The Design And Synthesis Of Novel Multifunctional Finishing Agents Containing Perlfuoroalkyl And Their Applications On Cotton Fabrics

As people‘s living standard continues to rise, the wear comfortable, sanitation and healthconsciousness for people has become increasing important.People required the textile not onlyhad good air permeability but also had multifunction such as water and oil repellent,antifouling and antibacterial properties.So the development of the multifunctional finishingagent in the textile field was very necessary. The novel multifunctonal finishing agents weredeveloped in this paper, at the same time how to reduce pollution of the finishing agent to theenvironment or adverse effects also need to be considered. We designed and prepared severalmultifunctional finishing agents began from the synthesis of functional monomers, one ofthem contained the short fluorine chain. This paper researched and analyzed deeply andsystematically their performance and provided the theoretical support for the design andresearch of the low-toxic high performance multifunctional finishing agents.We designed and synthesized sucessfully some functional acrylate monomers includingwater and oil repellent functional monomer containing the perfluoriated acrylate, theantibacterial functional monomer acrylate d1containing short chain quaternary ammoniumsalt, the antibacterial functional monomer acrylate d2containing long chain quaternaryammonium salt, the bishydroxyethyl sulfoue-containing acrylate monomer which could becrosslinked with cotton, the octadecyl acrylate monomer which can improve water and oilrepellent property and decrease cost.The intermediate products and monomer structure werecharacterized by infrared spectroscopy （FTIR）, nuclear magnetic resonance H spectrum （1HNMR）, nuclear magnetic resonance F spectrum (¹⁹F NMR), mass spectrometry, elementalanalysis and confirmed the design and synthesis method of these functional monomer wasfeasible.Water and oil repellent monomer, antibacterial monomer （d1, d2）, the crosslinkingmonomer and the auxiliary monomer were polymerized to get a functional emulsion byemulsion polymeriztion. The effects of the polymerization process are discussed fromemulsifier, initiator, monomer ratio, reaction temperature and time. The experimental resultsshow that: The appearance of the achieved emulsion polymer [PFAC1（including d1） andPFAC2（including d2）] had blue fluorescence and the monomer conversion rate was morethan94%when the mass ratios of m （fluoride monomer）: m （auxiliary monomer）: m（crosslinking monomer）: m （antibacterial monomer） were55:10:10:25;Hexadecyltrimethylammonium bromide, TO-10and the fluorine-containing surface ativeagent were mixed as emulsifier, the ratio of them was1:1:0.5, mass fractions of emulifier were5.0%of the total monomer; cumene hydroperoxide and ferrous sulfate were mixed asinitiator （The mole ratio was1:1）, the dosage of initiatore was0.6%of the totalmonomer,there were polymerization at40℃for4h. The comparative experiments show thatthe bacteriostatic rate and water and oil repellent property is worse than that of PFAC2.PFAC2was characterized by FTIR,¹⁹F NMR, particle size, GPC and DSC, the researchresults showed PFAC2contained the crosslinking monomer, the quaternary ammonium salt-containing acrylate, the fluorine acrylate and octadecyl acrylate. The average particle size ofemulsion PFAC2was54.97and the molecular distribution is narrow; Number-averagemolecular weight and weight-average molecular weight of PFAC2were12173.0and13390.3respectively, the molecular weight distribution factor was1.10, there were two glasstransition temperature includingT_g1=65.1℃and Tg3=131.7℃, it showed PFAC2is twophase existed.The optimal conditons of the finishing process for PFAC2were determined by testingthe changes of physical property, the mechanical property and antibacterial property of thetreated fabric with PFAC2: the fabric was padded through two dips and two nips, theconcentration of PFAC2was40g/l, The fabric was dried at100℃for3min and cured at170℃for3min. The water and oil repellency ratings of the cotton fabrics finished with PFAC2were100and6, respectively, The water and oil repellency rating of the fabric treated withPFAC2after30launderings was80and4, respectively, The treated cotton fabrics alsoshowed excellent repellency to the liquid such as coffee, ink, wine,synthetic blood, salad oil,sauce etc. The soil release rate of the treated fabric was4-5. The finished cotton fabricshowed a97.4%reduction in the number of Staphylococcus aureus（AATCC8099） and a90.5%reduction in the number of Escherichia coli.（AATCC6358）, the treated fabric was washed for10laundering cycles, and the reduction rates of Staphylococcus aureus（ATCC6538） andEscherichia coli.（ATCC8099） were98%and94.2%respectively. PFAC2can be applied withanti-wrinkle finishing agent2D resin in single bath, The anti-wrinkle property and washingdurability of the treated fabric with PFAC2and2D resin in single bath were improvedcompared with that of the treated fabric with PFAC2, The trace of formaldehyde producedbecause2D resin was decomposed when cured, it improved the early bacteriostatic effect oftreated fabric. The performance of the treated fabric was determined by type and structure ofthe softening agents when PFAC2was applied with cationic soft flake, amino silicone oil andthe reactvie silicone oil softe agent in single bath. A novel polyether glycol PFOX with low degree of polymeriztion which contained theshort fluorine chain pentafluoropropyl through the fluorinated oxetane opening ringpolymeriztion. The chemical structure of PFOX was characterized by FTIR,¹H NMR,¹⁹FNMR, MS and GPC. The results showed the targeted product was compliance with therequirements, Number-average molecular weight and weight-average molecular weight ofPFOX were2419and2709respectively, and the molecular weight distribution d was1.12.The cationic water-borne no silicone polyurethane （Polymer1） which contained shortfluorine chain was synthesized with the aliphatic isocyanate （IPDI）, PFOX,N-methyliminodiethanol and1,4-Bis（chloromethyl）benzene etc. as taw materials. Thecationic water-borne silicone-containing polyurethane （Polymer2） which contained shortfluorine chain was synthesized with the aliphatic isocyanate （IPDI）,PFOX,N-methyliminodiethanol,1,4-Bis（chloromethyl）benzene and3-aminopropyltrimethoxysilane coupling agent etc. as raw materials. The evaluation results from water and oil repellentproperty, the antibacterial property and washing durabillity of the treated fabric with polymer1and polymer2showed the comprehensive performance of polymer2was better than that ofpolymer1, the main reason is the polymer2containing the reactive groups-Si（OCH3）3cancrosslink with hydroxyl of cotton fiber under certain conditions and then improved thecombination fastness of polymer2and cotton fiber.The optimal conditons of the finishing process for polymer2were determined by testingthe changes of physical property, the mechanical property and antibacterial property of thetreated fabric with polymer2: the fabric was padded through two dips and two nips, thedosage of polymer2was40-50g/l, The fabric was dried at80℃and cured at170℃for3min.The water and oil repellency ratings of the cotton fabrics finished with polymer2were100and3, respectively, the contact angle of water on the treated fabric was155o, the reductionrates of Staphylococcus aureus（ATCC6538） and Escherichia coli.（AATCC8099） for treatedfabric were99%and96%respectively.The wrinkle recovery angle can reach230o, Thetreated fabric still had good effect on water and oil repellent, anti-bacterial after30launderings,it showed good washing durailbity.