing due to their special surface property and especially economical, low-toxic characteristics compared to fluorinated polyacrylate solutions. A novel cationic fluorine-containing polyacrylate soap-free latex (CFMBD) with core-shell structure was accordingly developed by co-polymerizing dodecafluoroheptyl methacrylate (DFMA), methyl methacrylate (MMA), butyl acrylate (BA), and dimethylaminoethyl methacrylate (DM) using a cationic reactive emulsifier, maleic acid double ester-octadecyl poly(ethyleneoxy)20 ether-ethylene trimethyl ammonium chloride (R303). Then CFMBD was utilized to treat the cotton fabric. Results showed that the as-prepared latex had due structure and its particles had uniform spherical core-shell structure with an average diameter of 125 nm. The core-shell CFMBD latex film thus had two Tg and its thermal property was improved due to the introduction of DFMA. CFMBD could form a smooth resin film on the treated fabric/fiber surface under FESEM observation. XPS analysis indicated the fluoroalkyl groups had the tendency to enrich at the film-air interface. Hydrophobicity of the CFMBD treated fabric was slightly superior to that of the fabric treated by general emulsion but their oleophobicity was identical. Contact angles of water and diiodomethane on the CFMBD treated fabric surface could attain 133.5 ° and 105.5 °, respectively. However, washing durability of the treated fabric by CFMBD showed improvement compared to the general emulsion. In addition, CFMBD didn’t influence whiteness of the treated fabric but would make it slightly stiff at high doses.

Synthesis of fluorine-containing latexes with core–shell structure by UV-initiated microemulsion polymerization

A core–shell structure of fluorine-containing polyacrylate latex was synthesized by UV-initiated two-stage microemulsion polymerization from styrene (St) and hexafluorobutyl acrylate (HFA) in the presence of Irgacure 2959 as hydrophilic photoinitiator at room temperature. The first polymerization stage took 12 min and the second stage took 10 min. The conversions of the first and the second polymerization stages were about 60 and 85 %, respectively. Fourier transform infrared (FTIR) spectra, transmission electron microscopy (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and contact angle analysis were used to characterize the properties of latexes and their films. The DLS analysis results indicated that the size of the fluorine-containing nanoparticle is about 20 nm. The TEM photos showed that the particles have core–shell structure and some of the cores are located in the center and the others deviate from the center of particles. From the FTIR and XPS results, we can infer that the fluorine monomer could be introduced into the copolymer and the fluorine-containing polyacrylate mainly occupies the shell part. The TGA results indicated that the fluorine-containing polyacrylate copolymers exhibited higher thermal stability than that of the fluorine-free one. The contact angle analysis results showed that fluorine monomers make the film surface more hydrophobic.

Synthesis and surface properties of semi-interpenetrating fluorine-containing polyacrylate and epoxy resin networks

Semi-interpenetrating polymer networks (Semi-IPNs) based on fluorine-containing polyacrylate and epoxy resin were synthesized by the simultaneous polymerization of fluorine-containing acrylate and epoxy resin. Fourier transform infrared (FTIR) spectrometry and X-ray photoelectron spectroscopy (XPS) analyses proved that the fluorine-containing groups have been introduced into Semi-IPNs successfully. In addition, XPS analysis intuitively showed that the fluorine content of the film-air interface of the interpenetrating fluorine-containing polyacrylate and epoxy resin networks (FPAER-SIPNs) film was much higher than that of the film-glass interface. It is noted that the introduction of fluorine-containing groups significantly improved the hydrophobic property of polymer networks. Moreover, when the fluorine content increased, the contact angle of water on FPAER-SIPNs film was increased obviously and the water uptake was decreased gradually. These results indicated that introducing fluorine-containing groups to SIPNs has potential advantage for improving the surface properties of epoxy resin.

Preparation of Fluorine-Containing Polyacrylate Emulsion by a UV-initiated Polymerization

A fluorine-containing polyacrylate emulsion was synthesized by a UV-initiated emulsion polymerization from methyl methacrylate (MMA) and hexafluorobutly methacrylate (HFMA) in the presence of 2-hydroxy-4-(2-hydroxyethoxy)-2-methyl-propiophenone (Irgacure 2959) as a hydrophilic photoinitiator at room temperature. The latex and films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (1H-NMR, 19F-NMR) spectrometry, transmission electron microscopy (TEM), recycling gel permeation chromatography (GPC), dynamic light scattering (DLS), and contact angle (CA) analysis, respectively. The effects of photoinitiator and emulsifier concentration on the polymerization were discussed. Compared to the corresponding thermal polymerization, UV-initiated polymerization of the MMA/HFMA emulsion could be accomplished at a much higher speed. The polymerization conversion in UV-initiated polymerization reached 95% within 10 min at an emulsifier concentration of 0.6 wt%, photoinitiator concentration of 0.4 wt%, and monomer concentration of 10 wt%.

Synthesis and Characterization of Fluorine-containing Polyacrylate Emulsion with Core-Shell Structure

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate (MMA) and butyl acrylate (BA) were used as main monomers and hexafluorobutyl methacrylate (HFMA) as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum (FT-IR), transmission electron microscopy (TEM), particle size analysis, X-ray photoelectron spectroscopy (XPS), contact angle (CA), differential scanning calorimetry (DSC) and thermogravimetry (TG) analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.

Synthesis and characterization of emulsifier-free core–shell fluorine-containing polyacrylate latex

Core–shell fluorine-containing polyacrylate latex particles with fluorine-containing polymer rich in shell were successfully prepared by emulsifier-free seeded emulsion polymerization of fluorine-containing acrylate and fluorine-free acrylate monomers in water with PMMA particles as seeds. The chemical composition and core–shell structure were investigated by Fourier transform infrared (FTIR) spectrometry and transmission electron microscopy (TEM), respectively. TEM, scanning electron microscopy (SEM) and dynamic light scattering (DLS) analysis indicated that the core–shell particles were uniform and possessed narrow size distributions. X-ray photoelectron spectroscopy (XPS) analysis revealed that a gradient concentration of fluorine excited in the structure of the core–shell fluorine-containing latex film from the film–air interface to the film–glass interface. In addition, compared with the latex film of core–shell fluorine-free polyacrylate prepared under the similar polymerization condition, the core–shell fluorine-containing latex film showed higher contact angle and thermal stability.

Synthesis and characterization of core-shell LIPN-fluorine-containing polyacrylate latex

Interpenetrating polymer network (IPN) fluorine-containing polyacrylate latex with core-shell structure has been prepared by semi-continuous emulsion polymerization of fluorine-containing acrylate and acrylate monomers in an aqueous medium composed of mixed emulsifiers. The chemical composition and core/shell structure are characterized by Fourier-transform infrared (FTIR) spectrometry and transmission electron microscopy (TEM). The cross-linking structure has been indicated by the improved ability of organic reagent endurance and thermal stability comparing with uncrossing core/shell structure. Meanwhile, the surface analysis of the latex film from X-ray photoelectron spectroscopy (XPS) reveals that a gradient concentration of fluorine exists in the structure of the latex film from the film–air interface to the film–glass interface.