The Construction And Regulation Of Polymer/inorganic Hybrid Nanogels And The Application In Textile Functional Finishing

Polymer/inorganic hybrid nanomaterials have attracted much attention in the fields of textile,sensing,catalysis and biomedicine due to their special optical,electrical,magnetic and catalytic properties of different components.Nowdays,polymer/inorganic hybrid nanomaterials are considered as attractive multiphase nanostructures.Complexity and diversity of macro properties of hybrid nanomaterials can be realized through the combination of organic and inorganic components.However,hybrid nanogels prepared by inorganic nanoparticles with simple physical coverage are prone to structural instability in aqueous dispersion.That means the functional inorganic nanoparticles escaped the polymer framework and into the aqueous phase.In this work,in order to improve the structural and performance stability of polymer/inorganic hybrid nanogels in aqueous media,Fe3O4 magnetic nanoparticles and silver nanoparticles were selected as inorganic elements,and the monomer N-vinylcaprolactam,quaternized 2-(dimethylamino)ethylmethacrylate and quaternized chitosan as organic structural elements.Network of polymer/inorganic hybrid nanogels were constructed through free radical polymerization,activators generated by electron transfer atom transfer radical polymerization(AGET ATRP)and biomacromolecular cross-linking reaction in inverse miniemulsions system.This study includes the following four aspects:(1)The surface chemical modification of functional inorganic nanoparticles and the construction of polymer/inorganic hybrid nanogels network,responsiveness properties and the mechanism of drug loading and release behavior regulation were studied.Particle characteristics,responsive properties and the loading and controlled release behavior of 5-fluorouracil loaded in PNVCL/Fe3O4 HNGs were systematically investigated.(2)The structural stability in aqueous dispersion,loading and release mechanism for the model protein BSA and antimicrobial properties of PQDMAEMA/Fe3O4 HNGs with magnetic and degradation constructed through activators generated by electron transfer for atom transfer radical polymerization were systematically studied.(3)The particle characteristics and surface chemical properties of QCS/Ag HNGs prepared by the cross-linking reaction of biomacromolecules were sysmatically studied.The key factors of the structural stability and antibacterial properties of HNGs in aqueous phase were elaborated through the regulation of the crosslinking degree of HNGs network.The antimicrobial properties and cytotoxicity of various components of HNGs were further analyzed and compared.(4)HNGs were grafted on the surface of cotton fabrics by chemical bonding.And the antimicrobial activity and durability antibacterial of cotton fabrics were evaluated.The research results show that:(1)Vinyl groups were attached to the surface of Fe3O4 MNPs by using 2-isocyanatoethyl methacrylate,the inorganic nanoparticles and polymer matrix was chemical bonding in the multi-responsiveness network of PNVCL/Fe3O4 hybrid nanogels,the dispersion stability of hybrid nanogels in aqueous dispersion was improved.In the network of hybrid nanogels,cross-linking agent containing two sulfur bonds was introduced.The thiol and two sulfur exchange reaction was degraded under reduction conditions,resulting in the decrease of crosslinking degree of the polymer matrix,finally,the hybrid nanogels network was degradation.The hydrogen bonding effect between the network of hybrid nanogels and 5-Fluorouracil(5-FU)was confirmed by FTIR characterization.The loading and release of 5-Fu loaded by the network of hybrid nanogels can be controlled effectively by the concentration of 5-FU,external temperature and reducing conditions.(2)The network with evenly particles dispersed of superparamagnetic cationic PQDMAEMA/Fe3O4 hybrid nanogels was constructed by AGET ATRP.The electrostatic interaction between hybrid nanogels and bovine serum albumin was increased with the increase of pH value under the same temperature.The loading rate and maximum loading capacity of BS A increased with the network of hybrid nanogels.However,the loading rate of BSA increased with the increase of temperature when the pH value fixed.With the temperature further increased,the hydrogen bonding between hybrid nanogels network and BSA was weakened and the loading capacity also decreased.In the absence of reducing agent,the release rate and maximum cumulative release of BSA increased with the decrease of pH value.In comparision with the pH value,the network of hybrid nanogels exhibited a faster release rate in the presence of reducing agents,which mainly due to the degradation of the hybrid nanogels network.(3)The network of QCS/Ag hybrid nanogels with synergistic antimicrobial activity was constructed by Schiff base crosslinking reaction between aldehyde group and amino group by using dialdehyde compounds as cross-linking agents.The crosslinking degree of the the network can be controlled by adjusting the amount of cross-linking agent,and the size and morphology of the hybrid nanogells in the oil and aqueous phases also changed.By discussing the antibacterial rate and antibacterial behavior of various components,the antibacterial mechanism of various components was clarified.It was found that the blending system and the hybrid nanogels exhibited excellent antimorcrobial activity at higher concentrations.However,the blending system has high cytotoxicity due to the presence of silver nanoparticles modified with amino.And the QCS/Ag hybrid nanogels exhibit low cytotoxicity with good antimicrobial activity.(4)QCS/Ag hybrid nanogels with excellent antimorcrobial activity were used for the grafting modification of cotton fabrics.After plasma treatment,reactive functional group(carboxyl group)was introduced into the surface of cotton fabric,and the chemical bonding between QCS/Ag hybrid nanogels and cotton fabrics was achieved by amidation reaction of carboxyl group and amino group at high temperature.This provides a reference method for the preparation of antimicrobial cotton fabric with excellent antibacterial properties and good washing resistance.In conclusion,the results of this work provide a reference for the design and construction of the network for multifunctional polymer/inorganic HNGs with good structure and stability in aqueous dispersion.In addition,it also has a certain reference significance and practical basis for the development and design of functional textile products with special properties.