丁香酚基复合涂层阻燃疏水棉织物的制备及其性能

Preparation and properties of flame retardant hydrophobic cottonfabric with eugenol-based composite coating

为解决棉织物使用过程中易燃易污的问题,采用简单的两步浸渍法对棉织物进行阻燃疏水整理。首先,用丁香酚和二氯化磷酸苯酯合成生物基阻燃剂二丁香基磷酸苯酯(DEP),并用其对棉织物进行阻燃整理。随后,利用甲基三甲氧基硅烷改性锆基金属有机框架(UiO-66)颗粒制备疏水剂,并将其用于阻燃棉织物的疏水整理。最后对所得阻燃疏水棉织物的结构、热稳定性、阻燃性、疏水性和耐污性能等进行研究。结果表明:相比于原棉织物,整理后棉织物的热稳定性能提高,燃烧后成炭明显,表明该复合涂层具有良好的阻燃效果;整理后的棉织物还表现出较好的疏水性能,疏水角为139°,并可耐多种常见污渍。该阻燃疏水复合涂层采用生物质为原料,绿色环保,且操作简便,在制备功能性纺织品方面具备较大的应用潜力。

Objective As the most commonly used natural fiber textile,cotton fabrics are widely applied for various end uses because of their biodegradability,moisture absorption and breathability,softness and wide range of sources.However,cotton fabrics also display extremely flammable,hydrophilic and easily contaminated.In order to solve these problems and further improve the applicability of cotton fabrics in daily life,a simple two-step impregnation method is proposed in this paper to add flame retardancy and hydrophobicity to cotton fabrics.Method Firstly,eugenol and phenyl dichlorophosphate were used to synthesize the bio-based flame retardant(DEP)by substitution reaction to prepare flame-retardant cotton fabrics.The phosphorus-containing substances in flame retardant can be decomposed in advance,catalyzing the dehydration of cotton fabrics into carbon and improve the thermal stability of cotton fabrics.Subsequently,zirconium based organometallic framework UiO-66 particles were modified with methyltrimethoxysilane to prepare the hydrophobic agent by simple surface modification,used for hydrophobic finishing of flame-retardant cotton fabrics.Low surface energy substances and micro-nano materials are combined on the surface of the fabrics to construct a micro-nano hydrophobic coating.Results The structure,thermal stability,flame retardancy,hydrophobic capacity and antifouling property of the obtained flame retardant and hydrophobic cotton fabrics were characterized by scanning electron micro-scope(SEM),thermogravimetric analysis(TGA),vertical burning test,water contact angle(WCA)and droplet diagram,respectively.Furthermore,the flame retardant mechanism and hydrophobic mechanism were further investigated.The chemical structure of the product in the FT-IR spectra(Fig.2)and 1H NMR spectra(Fig.3)both conform to the chemical structure of the flame retardant,demonstrating the successful synthesis of the flame retardant.The surface morphology of the treated cotton fabric and hydrophobic particles was observed by SEM,and the results showed that the flame retardant and hydrophobic agent were successfully and uniformly attached to the cotton fabric without destroying the original structure of the fabric and not affecting the normal morphology of the cotton fabric(Fig.4).That the residual char content at 800℃ranges from 1.7%of the raw cotton fabric to 8.6%of DEP3-UiO-66/MTM with an obvious char layer(Fig.5),indicating that the thermal stability of the treated cotton fabric has been improved,which also reflect the enhancement of flame retardancy of the treated cotton fabric.This is mainly attributed to the flame retardant role played by phosphorus-containing flame retardants in the condensed phase.The LOI of pure cotton and DEP3 were 18.5%and and 26.5%(Tab.2),respectively.The treated cotton fabric presented good char-forming ability after combustion(Fig.6),and the introduction of DEP flame retardant coating effectively improves the flame retardancy of cotton fabric.In addition,the treated fabrics show good hydrophobicity.Among them,the WCA of DEP3-UiO-66/MTM is as high as 139°and the slide angle is 28°(Fig.7).As can be seen from the droplet diagram of the treated cotton fabrics(Fig.8),DEP3-UiO-66/MTM can withstand a variety of common stains in life such as ink,mud,coffee,milk,tea,acid(hydrochloric acid dyed with methyl red),alkali(sodium hydroxide solution dyed with thymolphthalein)and water droplets,and remain rounded on the surface of the treated cotton fabrics,showing excellent anti-fouling performance.The whiteness and bending length of the flame retardant hydrophobic fabrics were 83.89%and 21.0 cm(Tab.3),respectively,which were not much different from those of pure cotton fabrics.Conclusion The results confirm that the modified cotton fabric has good flame-retardant,hydrophobic and antifouling properties.The flame retardant hydrophobic composite coating is constructed via a simple,efficient,eco-friendly way using biomass as the raw material,which is green,environment-friendly and easy to operate.The prepared flame retardant hydrophobic multifunctional fabrics have broad application prospects in protective clothing,medical equipment,clothing,decoration and industrial buildings.