Preparation and characterization of self-crosslinking acrylic emulsion with different fluorocarbon chain lengths

Purpose Fluorine materials have received the keen attention of many researchers because of their water repellency and low surface free energy. The purpose of this paper is to prepare self-crosslinking fluorocarbon polyacrylate latexes containing different fluorocarbon chain lengths by semi-continuous seeded emulsion polymerization technology. Design/methodology/approach Methyl methacrylate (MMA), butyl acrylate (BA), hydroxypropyl methacrylate (HPMA) and fluorine-containing monomers were used as main monomers. The fluorine-containing monomers included hexafluorobutyl methacrylate (HFMA), dodecafluoroheptyl methacrylate (DFMA) and trifluorooctyl methacrylate (TFMA). Potassium persulfate (KPS) was used as thermal decomposition initiator, non-ionic surfactant alkyl alcohol polyoxyethylene (25) ether (DNS-2500) and anionic surfactant sodium dodecylbenzene sulfonate (SDBS) as mixed emulsifier. Findings Through optimizing the reaction conditions, the uniform and stable latex is gained. The polymer of structure was characterized by Fourier transform infrared spectroscopy (FTIR). Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and contact angle (CA) were tested on latex films. The particle size and distribution range of emulsion were tested with nano particle size analyzer. After comprehensively comparing the latexes and films prepared by HFMA, DFMA and TFMA, the performance of DFMA monomer modified is better. Originality/value The self-crosslinking acrylic emulsion is prepared via semi-continuous seeded emulsion polymerization, which methyl methacrylate (MMA), butyl acrylate (BA), hydroxypropyl methacrylate (HPMA) and fluorine-containing monomers were used as main monomers. The fluorine-containing monomers were composed of hexafluorobutyl methacrylate (HFMA), dodecafluoroheptyl methacrylate (DFMA) and trifluorooctyl methacrylate (TFMA). Potassium persulfate (KPS) was used as thermal decomposition initiator, non-ionic surfactant alkyl alcohol polyoxyethylene (25) ether (DNS-2500) and anionic surfactant sodium dodecylbenzene sulfonate (SDBS) as mixed emulsifier. There are two main innovations. One is that the self-crosslinking acrylic emulsion is prepared successfully. The other is that the effects of monomers containing different fluorocarbon chain lengths on polyacrylate, such as monomer conversion rate, coagulation rate, mechanical stability, chemical stability, emulsion particle size and storage stability, are studied in detail.

Synthesis and application of non-bioaccumulable fluorinated surfactants: a review

Due to negative effects of conventional fluorinated surfactants with long perfluorocarbon chain (CxF2x+ 1, x≥7) like perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), these conventional long perfluorocarbon chain surfactants have been restricted in many industrial applications. Nowadays, their potential non-bioaccumulable alternatives have been developed to meet the requirements of environmental sustainable development. In this paper, the recent advances of potential non-bioaccumulable fluorinated surfactants with different fluorocarbon chain structures, including the short perfluorocarbon chain, the branched fluorocarbon chain, and the fluorocarbon chain with weak points, are reviewed from the aspects of synthesis processes, properties, and structure-activity relationships. And their applications in emulsion polymerization of fluorinated olefins, handling membrane proteins, and leather manufacture also are summarized. Furthermore, the challenges embedded in the current non-bioaccumulable fluorinated surfactants are also highlighted and discussed with the hope to provide a valuable reference for the prosperous development of fluorinated surfactants. Graphical abstract

Synthesis and Characterization of a Novel Class of Zwitterionic Fluorocarbon Surfactants Based on Perfluorobutyl

Perfluorooctane sulfonate (PFOS) and its derivatives had been banned due to their potential environmental hazards, although they possessed excellent surface activity. An effective method to solve this problem was to shorten the fluorocarbon chain of these surfactants from C°H17 to C4F9. As previous studies had shown, zwitterionic surfactants possess higher surface activity but have lower toxicity compared to other types of surfactants. In view of this, a class of novel zwitterionic fluorocarbon surfactants (n-CFNA-Br) with perfluorobutyl moiety was synthesized in this work. Their structures were characterized by FTIR, 1H NMR, 13C NMR, 19F NMR and MS. The results showed that all synthesized n-CFNA-Br had almost the same minimum surface tension, but their critical micelle concentration (CMC) decreased with increasing length of hydrophobic carbon chain. In pure water, the surface tension at the CMC (γCMC) of the four n-CFNA-Br were about 20 mN/m, and the CMC values were 7.73 mmol/L for 1-CFNA-Br, 4.70 mmol/L for 2-CFNA-Br, 4.13 mmol/L for 3-CFNA-Br, and 3.36 mmol/L for 4-CFNA-Br, indicating high efficiency and effectiveness. In 0.1 mol/L NaCl, the CMC values reduced to less than half of the CMC values measured in the pure aqueous surfactant solution, while the surface tensions γCMC remained almost unchanged, indicating good salinity tolerance of the synthesized surfactants. The acidic surfactant solutions exhibited similar CMC values to the saline solutions, but the surface tension γCMC increased slightly to 25 mN/m. However, further investigation showed that the n-CFNA-Br surfactants exhibited poor surface activity in alkaline solution (0.1 mol/L NaOH). In the pH range of 6.6 to 10.4, white precipitates appeared in the surfactant solutions after some time, indicating that the n-CFNA-Br are not suitable for use in alkaline systems with pH greater than 6.6.

An Experimental Investigation on Optimizing Liquid Repellency of Fluorochemical Urethane Finish and Its Effect on the Physical Properties of Polyester/Cotton Blended Fabric

This paper aims to optimize the liquid repellency performance of fluorochemical urethane (FU)—a patented technology with a shorter fluorocarbon chain (C4). FU is free from persistent bioaccumulative toxins such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS), unlike the long-chain fluorinated chemicals (>C6). Different sets of varied finish concentrations with an extender and a wetting agent were prepared to treat the 65/35% polyester/cotton blended fabric. The finish concentration was optimized based on the liquid repellency (water and oil-repellency) of the treated fabric and its laundering durability. In addition, the effect of the finish concentration on selected physical properties of the treated fabric was studied as well. The liquid repellency, laundering durability, and selected physical properties of the treated and untreated fabrics were analyzed using ASTM and AATCC standard test methods. The results of textile substrates treated with 60 g/L of FU show an optimum balance of desired liquid repellency without affecting the physical properties of the fabric significantly.