Photo-polymerized trifunctional acrylate resin/magnesium hydroxide fluids/cotton fabric composites with enhancing mechanical and moisture barrier properties
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In this paper, a facile and environmentally friendly approach was used to prepare acrylate resin-based cotton fabric composites via adding reactive Mg (OH)2 fluids (MHFs) into trimethylolpropane triacrylate (TPT) monomer followed by coating on the cotton fabrics by photo-polymerization. The morphology, thermal stability, rheological behavior, and mechanical properties of polymer composites are systematically characterized by various technologies. Mechanical test results demonstrates that tensile strength and young’s modulus of the polymer composites are as high as 46 MPa and 1440.27 MPa, respectively, which is 3.5 and 9.1 times that of polymer composite in the absent of MHFs meanwhile without sacrificing the toughness. Moreover, it is amazingly found that the addition of MHFs can effectively reduce water vapor transmission rate of composite. Herein, these advantages of MHFs can be easily applied as encapsulation layer in the field of smart cotton fabric and electrical device.
KeywordsMagnesium hydroxide Photo-polymerization Composites Stability Cotton fabric
Magnesium hydroxide (MH) has attracted considerable interests due to its many advantages of non-toxic, smoke-proof, anti-droplet, and high processable temperature [1, 2]. In addition, the huge surface area of nano-sized MH makes it an alternative halogen-free flame retardant. However, due to the low flame retardant efficiency of magnesium hydroxide, much higher content of MH is usually required to achieve good flame retardant effect in polymer composites. Moreover, MH are usually easy to form bigger agglomerates in the polymer matrix, and its poor interface compatibility with polymer matrix results in deterioration of the physical and mechanical properties of the composite [3, 4, 5, 6, 7]. Based on above analysis, it is very challenging to increase the flame retardant effect and keep good mechanical properties of composites. Many chemical and physical approaches are utilized to decorate the particles surface for improving the dispersion and interaction between MH and the polymer matrix [8, 9, 10, 11]. However, these modified particles made by these methods behave solid-like without solvent and do not undergo a microscopic solid-to-liquid transition below 100 °C.
In 2005, Giannilis et al. firstly grafted quaternized silane coupling agent on the surface of SiO2 and γ-Fe2O3 nanoparticles, and then ion exchanged with polyoxyethylene-functionalized organic long chain to obtain organic/inorganic liquid-like nanofluids . This hybrid material macroscopically exhibits liquid-like behavior and has low viscosity at room temperature. This new kind of nanoparticles, defined as solvent-free nanofluids, which not only enhance the processability of nanoparticles, but also impart novel functionalities to nanoparticles, has recently attracted the interest of researchers around the world . Until now, a series of fluids as filler have been synthesized and used to greatly improve the performance of composite. Zheng’ group et al. found a facile and green way to synthesize a series of liquid-like hybrid materials through surface grafting a short ion or nonionic oligomer such as graphene@ZnO , graphene@Fe3O4 , and MWCNT@Au  fluids, which achieve a homogeneous dispersion and compatibility in polymer. Yin et al. synthesized a series of SiO2 fluids  and halloysite fluids  (ion exchange reaction), graphene@SiO2 fluids  and CB fluids  (hydrogen bonding interaction) with liquid-like behavior at room temperature meantime using them as fillers to fabricate polymer composites for introducing the simultaneous reinforcement and plasticization effect. However, these nanofluids without reactive groups cannot serve as reactive components and participate in a chemical reactions during the polymerization or blending processes, limiting the potential applications. Hence, John et al [21, 22] fabricated CeO2 and SiO2 nanofluids with reactive groups by simultaneously grafting a silane coupling agent with a double bond group during the quaternization of nanoparticles. This new type of nanofluids can be used as a supramolecular cross-linker and plasticizers with effects of toughening and reinforcement in nanocomposites.
Over the past two decades, fiber-reinforced composite have drawn great attention in scientific researches and industrial application for their potential capacity in aerospace [23, 24, 25], reinforced materials , and functional textile [27, 28, 29]. Among them, cotton fabrics as one of cellulose materials are economical, biodegradable materials that are woven from interlacing fibers and have an inherent wave-like surface structure. The porous fabric structure possesses some particular properties such as low density, high porosity, excellent wettability, and special softness . However, poor mechanical strength and durability caused by the cotton fabric structure limit their large-scale applications.
In this paper, we synthesized a solvent-free UV-curable polymer nanocomposite [Mg(OH)2 fliuds (MHFs)-poly(trimethylolpropane triacrylate) (PTPT)]-coated hybrid cotton fabric (MHFs/PTPT/Cotton). Herein, to enhance the compatibility of MH with the polymer, the MH particles surface are modified using polysiloxane quaternary ammonium salt (DC5700) and methacryloxypropyltrimethoxylsilane. Subsequent, reactive acrylic acid groups of MHFs surface can take part in a chemical reaction with acrylate resin under UV-irradiation in the presence of a photoinitiator to form crosslinking network. Using this simple method, MH particles are fixed firmly on the fabric surface by acrylate resin due to the crosslink reaction between MHFs and acrylate resin. The as-prepared MHFs/acrylate resin-based cotton composite synchronously achieve the reinforcement and toughness as well as improving moisture barrier property, which has an important application prospect in functional textiles and polymer composite.
2 Experimental section
Cotton fabric was purchased from Shijiazhuang Yong sheng Textile Industry.
Mg(NO3)2•6H2O, sodium hydroxide, and chloroform were purchased from Aldrich. Trimethylolpropane triacrylate (TPT) was purchased from Aldrich. DC5700 [(CH3O)3Si(CH2)3N+(CH)3(CH3)2(C18H37)Cl−] in methanol (40 mass%) was provided by Gelest from Aldrich. Surfactant nonylphenoxy poly(ethyleneoxy) ethanol potassium sulfate (NPEP) [C9H19-C6H4-O(CH2CH2O)10SO3−K+] was used as supplied by Sigma-Aldrich. Methacryloxy propyltrimethoxyl silane (MPS) was provided by Tokyo Chemical Industry (TCI). Other organic solvents were used without purification.
2.2 Preparation of MHFs
2.3 Preparation of MHFs/PTPT/cotton composites
Here, Wt is the weight of MHFs/PTPT/cotton composites at different measurement time and W0 is the initial weight of MHFs/PTPT/cotton composites.
3 Results and discussions
Figure 4b shows the ATR-IR spectra of cotton and MHFs/PTPT/cotton composites and it can provide indirect evidence for the existence of the hydrogen bonding interaction between MHFs/PTPT and cotton. There is a strong band at 3313 cm−1 in the cotton curve, demonstrating that combination of the free bond and hydrogen-bonded O–H stretching. Compared with the cotton sample, the bands in MHFs/PTPT composites shifted to higher wavenumber, indicating the hydrogen bonding formation of ether groups (C–O–C) of PTPT with hydroxyl groups of cotton . In addition, the peak position slightly shifts from 3433 cm−1 for MHF/PTPT/cotton to 3446 cm−1 for 1-MHF/PTPT/cotton, implying that the increment of MHFs content in composite result in the number increase of hydrogen bonding. In the meanwhile, the band at 1029 cm−1 of cotton corresponded to C–OH shifts to higher wavenumber (1186 cm−1) of MHFs/PTPT/cotton and strengthens, further demonstrating that more hydrogen bonding generate. Owing to the hydrogen bonding interaction, MHFs/PTPT can tightly adhere to the surface of cotton fabrics and improve the mechanical properties of MHFs/PTPT/cotton composites.
Surface hardness of pure cotton, PTPT, 1-MHFs/PTPT/cotton, 4-MHFs/PTPT/cotton, and 5-MHFs/PTPT/cotton
Functionalized MHFs as reactive filler were dispersed in TPT monomer without solvent to fabricate high performance MHFs/PTPT/cotton composites via UV photo-polymerization. These results demonstrated that the addition of MHFs have dual effects as crosslinking points and plasticizing could synchronously achieve the reinforcement and toughness of MHFs/PTPT/cotton fabrics meanwhile obviously improving the moisture barrier property due to solvation effect and barrier property of MHFs. It is believed that MHFs/PTPT composites as encapsulation layer has potential application in various flexible fabric and other electronic devices.
This work was partially supported by the National Natural Science Foundation of China (51403165), Natural Science Foundation of Hubei Province (2018CFB685, 2018CFB267), Graduate Innovation Fund of Wuhan Textile University (52300200101), the Foundation of Wuhan Textile University (183004) and Open Project Program of High-Tech Organic Fibers Key Laboratory of Sichuan Province (PLN2016-02) and Opening Project of Guangxi Key Laboratory of Calcium Carbonate Resources Comprehensive Utilization (HZXYKFKT201808), and the Innovation and Entrepreneurship Program of Hubei province (201810495060).
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
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