Polymerization of a hydantoinylsiloxane on particles of silicon dioxide to produce a biocidal sand

The monomer 3‐triethoxysilylpropyl‐5,5‐dimethylhydantoin has been polymerized on the surfaces of sand particles to produce an adhered film that, upon chlorination with dilute sodium hypochlorite bleach, becomes biocidal. The biocidal efficacy of this coated sand has been demonstrated in a cartridge filter experiment against the bacterial pathogens Staphylococcus aureus and Escherichia coli. Complete inactivation was observed within 1 min of contact for the former bacterium and in the interval of 1–5 min for the latter. Upon a loss of biocidal activity due to the depletion of bound chlorine, the coated sand particles can be recharged by further exposure to dilute bleach. Synthetic methods and test data are presented. Potential uses of biocidal sand include disinfection and odor control in water treatment facilities and recirculating baths. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1161–1166, 2005     

Antimicrobial silica and sand particles functionalized with an N‐halamine acrylamidesiloxane copolymer

The monomer 2‐acrylamido‐2‐methyl‐1‐(5‐methylhydantoinyl)propane (HA) was copolymerized with 3‐(trimethoxysilyl)propyl methacrylate (SL) and covalently attached onto silica gel and sand particles. As a result HASL copolymer‐grafted silica gel and sand particles (HASL SGPs and SPs) were obtained. These two types of HASL SGPs and SPs provided excellent biocidal efficacy against Gram positive S. aureus and Gram negative E. coli O157:H7 bacteria when the copolymer‐grafted particles were exposed to dilute sodium hypochlorite (household bleach) solution. In a flowing water application, seven logs of bacteria were inactivated within 10 s of contact time with the particles packed into a column. The treated particles also exhibited good washing and storage stabilities. The chlorine loss during extensive flow could be recovered by further exposure to dilute bleach solution. The antimicrobial particles have potential application for use in inexpensive disinfecting water filters for slow water flows. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43413.     

Modification of silica gel,cellulose, and polyurethane with a sterically hindered N‐halamine moiety to produce antimicrobial activity

The sterically hindered amine monomer 4‐[3‐triethoxysilylpropoxyl]‐2,2,6,6‐tetramethylpiperidine has been synthesized and covalently bonded to the surfaces of silica gel particles and cellulose (cotton) and copolymerized in a polyurethane coating formulation. Upon exposure to dilute sodium hypochlorite (household bleach), a very stable N‐Cl bond is formed in situ at the hindered amine nitrogen site. This source of oxidative chlorine provides an antimicrobial function to the silica gel, cotton, and polyurethane. Stability, regenerability, and biocidal efficacy data are presented. The new N‐halamine materials were remarkably effective against Staphylococcus aureus and Escherichia coli O157 : H7 in brief periods of contact. The materials should find application in water treatment and medical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Biocidal polystyrene beads. III. Comparison of N‐halamine and quat functional groups

A comparison has been made between the biocidal efficacies of N‐chlorinated polymeric beads and two derivatives of polyquat beads. Biocidal effects were measured after brief contact exposures of aqueous suspensions of either Staphylococcus aureus or Escherichia coli to the water‐insoluble beads. The polymeric backbone was held the same in all three types of beads, so they differed only in their biocidal derivative moieties. In all cases, functionalization of crosslinked chloromethylated polystyrene beads was performed to introduce the biocidal properties. Synthetic methods and test data will be presented. The most effective biocide, as measured by degree of inactivation in the shortest contact time of the two species of bacteria, was the N‐chlorinated hydantoinyl derivative of methylated polystyrene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 363–367, 2004     

Biocidal polystyrene beads. IV. Functionalized methylated polystyrene

Crosslinked chloromethylated polystyrene beads were reacted with hydantoin and imidazolidinone derivatives to produce functionalized beads which could be rendered biocidal upon reaction with free chlorine or bromine. The biocidal efficacies of the N‐chlorinated, and in one case, the N‐brominated polymeric beads against Staphylococcus aureus and Escherichia coli O157:H7 in aqueous suspension have been determined. Synthetic methods and test data have been presented. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 368–372, 2004     

Antimicrobial functionalization of poly(ethylene terephthalate) fabrics with waterborne N‐halamine epoxides

A water dispersible terpolymer of [2‐(methacryloyloxy)ethyl]trimethylammonium chloride, glycidyl methacrylate and hydantoinyl acrylamide was synthesized and coated on poly(ethylene terephthalate) fabrics through a pad‐dry‐cure procedure. The coatings were rendered biocidal upon exposure to dilute household bleach solution. The halogenated fabrics exhibited great antimicrobial functionality with about six logs inactivation of S. aureus and E. coli O157:H7 within only two min of contact time. Moreover, the coatings were found to be very stable against repeated washings and UVA light exposure. It was shown that [2‐(methacryloyloxy)ethyl]trimethylammonium monomer is very useful in preparing waterborne N‐halamines which can impart rechargeable, effective, and stable antimicrobial coatings to poly(ethylene terephthalate) fabrics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43088.     

Multifunctional cotton fabric: Antimicrobial and durable press

2‐Amino‐2‐methyl‐1‐propanol (AMP) was coated onto cotton fabric with 1,2,3,4‐butanetetracarboxylic acid (BTCA) as a crosslinking agent to simultaneously impart antimicrobial and durable‐press functionalities. The coatings were characterized and confirmed by attenuated total reflectance–IR and thermogravimetric analysis. The coated fabrics were rendered biocidal upon exposure to dilute household bleach, and the chlorinated swatches exhibited about 6 log reductions of Escherichia coli O157:H7 and Staphylococcus aureus within 5 min of contact time. A concentration of 1.5 wt % AMP was sufficient to produce this biocidal efficacy. Increasing the BTCA content of the coating improved the wrinkle recovery angle. The coatings were very stable toward repeated laundering, and they exhibited sufficient halogen storage stabilities for industrial applications. A photolytic decomposition was observed when the coatings were exposed to UVA light. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Antimicrobial polyester

Two N‐halamine siloxane precursors, 5,5‐dimethyl‐3‐(3′‐triethoxysilylpropyl)hydantoin and 3‐(3′‐triethoxysilylpropyl)‐7,7,9,9‐tetramethyl‐1,3,8‐triazaspiro[4.5]decane‐2,4‐dione, have been synthesized and coated onto polyester fiber surfaces. The coated polyester was rendered biocidal after exposure to household bleach solution by converting the heterocyclic precursors to N‐halamine moieties. The thermal properties of these coated polyester samples were determined with differential scanning calorimetry. The chlorinated polyester swatches were challenged with Staphylococcus aureus (ATCC 6538) and Escherichia coli O157 : H7 (ATCC 43895) with contact times ranging from 1 to 30 min. The biocidal testing showed that the chlorinated samples inactivated S. aureus and E. coli O157 : H7 within 5 and 30 min of contact, respectively. Standard washing tests indicated that the chlorinated coated fibers were very resistant to loss of the coating through hydrolyses. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and application to cellulose of reactive dye precursor of anti‐bacterial N‐halamine

To achieve textile dyeing and functional finishing in one process, a bleach‐resistant reactive dye precursor to anti‐bacterial N‐halamine was synthesised by reacting a type of dichlorotriazine reactive dye with 4‐amino‐2,2,6,6‐tetramethylpiperidine. The synthesised compound, which can be transformed to an N‐halamine molecule by exposure to dilute bleach solution, was used to dye cotton fabrics. After exposure to a dilute sodium hypochlorite solution, dyed cotton fabrics showed excellent anti‐bacterial properties against Staphylococcus aureus and Escherichia coli O157:H7, facilitating a ca. 6‐log reduction in bacteria within a short period of contact. Compared with the dichlorotriazine reactive dye, the reactive dye precursor demonstrated comparable dyeing properties including exhaustion and fixation values. No differences in rub fastness, wash fastness or bleach fastness were detected between fabrics dyed with, respectively, dichlorotriazine reactive dye and the reactive dye precursor to N‐halamine.     

Amidoxime copolymer beads containing Cu/Cu2O microparticles as a biocidal material for water disinfection

Macroporous crosslinked acrylonitrile‐divinylbenzene copolymer beads were synthesized by suspension polymerization technique. The beads were chemically modified to have amidoxime functional group, which was used as a solid support for anchoring copper microparticles. The copper ions loaded on the copolymer beads were reduced using strong reducing agent to have copper microparticles on the amidoxime copolymer beads. The size of copper particles formed depends upon the amount of copper ions loaded on the beads. The formation of copper microparticles on the copolymer was confirmed by instrumental analysis. The copper containing amidoxime copolymer beads were investigated for the biocidal activity. The size and the distribution of copper particles on the amidoxime copolymer beads influenced their biocidal activity. The biocidal activity was tested against two Gram‐positive bacteria, Bacillus subtilis and Staphylococcus aureus, and against two Gram‐negative bacteria, Pseudomonas aeruginosa and Escherichia coli. The beads containing copper particles showed better biocidal activity against the Gram‐negative bacteria when compared with the Gram‐positive organisms. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

N‐(hydroxymethyl) acrylamide as a multifunctional finish to cotton and a tether for grafting methacrylamide for biocidal coatings

N‐(hydroxymethyl) acrylamide (NMA) was immobilized on cotton surfaces through etherification, and then methacrylamide (MA) was grafted onto the treated surface. The coatings were characterized by ATR‐IR spectroscopy and were rendered biocidal upon exposure to dilute household bleach. The treated fabrics were challenged with Gram‐negative and Gram‐positive bacteria; both NMA and NMA/MA‐treated fabrics inactivated about 8 logs of Escherichia coli O157:H7 and Staphylococcus aureus within only 5 min of contact time. The coatings were also quite stable toward ultraviolet (UVA) light exposure and repeated laundering. Moreover, a substantial improvement in wrinkle recovery angle was obtained for the NMA/MA‐treated fabrics. The new acyclic acrylamide N‐halamine coating should be less expensive to produce and use than previous cyclic N‐halamine coatings developed in these laboratories. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Antimicrobial N‐halamine coatings synthesized via vapor‐phase assisted polymerization

An N‐halamine monomer, 3‐allyl‐5,5‐dimethylhydantoin (ADMH), was synthesized by a Gabriel reaction of 5,5‐dimethylhydantoin and 3‐bromopropene. Antimicrobial coatings of poly[1‐(4,4‐dimethyl‐2,5‐dioxoimidazolidin‐1‐methyl)ethylene] were prepared on plasma‐treated PET fabrics via a vapor‐phase assisted polymerization (VAP) process using gasified ADMH as monomer. The coatings endow the PET fabrics with an antimicrobial efficiency greater than 80% for both Escherichia coli and Staphylococcus aureus after chlorination of the N‐halamine polymer with dilute bleach solution. The obtained antimicrobial effect has remarkable durability that can bear over 30 times of stringent laundering tests. Compared with other antimicrobial finishing methods, the VAP methodology offers great advantages in needless of organic solvents and small consumption of monomer. It has potential applications in a wide variety of fields such as hygienic clothing, underwear, socks, and medical textiles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41824.     

Novel regenerable N‐halamine polymeric biocides. II. Grafting hydantoin‐containing monomers onto cotton cellulose

A novel cyclic‐amine monomer, 3‐allyl‐5,5‐dimethylhydantoin (ADMH) was synthesized with good yield by the reaction of allyl bromide with 5,5‐dimethylhydantoin (DMH), and was characterized by FTIR and ¹H‐NMR spectra. ADMH alone cannot be grafted onto other polymers. However, the presence of acrylonitrile markedly enhanced the ADMH graft yield onto cotton cellulose. The influence of reaction conditions on the graft copolymerization was investigated. After chlorine bleach treatment, hydantoin units in the grafted copolymers were easily transformed into N‐halamine structures. Grafted samples exhibited potent antibacterial activity against Escherichia coli, and the functional properties were shown to be durable and regenerable. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 617–624, 2001     

Preparation and optical properties of an all‐polymer light modulator using colored N‐isopropylacrylamide gel particles in a gel‐in‐gel system

A novel all‐polymer light modulator with a gel‐in‐gel system was developed. The gel‐in‐gel system was constructed with colored gel particles responsive to stimuli held independently in another stimuli‐nonresponsive gel matrix. Well‐known thermoresponsive N‐isopropylacrylamide (NIPAM) gel particles containing a pigment were dispersed and fixed in an outer stimuli‐nonresponsive gel matrix. When poly(vinyl alcohol)–styrylpyridinium (PVA–SbQ) was used for the outer gel matrix, the light modulator showed excellent color‐changing properties because the PVA–SbQ matrix was selectively formed around the NIPAM gel particles and the particles exhibited a large volume change in the matrix. The temperature when the outer gel matrix was formed affected the haze of the light modulator. When the outer gel matrix was formed in the swollen state of the NIPAM gels, the haze of a light modulator increased with heating. On the contrary, the haze of a light modulator prepared in the shrunken state of the NIPAM gels decreased with heating. The response time of the color change was less than 1 s. The gel‐in‐gel system made a very fast macroscopic color change, taking advantage of the fast response of the micrometer‐sized gel particles. We believe that a light modulator with a gel‐in‐gel system may find various applications in optical devices. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2295–2303, 2007     

Synthesis of polysiloxane with 5,5‐dimethylhydantoin‐based N‐halamine pendants for biocidal functionalization of polyethylene by supercritical impregnation

An N‐halamine precursor 3‐(3‐hydroxypropyl)‐5,5‐dimethylhydantoin (HPDMH) has been synthesized. The N‐halamine precursor was reacted with poly(methylhydrosiloxane) (PMHS) to produce a biocidal polysiloxane with 5,5‐dimethylhydantoin‐based N‐halamine pendants through silane alcoholysis and subsequent chlorination of hydantoin ring with tert‐butyl hypochlorite. The N‐halamine polysiloxane was impregnated into inert polyethylene (PE) fibers and formed a 68‐nm coating layer in supercritical carbon dioxide (scCO₂) for antibacterial application. The PE fibers before and after impregnation were characterized by XPS and SEM. The N‐halamine polysiloxane impregnated PE samples provided effective biocidal activities against both Staphylococcus aureus and Escherichia coli compared with unmodified ones that did not display obvious antibacterial activities. The coating layer on PE substrate was stable toward washing cycles, storage, and UV irradiation and the rechargeability of lost active chlorines was good. The scCO₂ impregnation approach uses environmentally friendly CO₂ as solvent and can be applied to both reactive and nonreactive substrates since it does not require covalent bonds to tether biocidal moieties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44721.     

Novel regenerable N‐halamine polymeric biocides. III. Grafting hydantoin‐containing monomers onto synthetic fabrics

A novel cyclic‐amine monomer, 3‐allyl‐5,5‐dimethylhydantoin (ADMH) was synthesized and characterized. ADMH alone could not be grafted onto ordinary polymers. However, the presence of triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TATAT) remarkably enhanced the ADMH grafting yield onto synthetic fabrics. The influences of reaction conditions on the grafting copolymerization were investigated. After chlorine bleach treatment, hydantoin units in the grafted copolymers were transformed into N‐halamine structures. Treated samples exhibited potent antibacterial activity against Escherichia coli, and the functional properties were shown to be durable and regenerable. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1517–1525, 2001     

Antibacterial property on Gram‐positive bacteria of polypyrrole‐coated fabrics

Antibacterial activity against Gram‐negative bacteria of polypyrrole‐coated fabrics has been demonstrated in the past. In this work, biocidal efficacy of polypyrrole has been evaluated against Gram‐positive bacteria on textiles with different polypyrrole loading. Excellent bacterial reduction (≥99%) was found on cotton fabrics containing more than ～9 wt % of polypyrrole. Polypyrrole loading can be greatly reduced in presence of silver. Silver‐containing fabrics used in this work alone does not guarantee a complete biocidal effect, but the addition of just 2 wt % of polypyrrole showed a bacteria reduction of 99%. Moreover, stability to different washing procedures of the antibacterial activity was evaluated. Fabrics were characterized by scanning electron microscopy, energy dispersive X‐ray analysis, and infrared spectroscopy. Stability of the coating was assessed by abrasion tests. PPy showed excellent fastness to abrasion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41670.     

Durable antibacterial finish on cotton fabric by using chitosan‐based polymeric core‐shell particles

Cotton fabric with excellent antibacterial durability was obtained when treated with chitosan‐containing core‐shell particles without any chemical binders. These amphiphilic nanosized particles with antibacterial chitosan shells covalently grafted onto polymer cores were prepared via a surfactant‐free emulsion copolymerization in aqueous chitosan. Herein, two core‐shell particles, one with poly(n‐butyl acrylate) soft core and another with crosslinked poly(N‐isopropylamide) hard core, were synthesized and applied to cotton fabric by a conventional pad‐dry‐cure process. Antimicrobial activity was evaluated quantitatively using a Shake Flask Method in which the reduction of the number of Staphylococcus aureus cells was counted. The results showed that treated fabric had an excellent antibacterial property with bacterial reduction higher than 99%. The antibacterial activity maintained at over 90% reduction level even after 50 times of home laundering. The fabric surface morphology as well as the effect of latex particles with different core flexibilities on fabric hand, air permeability, break tensile strength, and elongation was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1787–1793, 2006     

Preparation of antibacterial cellulose with s‐triazine‐based quaternarized N‐halamine

To reduce the neutral salt used in the textile finishing with s‐triazine derivatives, a novel s‐triazine‐based quaternarized N‐halamine precursor was synthesized by two simple steps and characterized by H‐NMR and FT‐IR. This compound can be effectively coated onto cellulose by nucleophilic substitution process without neutral salt. The treated cellulose was rendered with powerful biocidal efficacy after transferring to an N‐halamine structure by exposing to dilute sodium hypochlorite solution through the synergistic antimicrobial effect quaternary ammonium salt and N‐halamine. The chlorinated samples could inactivate 6‐logs of Staphylococcus aureus and Escherichia coli O157:H7 within 1 min and 5 min, respectively. In addition, about 50% of oxidant chlorine remained after 50 washing cycles and 30 days storage, and all of the lost active chlorines in the N‐halamine molecules recovered after exposing to bleach solution. With these advantages, the as‐prepared antimicrobial fabrics will have potential application, especially in the medical and healthcare textiles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44998.     

Synthesis of lactose‐containing glycopolymer‐grafted silica gel particles

The surface free‐radical graft polymerization of 2‐O‐meth‐acryloyloxyethoxyl‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D ‐galactopyranosyl)‐(1‐4)‐2,3,6‐tri‐O‐acetyl‐β‐D ‐glucopyranoside onto silica gel particles has been carried out with azobis (isobutyronitrile) as initiator. The grafting reaction conditions and the glycopolymer‐grafted silica gel particles have been investigated in detail. Chromatographic experiments have been attempted on glycopolymer‐modified silica gel particles as a stationary phase under normal phase conditions, and it was found that a certain separation effect of the quercetin and its derivant isorhamnetin was achieved. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010