Fluorinated Acrylate Copolymer Research Articles

Preparation, characterization, and application of fluorinated acrylate copolymer for the conservation of stone building heritages in Putuo Zongcheng Temple, China

Abstract To prevent the weathering deterioration of stone building heritages in Putuo Zongcheng Temple, the fluorinated acrylate copolymer was prepared with methyl methacrylate, n-butyl acrylate, and 2,2,3,4,4,4-hexafluorobutyl methacrylate as monomers. The structure and surface morphology of the copolymer were described by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). The antiaging of the copolymer was studied by the ultraviolet aging test; the contact angle and imbibition spontaneous tests were performed to estimate the wettability alteration of the copolymer emulsion. Results show that the fluorinated copolymer with 32.54 % HFMA content possesses optimal aging resistance and superb hydrophobicity. The contact angles of coated samples range from 96.90° to 125.80°. Considering the influence of water on rock weathering, the fluorinated copolymer coating is a potential method to avoid the degrading of stone heritages.

Synthesis and properties of fluorinated acrylate copolymers prepared by emulsion polymerization

In this study, fluorinated acrylic emulsion (FAE) was prepared by emulsion polymerization using a reactive emulsifier as the surfactant and ammonium persulfate (APS) as the initiator. The structure of the FAE was characterized by Fourier transform infrared spectroscopy (FT-IR). The properties of FAEs were characterized by X-ray photoelectron spectroscopy (XPS), contact angle, and thermogravimetric analysis (TGA). In XPS spectra, a fluorine-containing group was identified on the film and thermal stability and contact angle of the acrylic emulsion of fluorine-containing group were increased.

Surface modification of sodium bicarbonate ultrafine powder extinguishing agent by environmental friendly fluorinated acrylate copolymers

Common ultrafine powder fire extinguishing agent couldn't put out the oil fire. To solve this problem, a simple and controllable way for preparing hydrophobic and oleophobic fire extinguishing agent was developed. Firstly, fluorinated acrylate copolymers (FP) with different fluorine contents were prepared and used to modify the extinguishing agent. Unlike perfluorooctane sulphonate/ perfluorooctanoic acids (PFOS/PFOA) with C8-fluorocarbon chains widely used as modifiers, the prepared FP with C6-fluorocarbon chains not only met the environmental standards, but also possessed excellent properties. Subsequently, the fluorine contents of particles modified by two FP were 19.3% and 37.4% respectively. The contact angles of deionized water were 103.5° and 117° respectively, and those of aviation kerosene were 68° and 120.5° respectively. They possessed outstanding hydrophobicity, but particles modified by FP2 had better oleophobicity. Finally, the particles covered the surface of fuel, which prevented the fuel from evaporating. Combined with the effect of interrupting the combustion chain reaction, the flame was gradually extinguished.

Preparation of cationic fluorinated acrylate copolymer latex and its application on cotton fabric

Coupled with the improvement in people’s living standards, the demand for textiles having a special performance like water repellency is mushrooming. In this study, the cationic fluorinated acrylate copolymer latex particles with a core–shell structure were synthesized via semicontinuous seed emulsion polymerization process, using Span 80, Tween 80, and dodecyltrimethylammonium chloride as composite emulsifier and (2-(acryloyloxy)ethyl)trimethylammonium chloride as a cationic monomer. Cationic fluorinated acrylate copolymers were successfully confirmed through the FTIR, 1H NMR, and XPS analyses. In addition, the homogeneous latex particles (~ 132 nm of average size) with an evident core–shell structure were observed by TEM analysis, and a stable positive charge (48 ± 5 mV) on the surface of latex particles was demonstrated by zeta potential analysis. Meanwhile, the results showed that the dosage of dodecafluoroheptyl methacrylate (DFMA) played a vital role in the hydrophobicity of the latex films and the one with the best water repellency was identified with 10 g of DFMA dosage. Furthermore, the cotton fabric finishing experiments demonstrated that, after finishing by the cationic fluorinated acrylate copolymer emulsion, the treated cotton fabric exhibited excellent hydrophobicity even at low concentration, with > 130° of the water contact angle and > 60 min of the static absorbing time.

Electrospun polyvinylidene fluoride/fluorinated acrylate copolymer tree-like nanofiber membrane with high flux and salt rejection ratio for direct contact membrane distillation

A hierarchical tree-like nanofiber membrane (TLNM) with high hydrophobicity was prepared via electrospinning polyvinylidene fluoride (PVDF) blended with tetrabutylammonium chloride (TBAC) and fluorinated acrylate copolymer (FA). Then, the hydrophobicity of PVDF/TBAC/FA TLNMs was further enhanced after ultrasonic treatment. The introduction of TBAC and FA promoted the formation of tree-like structures and the as-prepared PVDF/TBAC/FA TLNMs showed strong hydrophobicity with a water contact angle of 137 ± 3°, extremely small pore size of 0.21–0.26 μm, outstanding mechanical strength of 7.90 MPa and high liquid entry pressure of 0.23 MPa, making the membrane possess excellent performance in the direct contact membrane distillation (DCMD) process. The PVDF/TBAC/3% FA TLNMs with a thickness of 60 ± 3 μm showed a superior permeate flux of 54.39 L/m2 h and the salt rejection rate kept above 99.5% after 9 h using a 3.5 wt% NaCl as the feed solution while with the feed and permeate temperatures were set as 60 °C and 20 °C, respectively. This work highlights the promising application of this TLNMs in the field of membrane distillation.

A green and facile method to fabricate superhydrophobic coatings

ABSTRACTIn this work, we reported a green and facile method to fabricate superhydrophobic coatings via blending TiO2 nanoparticles and fluorinated acrylate copolymers. The fluorinated acrylate copolymers were synthesised with the method of solution polymerisation using ethanol as solvent. The integration of TiO2 nanoparticles and the fluorinated acrylate copolymers satisfied two necessary conditions of multi-scale nano/microstructures and low surface energy for fabricating superhydrophobic coatings. It was found that the water contact angle and contact angle hysteresis of the as-prepared coatings were respectively 156.3° and 3.7°, and it indicated that the coatings had excellent superhydrophobicity and self-cleaning ability. In particular, these coatings showed good thermal stabilities. Owing to its flexibility, simplicity and non-toxicity, the method is not only a facile and inexpensive way to achieve the lotus effect but could also create coatings with high values in practical application.

Research of Fluorinated Acrylate Copolymer on Flax Fabric

A fluorine-containing acrylate copolymer emulsion was prepared in this study, which was applied to finishing linen fabric. Dodecafluloroheptry methacrylate (G04) was used as a modified monomer, butylacrylate (BA) and methylacrylate (MMA) as soft and hard monomers. respectively, and acrylic acid as a functional monomer. Structure and properties of the products were characterised and analyzed by FTIR, TEM, PSD and CA measurements, respectively. The water and air permeability as well as the breaking force of the fabric treated were also investigated. The results showed that the fluorine-containing acrylate copolymer emulsion obtained had a core-shell structure, and the microsphere was of nanoscale size. Because of the latex film on the fabric surface, it became smooth and flat. And the increase in G04 was beneficial to the mechanical properties, waterproofness and antifouling ability of the linen fabric. When the content of G04 were increased from 0% to 20%, the water in the linen sample and hexadecane contact angles to the copolymer film increased from 113.02° to 136.08° and from 65.1° to 87.6°, respectively. Furthermore the breaking force of the linen samples was enhanced from 648 N to 721 N. However, the increasing content of G04 had negative effects on the flexural rigidity as well as water and air permeability of the fabric, which were essential requirements for the fabric’s application. However, the wash resistance was excellent and the wear-resistance of the finished linen fabric was better than the unfinished linen fabric.

Pulmonary injury associated with spray of a water-based nano-sized waterproofing product: a case study

BackgroundIn most reported cases of lung trauma with water proofing products, volatile organic compounds (VOC) have a prominent role. Here we report on a case involving ten workers exposed to a sprayed product containing nanoparticles in a water solution with only a few percent VOC.Case presentationTen workers suffered from respiratory symptoms following spray impregnation of hardwood furniture using a waterproofing product that contained positively charged fluorinated acrylate copolymer solid cores with a median diameter of 70 nm (1.3 w%) in aqueous suspension with 3.3 w% VOC and 0.3 w% quaternary ammonium. The worker who applied one liter of the product in a wood workshop, using an air mix spray gun, did not report any health complaints. Another worker, who entered the workshop 3 h later and had rolled and smoked two cigarettes, was hospitalized with severe chemical pneumonitis. A chest X-ray (CXR) showed bilateral infiltrative impairment in the lower lobe regions. On the next day a second CXR showed increased patchiness marking in all fields. A high-resolution Computer Tomography (CT)-scan demonstrated extensive bilateral areas of ground-glass opacities predominantly in the lower regions of the upper lobes, the right middle lobe and the apical regions of the lower lobes, compatible with severe chemical pneumonitis. On the following morning, nine workers in an adjacent workplace in the same building, experienced dry cough, chest tightness and substernal pain upon physical exercise. Reconstruction of the spray application in a climate chamber confirmed trimethyl silanol, glycol ethers and fluoroalkenes in the gas phase. Immediately after the spray application, aerosols were observed at a maximum concentration of 6.3 × 104 cm−3. Mass concentrations were 0.095 and 10 mg/m3 in the size ranges 5.6-560 nm and 0.22-30 μm, respectively, decreasing to less than 10 μg/m3 in both size ranges after 15 h.ConclusionThe hospitalized worker had smoked cigarettes contaminated with fluoropolymers which is a plausible explanation for the lung trauma. Respiratory symptoms in the nine workers may be caused by inhalation of particles that became airborne by resuspension from surfaces when workers entered the adjacent workplace the next day. A contribution from VOC appears less likely because measurements and modelling showed that concentrations in the mg/m3 range could have occurred only if the building was assumed to be completely airtight.

Synthesis of core-shell fluorinated acrylate copolymers and its application as finishing agent for textile

Core-shell fluorinated acrylate copolymers emulsion was thus synthesized via the core-shell emulsion polymerization with the fluorinated monomers and acrylic monomers as the main raw materials and its properties were studied. PFMA, the fluorinated acrylate monomers, was synthesized by the esterification of perfluorooctanoyl chloride (PFOC) and hydroxypropyl methacrylate (HPMA). Then the core-shell fluorinated acrylate copolymers emulsion with a poly(MMA/BA/St) core and a poly(PFMA/MMA/BA) shell was synthesized via a starved semi-continuous core-shell emulsion polymerization method by using KPS and sodium bicarbonate as the initiator/buffer system and SDS/Twain 80 as the commixture emulsifier. Lastly, the synthesized copolymers was applied as textile finishing agent for cotton textile. The results of FT-IR and NMR indicated that PFMA had been synthesized as expected and effectively combined in the emulsion copolymerization. The GPC, zeta potential, TEM and DSC showed that the particles had uniform spherical core-shell structure with a diameter of 65-150 nm, and the distribution and emulsion stability was satisfactory. As XPS, FESEM and AFM shown, a hydrophobic structure which was similar to the structure of the lotus leaf were formed and the surface hydrophobicity of the films can be improved. Based on the analysis of DSC, thermal stabilities of the films were enhanced with the increase of fluorine content. Besides, FESEM of textiles showed that the surface of treated textiles were smooth and the edges were clear and visible, indicating significant improvement of the performance on water and oil repellent.

Facile fabrication of superhydrophobic coatings based on two silica sols

Superhydrophobic coatings were successfully fabricated by using two silica sols and fluorinated acrylate copolymers through the organic-inorganic hybrid method. The two silica sols contained different nanoparticles, namely, silica nanoparticles with many hydroxyl groups on their surfaces and silica nanoparticles with many long-chain alkyls on their surfaces. The integration of these two silica sols and fluorinated acrylate copolymers satisfied two necessary conditions of multi-scale nano/microstructures and low surface energy for fabricating superhydrophobic coatings. The superhydrophobic surfaces were constructed by using appropriate weight ratios of silica/copolymers and silica sol (methanol) contents. The superhydrophobic coatings displayed a water contact angle as high as 156.2° and contact angle hysteresis of 2.4°, which indicated their good self-cleaning capability. In particular, these coatings showed good mechanical properties and excellent thermal stabilities. The method is not only a facile and inexpensive way to achieve the lotus effect but could also create coatings with high values in practical application.

Thermal and optical properties of Tb(III), Eu(III) and Tb(III)/Eu(III) co-complexed silicone fluorinated acrylate copolymer

Tb(III), Eu(III) and Tb(III)/Eu(III) activated silicone fluorinated acrylate (SFA) have been successfully synthesized using the method of semi-continuous emulsion polymerization. The copolymers are characterized by flourier transform infrared (FT-IR), thermal gravity analysis (TGA), photoluminescence excitation (PLE) and emission (PL) spectroscopy. The copolymer containing Tb(III) and Eu(III) ions display green and red luminescent colors under UV light excitation, respectively. The TGA curves show the thermal decomposition temperatures of the copolymers are up to about 300°C. The PL spectra show a strong green emission at 546nm (5D4→7F5) of Tb(III) complexed copolymers, and show a prominent red emission at 615nm (5D0→7F2) of Eu(III) complexed copolymers. Different concentrations of Eu(III) and Tb(III) ions are introduced into the copolymer and the energy transfer from Tb(III) to Eu(III) ions in the copolymer was found. Thus, based on the results it can be suggested that SFA:Eu(III), SFA:Tb(III) and SFA:Tb(III)/Eu(III) can be used potentially as luminescent materials.

Preparation and Characterization of Fluorinated Acrylate Copolymer Emulsion

A fluorinated acrylate copolymer emulsion with core-shell structure was synthesized by semi-continuous emulsion polymerization using methyl methacrylate (MMA ), butyl acrylate (BA) as the raw material, hexafluorobutyl methacrylate as fluorinated acrylate monomer, ammonium persulfate (APS) as initiator, sodium dodecyl sulfate (SDS) and polyoxyethylene octyl phenyl ether (OP-10) as emulsifier and taking water as dispersion medium. The as-prepared latexes are characterized by Fourier transforms infrared (FT-IR) spectroscopy. The hydro-oleophobic of copolymer is determined by contact angle meter. The typical core-shell structure is proved by differential scanning calorimetry (DSC). The results show that the copolymer emulsion has good hydro-oleophobic when the content of hexafluorobutyl methacrylate is 15%, used the delay loading method, the water contact angle of the coating surface is 104 °, the hexadecane contact angle is 75 °. Key words: fluorinated acrylate; copolymer; emulsion; hydro-oleophobic; contact angle

A combined experiment and molecular dynamics simulation study on the influence of the crosslinking on the crystallization of comb fluorinated acrylate copolymers

Hydrophobic coatings for practical applications demand good durability of hydrophobicity and excellent adhesion. Therefore, the preparation of crosslinked crystalline polymers with perfluoroalkyl side-chains and long alkyl side-chains were proposed. In this paper, the influence of the crosslinking on the crystallization of fluorinated acrylate copolymers was investigated through experimental and molecular dynamic simulation results. According to the FT-IR spectroscopy, XRD data and DSC curves, P(SA-co-HEMA-co-FOEMA) was amorphous, while P(SA-co-FOEMA) and the cured resin formed crystalline polymers with hexagonal packing of alkyl side-chains, and the degree of crystallinity in the cured resin is larger than that in P(SA-co-FOEMA). These phenomenons were further interpreted through the snapshots of the equilibrated systems, the radial distribution function, and the concentration profiles. Intramolecular hydrogen bonds and arrangement of main-chains, corresponding to the embedding of N3300, were considered to contribute to these phenomenons. These findings could be expanded to other comb-shape crystalline polymers for preparing functional surfaces and smart materials.

Synthesis and characterization of self-crosslinking fluorinated polyacrylate soap-free latices with core–shell structure

Novel self-crosslinking fluorinated polyacrylate soap-free latices (FMBN) with core–shell structure were synthesized by semicontinuous seeded emulsion polymerization method from dodecafluoroheptyl methacrylate (DFMA), methyl methacrylate (MMA), butyl acrylate (BA), and N-methylolamide (NMA) in the presence of a polymerizable emulsifier-ammonium allyloxtmethylate nonylphenol ethoxylates sulfate (DNS-86). Effects of the DNS-86 and DFMA amounts on stability and properties of the FMBN emulsions were studied. Besides, the latices and their film were characterized by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (1H NMR) spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM), laser particle size analyzer, differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), contact angle goniometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. FT-IR spectra and 1H NMR spectrum showed that DFMA successfully participated in soap-free emulsion polymerization and monomers formed the fluorinated acrylate copolymer. The resulted latex particles had the core–shell structure. The films formed from the FMBN latices thus had two Tg. Their thermal stability and Tg of the shell phase increased gradually with augment of DFMA amount in polymer. XPS, AFM and hydrophobicity analyses indicated the fluoroalkyl groups had the tendency to enrich at the film–air interface. This enrichment of fluorine at the film–air interface was more evident after the annealing process. Water contact angles of the FMBN film before and after the annealing process could attain 115.5° and 117.5°, individually.

Preparation and characterization of silica/fluorinated acrylate copolymers hybrid films and the investigation of their icephobicity

Inexpensive hydrophobic and icephobic coatings and films were obtained by a simple method. These coatings were prepared by mixing silica sol and fluorinated acrylate copolymers. There was a phase separation process in the film-forming which can provide the excellent performance. Small amount (about 2 wt.%) of fluorinated (methyl) acrylate was used in all of these coatings. The coatings were eco-friendly by using ethanol as the solvent system. Scanning electron microscopy, atomic force microscope, energy dispersive X-ray fluorescence spectrometer, water contact angle, thermal gravimetric analysis and tests of adhesion and hardness had been performed to characterize the morphological feature, chemical composition, hydrophobicity and icephobicity of the surface, thermal stability and mechanical properties of the coatings. The results showed that the films had good hydrophobicity, high thermal stability and excellent mechanical properties of adhesion strength and pencil hardness. Furthermore, by testing their properties of delaying water droplet from icing, it was found that ice formation was delayed for 90min compared with the glass surface at −5.6°C. The hybrid coatings may be suitable for large-scale and practical application owing to its flexibility and simplicity.

CORRELATION BETWEEN CRYSTALLIZATION BEHAVIOR OF FLUORINATED ACRYLATE COPOLYMERS AND THE SURFACE WETTING PROPERTY OF THEIR FILMS

A series of fluorinated acrylate copolymers were synthesized via free radical copolymerization by using monomers of 2-(perflurooctyl)ethyl methacrylate(FOEMA) and n-alkyl acrylates(RAs)(n=4,8,12,16,18) with various lengths of side chains.The crystalline behavior of the copolymers was characterized by X-ray diffraction(XRD) and differential scanning calorimetry(DSC).It is found that the crystallization of acrylate copolymers is in close connection with the side-chain length of acrylates.The copolymers crystallized at room temperature when the side-chain length number n was 16 or 18,however,no crystallization was observed for the copolymers with n less than 16 under the same condition.The crystallization enthalpy changes of RA-co-FOEMA copolymers were determined from the DSC thermograms.The copolymer with n=16 has the minimum entropy change at constant pressure compared with other three crystallized copolymers through thermodynamic calculation,which indicated this copolymer was the most ordered one.The F/C atomic ratios and composition of functional groups on the surfaces of RA/FOEMA copolymer films were determined by multifunctional photoelectron spectroscopy(XPS),and the static contact angles of n-hexadecane and water on films were measured.The F/C ratios increased from 0.39 to 0.71 with increase in the side-chain length of RA/FOEMA copolymers.When n was 16 or 18,the copolymers demonstrated much more composition of non-polar groups(—CF3 and —CF2) and fewer polar groups(—C-O and —C—O—C-O) on the film surfaces,leading to the rapid increase in the n-hexadecane static contact angles on the films of copolymers.It may suggest that crystallization of hydrocarbon side-chain of copolymers can promote fluorinated component to migrate to the polymer-air interface during the process of film forming and hence improve the hydrophobicity and oleophobicity of the films.

Comparison and Thermodynamic Analysis of Crystallinity of Noncrosslinking and Crosslinking Fluorinated Acrylate Copolymers Films

In this manuscript two different fluorinated acrylate copolymers films, one was non-crosslinking Stearyl acrylate/2-(perfluorooctyl) ethyl methacrylate (SA/FOEMA) and another was cross-linked SA/2-hydroxyethyl methacrylate(HEMA)/FOEMA/hexamethylene diisocyanate trimers (N3300), were prepared and their crystallinities were investigated by means of X-ray diffraction (XRD) and differential scanning calorimetry (DSC). It can be shown from the XRD results that the value of crystallinities of SA/FOEMA and SA/HEMA/FOEMA/N3300 copolymer were 80.95% and 84.02%, respectively. Based on DSC curves and theoretical thermodynamic analysis , it is indicated that crosslinking can improve crystallinity of copolymer composed of SA and FOEMA.

Preparation and characterization of fluorinated acrylate copolymer latexes by miniemulsion polymerization under microwave irradiation

Abstract Fluoroacrylate copolymer miniemulsion was prepared by miniemulsion polymerization under microwave irradiation. The composition of the copolymer was determined by FTIR, DSC, 1H NMR and 19F NMR. The morphology, size, and size distribution of the latex particles as well as changes in the size during polymerization were characterized by TEM and photon correlation spectroscopy (PCS). The effects of kinetic parameters on the polymerization were evaluated. The particle size of latex underwent almost no change during microwave irradiation polymerization. The diameters of latex particles prepared by microwave irradiation were smaller and more monodispersed than those prepared by conventional heating and the latex had good centrifugal stability. Polymerization under microwave irradiation had a higher reaction rate and higher conversion than traditional heating. By using 10 wt% fluoromonomer, the surface energy of the latex film could be reduced from 27.24 mJ/m2 (latex film of fluorine-free) to 17.59 mJ/m2 and the decomposition temperature increased by 25 °C.

Surface properties and chain structure of fluorinated acrylate copolymers prepared by emulsion polymerization

The fluorinated copolymer poly (MMA–co–FMA), composed of methyl methacrylate (MMA) and 2-perfluorooctylethyl methacrylate (FMA), was prepared by emulsion polymerization using a pre-emulsified monomer addition process. The results showed that the contact angle of water on its solvent-borne film increased dramatically and reached 118o when the FMA content in the copolymer was only 0.65 mol%, approaching that of poly(2-perfluorooctylethyl methacrylate) homopolymer. Unlike the copolymer prepared by solution polymerization, X-ray photoelectron spectroscopy (XPS), and sum frequency generation (SFG) vibrational spectroscopy analysis results indicated that the fluorinated moieties in this polymer were very easily segregated at the surface of the film. The interfacial structure and properties of this polymer in solution were investigated using SFG, surface tension, and dynamic laser light scattering (DLS). It was found that emulsion polymerization produced a chain structure of the fluorinated copolymer similar to that of FMA capped PMMA, thereby providing a possible way to produce fluorinated end-capped polymers using a popular polymerization method.

Miniemulsion polymerization of a fluorinated acrylate copolymer: Kinetic studies and nanolatex morphology characterization

AbstractA stable fluoroacrylate copolymer emulsion was successfully prepared by miniemulsion polymerization with fluoroacrylate, lauryl methylacrylate, and methyl methacrylate as monomers. Extremely hydrophobic fluoroacrylate, instead of conventional cosurfactants, was used as a reactive cosurfactant to stabilize the miniemulsions. The results indicated that fluoroacrylate retarded Ostwald ripening and allowed the production of stable miniemulsions. The chemical compositions of the copolymer were studied with Fourier transform infrared and 1H‐NMR. The average composition of the copolymers prepared with miniemulsions was in good agreement with the feed ratio according to 1H‐NMR from the integration ratios corresponding to typical protons of the individual monomers. The particle size distribution and morphology of the latex particles were determined with laser particle analysis and transmission electron microscopy. The particle size of the latex underwent no change in the process of miniemulsion polymerization, but the particle size distributions were broader than those of conventional emulsion polymerization. The effects of various reaction parameters, including the temperature and concentrations of the emulsifier and initiator, on the miniemulsion polymerization were also investigated, and the polymerization rate and conversion increased with increasing concentrations of nonylphenol polyethoxylate (with an average of 40 ethylene oxide units per molecule), cetyltrimethylammonium, and 2,2′‐azobisisobutyronitrile. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 641–647, 2007