O-一氯均三嗪-N,N,N-三甲基壳聚糖的合成及其在羊毛织物抗菌中的应用

采用甲醛甲酸法合成N,N,N-三甲基壳聚糖（TMC）,再用三氯均三嗪与TMC反应,合成带有可与纤维反应的水溶性O-一氯均三嗪-N,N,N-三甲基壳聚糖（MCT-TMC）。采用FTIR、XRD、热重和元素分析等对产物进行表征,并测试其抗菌性能。将产物对羊毛织物进行抗菌整理,研究整理时间和浓度等工艺条件对抗菌性能的影响。结果表明,TMC和MCT-TMC具有较好的抗菌性能;将其用于羊毛织物抗菌整理的最佳工艺条件为：整理时间60min,整理浓度分别为3%（owf）和2%（owf）;经TMC整理的织物对E.coli和S.aureus的抑菌率分别为97.8%和99.2%,MCT-TMC整理的织物对E.coli和S.aureus的抑菌率分别为98.6%和99.8%。MCT-TMC整理羊毛织物的耐洗涤性能比TMC有显著提高,洗涤后抑菌率仍达到90%以上。     

The preparation of poly[N(n-butoxymethyl) methacrylamide] grafted silk fibers by polymerization using a low pH system

The graft polymerizations of the N(n-butoxymethyl) methacrylamide (BMA) monomer onto silk fibers were effected after reducing the pH of the grafting system to 2.5 by the addition of a formic acid solution. We compared the grafting efficiencies, surface characteristics, and thermal behaviors, as well as the whiteness levels and the extent of reduction of the rate of yellowing following UV irradiation, with the equivalent features of poly(BMA)-grafted silk fibers, prepared under normal (pH 6) conditions. The grafting efficiency [as poly(BMA) weight gain] onto silk fiber that was attained was almost 100% through optimization of the pH environment in the polymerization system by the addition of formic acid. The stiffness of the silk fabrics observed, following the conventional grafting, was markedly higher than that of equivalent silks after the polymerization at pH 2.5. The rates of yellowness index increase, for these latter silk fabrics following UV irradiation were also reduced, specifically in the initial irradiation period (up to 60 h). The SEM of the grafted silk fabrics reveal the absence of granules on the surface of the grafted silk fiber, when the silk was grafted with poly(BMA), after reducing the pH of the grafting system to 2.5. These findings suggest that the BMA monomer was polymerized specifically within the silk fiber and not on the surface. It is suggested that the increase in the polymer weight gain, and the reduced adverse effect on the fabric handle, arise because of the modified polymer location. © 1993 John Wiley & Sons, Inc.     

Graft polymerization of 1,1-dihydroperfluorobutyl acrylate onto cellulose fabric

1,1-Dihydroperfluorobutyl acrylate was prepared and grafted onto cellulose fabric by means of γ-ray preirradiation to produce oil and water repellency. A 2% grafting was sufficient to impart oil and water repellency to cellulose fabric. In the case of 19.1% or 29.4% grafted fabrics, the grafting decreased rapidly with laundering, and the laundered fabric which possessed no oil and water repellency still had about 10% grafting of the perfluoro compound. Thus, the apparent graft polymerization takes place both on the surface and in the inner structure of the cellulose fiber; the polymer grafted onto the surface imparts oil and water repellency and is easily removed by laundering, whereas the polymer grafted onto the inner structure is hardly eliminated but does not impart oil and water repellency to the fabric.     

Kinetics study of radiation‐grafting of acrylic acid,acrylonitrile, and their mixture onto wool fabric

The effect of monomer concentration, exposure time, irradiation temperature, and weaving direction on the kinetics of grafting acrylic acid (AA), acrylonitrile (AN), and their mixture onto wool fabric has been studied at the dose rate of 1.38 Gy/s. The degree of grafting is found to depend on the methanol‐to‐water solvent ratio and fabric‐to‐liquor ratio. The grafting rate and rate constant are dependent on irradiation temperature, type of grafted monomer, and weaving direction. The grafting rates increase with the increase in irradiation temperature (276–308 K). The calculated activation energy is nearly the same (16.4–17.2 kJ mol^?1) and the preexponential rate constant is dependent on the type of grafted monomer. The grafting of AA, AN, and their mixture are confirmed from the dyeing affinity of grafted fabrics towards Sandocryl Blue (SB), a basic dye. The formation of wool grafts and structural changes resulting from grafting were verified by using FTIR spectrometry and X‐ray diffraction analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4328–4340, 2006     

Multifunctional wool fiber treated with <Emphasis Type="Italic">ɛ</Emphasis>-polylysine

A creative method for fabricating environmentally-benign multifunctional wool fibers was established and reported. Through coating the wool fibers with ɛ-polylysine, the surface morphology and biochemical properties of the fibers were altered, enhancing their antimicrobial, hygroscopic and finished properties. The process of ɛ-polylysine coating was dependent on the solution environment, which influenced the electrostatic interactions between ɛ-polylysine molecules and wool fibers. The results showed that a maximum ɛ-polylysine coating (23.60 mg/g) on the surface of wool fibers was reached when wool fibers were soaked at 50 °C for 2 h in the solution with 10% on weight of fabric (owf) ɛ-polylysine and pH 8.0. The coated wool fiber showed promising antimicrobial rates of 96.98% and 97.93% against Escherichia coli and Micrococcus luteus, respectively. The wool fiber coated with the ɛ-polylysine was more hydrophilic than the uncoated wool fabrics. The functional wool fibers after water scrubbing for two times still have good antibacterial efficiency against Escherichia coli and Micrococcus luteus, and antimicrobial rates were 96.77% and 97.33%, respectively. This study shows that wool fibers modified by the nontoxic ɛ-polylysine have a great potential to be used in constructing multifunctional textiles.     

Surface modification of synthetic fiber nonwoven fabrics with poly(acrylic acid) chains prepared by corona discharge induced grafting

The surface modification of synthetic fiber fabrics via corona discharge treatment and subsequent graft polymerization was investigated. Polyethylene (PE) nonwoven fabric and polyamide-6 (PA-6) nonwoven fabric were used as base fabrics. Acrylic acid (AAc) was graft polymerized onto the fabrics via corona discharge pre-treatment. The grafted amounts of PAAc were dependent on the grafting time, that of PA-6 being higher than that of PE. It was confirmed that the surface of the fibers constructing the fabric was fully covered with PAAc after the 20 min reaction. The surface of the PAAc grafted fabrics was characterized by X-ray photoelectron spectroscopy. The leakage of electrostatic charge from the fabric was determined and the dyeability was studied with methylene blue. The period of time in which the charge potential attenuated to 1/2 of the initial potential decreased drastically by grafting with PAAc. The grafted amount was enough for dyeing the entire fabrics.     

Lipases improve the grafting of poly(ethylene terephthalate) fabrics with acrylic acid

In this study, poly(ethylene terephthalate) (PET) fabrics were modified with two types of commercial lipases, namely, Lipex and Lipolase, and grafted with acrylic acid (AA) to improve their absorption properties. The effects of the enzyme concentration, reaction temperature, time, and pH on the grafting of AA onto PET were investigated. The pretreatment of PET with lipases increased the amount of AA that was introduced to the PET fibers, whereas AA grafting onto the untreated PET fabrics led to lower graft yields. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the AA‐grafted pretreated polyester fabrics. A new band appearing at 1546 cm^?1 in the Fourier transform infrared spectrum implied that AA was introduced onto the PET fabrics. The surfaces of the fabric fibers presented in scanning electron microscopy micrographs clearly indicated the formation of a layer of grafted poly (acrylic acid). The results show that the density of surface grafting was improved by the lipase pretreatment. The increase in grafting was higher for Lipex than for Lipolase. The highest graft yield was obtained with 1% Lipex and Lipolase for 30 min at pH values of 7 and 5, respectively. There were no significant changes in the tenacity or weight reduction of the fabrics. The moisture content of the samples increased linearly with increasing graft yield. This was higher for the pretreated fabrics grafted with Lipex. A higher color strength was obtained for grafted PET samples that were pretreated with Lipex when they were dyed in alkaline aqueous solutions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dyeing of glass fiber fabrics having amino groups with acid dyestuff and after-chroming

The glass fiber fabrics treated with a coupling agent that contains aminoethyl groups are used as a dye with a procedure similar to that for nylon with acid dyestuff and after-chroming. Furthermore, we investigated the dyeing parameters and physical properties. Results revealed that the glass fiber fabrics treated with the coupling agent were dyeable. The best conditions for acid dyestuff are at pH = 6 and at 5% owf (on the weight of fiber) concentration of dyestuff; for after-chroming, they are at 1.4% owf concentration of potassium dichromate and at 70°C for 50 min. In addition, the fabrics dyed have much better colorfastness (4–5 grade), and the average dyeing evenness is lower than 1.5. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1039–1048, 1997     

Preparation of chelating fabrics by radiation‐induced grafting of itaconic acid and acrylonitrile onto polypropylene nonwoven fabrics and subsequent amination of graft copolymer

A mixture of acrylonitrile (AN) and itaconic acid (IA) was cografted onto polypropylene (PP) nonwoven fabrics by preirradiation method. The effects of graft polymerization conditions such as temperature, reaction time, Mohr's salt concentration, solvent mixture ratio, and comonomer composition on the total grafting yield were investigated. The addition of AN as a comonomer increased the amount of IA that reacted with PP fabrics. An increase in the temperature from 40 to 60°C increased the grafting rate, but the final grafting yield decreased at high temperature. The addition of 0.01 wt % Mohr's salt to the reaction medium leaded to a sharp increase of grafting yield. The accelerative effect of solvent medium on the grating yield was higher in dimethylformamide (DMF) and methanol mixtures, when compared with DMF or methanol. Chelating fabrics was synthesized by subsequent amination of grafted fabric with ethylene diamine (EDA) and phenylhydrazine (PH). The conversion yield reached maximum value at about 90% for 80% PP‐g‐AN‐IA fabrics at 90°C. At same amination conditions, the conversion yield is higher when PP‐g‐AN‐IA fabrics react with EDA compared with PH. FT‐IR data indicate that amine groups were introduced onto PP‐g‐AN‐IA fabric through amide linkage between grafted AN or IA and EDA or PH. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of surface properties of wool fabric with linde type a nano‐zeolite

Wool is a naturally occurring composite fiber consisting of keratin and keratin‐associated proteins as the key molecular components. The outermost surface of wool comprises a lipid layer that renders the surface hydrophobic, which hinders certain fabric processing steps and moisture management properties of wool fabrics. In this study, Linde Type A (LTA) nano‐zeolite (a Na⁺‐, Ca²⁺‐, and K⁺‐exchanged type A zeolite) was integrated onto the surface of wool using 3‐mercaptopropyl trimethoxy silane as a bridging agent. The resultant surface morphology, hydrophilicity, and mechanical performance of the treated wool fabrics were evaluated. Notably, the surface hydrophilicity of wool increased dramatically. When wool was treated with a dispersion of 1 wt % zeolite and 0.2 wt % silane, the water contact angle decreased from an average value of 148° to 50° over a period of approximately 5 min. Scanning electron microscopic imaging indicated good coverage of the wool surface with zeolite particles, and infrared spectroscopic evaluation demonstrated strong bonding of the zeolite to wool keratins. The zeolite application showed no adverse effects on the tensile and other mechanical properties of the fabric. This study indicates that zeolite‐based treatment is potentially an efficient approach to increasing the surface hydrophilicity and modifying other key surface properties such as softness of wool and wool fabrics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42392.     

Photoinduced grafting of vinyl benzyl trimethyl ammonium chloride on polyester nonwoven fabric with surfactant coating and its anion‐exchange properties

Vinyl benzyl trimethyl ammonium chloride (VBTAC) could be efficiently and stably grafted onto polyester fiber coated with a surfactant polyester (PET) by a photoirradiation‐induced graft polymerization with benzophenone as the photoinitiator without any cografting monomer required. The degree of VBTAC grafting could be controlled simply by the irradiation time and concentration of VBTAC in the monomer solution. The anion‐exchange capacity (AEC) of the PET‐g‐VBTAC fabrics increased with increasing degree of grafting up to 80 ± 5% and then leveled off. The maximum AEC of PET‐g‐VBTAC was 2.2 mequiv/g; this was similar to that of a commercial anion‐exchange resin (2.16 ± 0.04 mequiv/g) and much higher than those of nylon‐g‐VBTAC–2‐hydroxyethyl methacrylate fabrics (≤1.0 mequiv/g) prepared with a conventional cografting system. The grafted fabric was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy studies, and the sorption selectivity for anions and regeneration efficiency were estimated. The results suggest that the grafting system, in which VBTAC alone was grafted onto PET fiber coated with surfactant, was more practical and effective for the preparation of the VBTAC‐containing anion exchanger, and the resulting PET‐g‐VBTAC fabrics could be used as an effective anion exchanger. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41674.     

Chemical grafting of curcumin at polyethylene terephthalate woven fabric surface using a prior surface activation with ultraviolet excimer lamp

Durable curcumin‐treated antibacterial polyethylene terephthalate (PET) fabrics (against Staphylococcus aureus) were produced by dyeing with curcumin after surface activation using vacuum ultraviolet excimer lamp at 172 nm. Surface change properties of the exposed fabrics were characterized by surface analysis methods such as wettability, atomic force microscopy, and X‐ray photoelectron spectroscopy. Results show an increase in surface hydrophilicity with a water contact angle of the PET fabric reaching 24° after 10 min excimer irradiation, which could be attributed to an increase in carboxyl group formation as confirmed by X‐ray photoelectron spectroscopy measurements. Varying concentrations of curcumin were immobilized onto untreated and vacuum ultraviolet‐irradiated PET samples using diffusion method at 90°C, and the treated fabrics characterized using K/S (color strength) values at 440 nm. K/S values increased when the PET surface was subjected to a prior excimer irradiation, because of grafting of curcumin at the PET surface. Increased excimer irradiation time increased grafting of curcumin because the inner fabric fiber surfaces were also more thoroughly treated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of novel pyridinium N‐chloramine precursors and its antimicrobial application on cotton fabrics

To control pathogenic microbial contamination on polymeric material surface, it is pivotal to develop materials with efficacious antimicrobial activity. Two pyridinium N‐chloramine precursors containing a siloxane handle were synthesized, characterized, and grafted onto cotton fabrics. The attenuated total reflectance spectra and scanning electron microscope photo analysis indicated that the cotton fabric surface was successfully modified. The resultant chlorinated fabric samples were challenged against bacteria Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 25923. Results showed that: (1) the surface modified cotton fabrics displayed satisfactory biocidal efficacy; (2) the precursor structure played a major role on surface grafting and antibacterial activity. This work provides two promising pyridinium N‐chloramine precursors which hold potential application for preparing antibacterial textile materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45323.     

Antibacterial activities of acrylic acid-grafted polypropylene fabric and its metallic salt

Acrylic acid (AAc) was grafted onto polypropylene (PP) fabric by a preirradiation method using a ⁶⁰Co gamma ray. The effects of the absorbed dose, the reaction temperature, reaction time, storage time, as well as the addition effect of ferrous ion and sulphuric acid on the degree of grafting, were determined. It was shown that the synergistic effect of a strong acid with ferrous sulfate can increase the grafting yield. Antibacterial activities on metallic complexes of acrylic acid-grafted polypropylene (AAc-g-PP) fabric were evaluated by a viable cell counting method. An Ag complexed fabric had strong biocidal effect for all bacteria. Fe, Cu, and Zn complexed fabrics had different antibacterial activities depending on each bacterium. However, AAc-g-PP fabric and Ni-complexed fabric did not have bactericidal effect. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2213–2220, 1998     

GMA改性磷酸腺苷的制备及其对棉织物的阻燃整理

为了提高磷酸腺苷单体在棉织物上的接枝改性程度及其阻燃效果，采用甲基丙烯酸缩水甘油酯（GMA）对一磷酸腺苷（AMP）、二磷酸腺苷（ADP）、三磷酸腺苷（ATP）进行改性，制得三种带有不饱和双键的阻燃单体AMP-m-GMA、ADP-m-GMA、ATP-m-GMA；然后通过紫外光接枝法将三种阻燃单体分别接枝到棉织物上，制备光接枝AMP-m-GMA、ADP-m-GMA和ATP-m-GMA阻燃棉织物；对三种阻燃单体进行了结构表征和热稳定性分析，并探究了三种阻燃单体光接枝阻燃棉织物的热稳定性、阻燃性能、燃烧行为和残炭结构。结果表明，三种磷酸腺苷通过GMA环氧基开环引入不饱和双键，且具有良好的热稳定性。相比于原棉织物，三种阻燃棉织物的最大热降解速率分别降低了60.0%、52.0%、60.0%，极限氧指数由16.1%分别提升到25.4%、27.4%、26.4%，织物热释放速率分别下降了15.09%、60.47%、37.82%，说明三种磷酸腺苷阻燃单体均有助于棉织物形成致密炭层，阻止热量扩散，获得良好的阻燃效果。其中，光接枝ADP-m-GMA阻燃棉织物的增重率可达22.4%，燃烧后损毁长度由30 cm缩短至14.2 cm，表现出更优异的阻燃性能。     

The graft photopolymerization of acrylates and methacrylates on wool in dimethyl sulfoxide

Irradiation of wool by short-wavelength ultraviolet light in the presence of acrylate or methacrylate esters in dimethyl sulfoxide causes intermediate grafts (2%–10%) of polymer on the surface of the wool. The amount of grafting and homopolymerization and the evenness and regularity of photografted polymer are dependent upon the monomer used. With methyl acrylate, the reaction time, monomer concentration, and introduction of water as cosolvent affect the degree of fiber grafting and the amount and molecular weight of accompanying homopolymer. Polymers grafted onto wool by this technique change the tensile properties and the water desorption characteristics of the wool.     

Novel feature of nano‐titanium dioxide on textiles: Antifelting and antibacterial wool

In this study, the antifelting and antibacterial features of wool samples treated with nanoparticles of titanium dioxide (TiO₂) were evaluated. To examine the antifelting properties of the treated samples, the fabric shrinkage after washing was determined. The antimicrobial activity was assessed through the calculation of bacterial reduction against Escherichia coli (Gram‐negative) and Staphylococcus aureus (Gram‐positive) bacteria. TiO₂ was stabilized on the wool fabric surface by means of carboxylic acids, including citric acid (CA) and butane tetracarboxylic acid (BTCA). Both oxidized samples with potassium permanganate and nonoxidized wool fabrics were used in this study. The relations between both the TiO₂ and carboxylic acid concentrations in the impregnated bath and the antifelting and antibacterial properties are discussed. With increasing concentration in the impregnated bath, the amount of TiO₂ nanoparticles on the surface of the wool increased; subsequently, lower shrinkage and higher antibacterial properties were obtained. The existence of TiO₂ nanoparticles on the surface of the treated samples was proven with scanning electron microscopy images and energy‐dispersive spectrometry. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improving the colour fastness of dyed nylon‐6 fabric by graft copolymerisation and curing of acrylic acid

The influence of grafting and grafting–curing of acrylic acid on the colour fastness of nylon‐6 fabric dyed with an acid dye of low wash fastness was investigated. The variables involved in grafting were initially optimised for pristine nylon‐6 fabric prior to grafting the same monomer onto the dyed fabrics. The highest graft yield achieved for the pristine and dyed nylon‐6 fabrics was 44 and 14% respectively. Grey scale testing and colorimetric analysis revealed that the highest colour fastness and the smallest drop in colour strength belonged to the dyed–grafted–cured nylon‐6 fabric. The colour components were measured, and the total colour difference of each sample after five washing cycles was computed. The specific colour difference showed that the implementation of either grafting or grafting–curing processes will alter the reference colour of the dyed fabric. The tensile strength of the grafted and grafted–cured fabrics was respectively 2.7 and 6.3% lower than that of dyed nylon‐6.     

New Approach for Imparting Antimicrobial Properties for Polyamide and Wool Containing Fabrics

Direct fiber polymer/antibiotic interaction is a promising means of providing infection resistance textile fabrics. Ionic interaction between cationic reactive groups (antibiotic) and carboxylic groups in wool, wool/polyamide, wool/polyester, and polyamide was used as a tool to develop desirable, durable antimicrobial fabrics.

The finishing conditions such as pH, finishing temperature, and time were studied.

The results revealed that pH of the finishing bath and the antibiotic concentration as well as finishing temperature were very critical parameters in affecting exhaustion of the antibiotic by the fabric along with the extent of ionic interactions. Sorption of doxymycin antibiotic follows the descending order: wool > wool blends>polyamide. Zone of inhibition of all treated fabrics is governed by the pH and follows the descending order: pH 6.5 > pH9 > pH 2.3.

FTIR Spectroscopy confirmed the ionic interaction between wool 100%, wool/polyamide (50%/50%) and doxymycin, because of appearance of new bands at 1641 cm^?1 which attributed to NH₂ deformation amide I and band at 1514 cm^?1 corresponding to amide II (in case of wool 100%). For wool/polyamide blend it is noticed that appearance of new bands at 1415 cm^?1 corresponding to C-N stretching (amide III band for CONH₂, in addition to the appearance of new band at 927 cm^?1 which could be assignments for CO-NH in plane.

Reusing of the treatment bath was tried and proved to be very effective approach to produce infection-resistant biomaterials for medical applications.     

Synthesis and characterization of novel grafted amphoteric poly(propylene) fabrics

Novel grafted amphoteric poly(propylene) (PP) fabrics were prepared by γ‐irradiation, which induced grafting of methacrylic acid (MA) onto PP fabric. A subsequent reaction of PP–MA grafted chains with freshly prepared (3‐chloro‐2‐hydroxylpropyl)amine or diamine chloride compounds followed by purification yielded the corresponding amphoteric PP fabrics. The latter were characterized by elemental microanalysis for the determination of the percentage nitrogen. Fourier transform infrared and scanning electron microscopy were performed on methacrylic and amphoteric PP fabrics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2504–2510, 2003