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     

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     

Synthesis and properties of some fluorescent 1,8‐naphthalimide derivatives and their copolymers with methyl methacrylate

Six new fluorescent derivatives of 1,8‐naphthalimide were synthesized. Three were dyes, and three were fluorescent whitening agents (FWAs) containing a tetramethylpiperidine (TMP) stabilizer fragment. The FWAs were obtained under phase‐transfer catalysis conditions. Five of the compounds were copolymerized with methyl methacrylate, so copolymers with an intense color and/or fluorescence stable against solvents were obtained. The chemical bonding of the synthesized monomers in the polymers was confirmed spectrophotometrically. The participation of the monomer compounds did not significantly affect the process of copolymerization or the molecular masses of the obtained copolymers. The quantity of chemically bonded naphthalimide monomer in the copolymers was determined to be over 60%. The spectral properties of the compounds and their photostability in solution and in the copolymers were studied. The influence of the compounds on the photostability of the copolymers was determined. The compounds, especially those containing a stabilizer (TMP) fragment in their molecules, showed a positive stabilizing effect on the photodegradation of poly(methyl methacrylate). Polyamide fabrics with 2‐allyl‐6‐hydrazino‐benzo[de]isoquinoline‐1,3‐dione, 2‐allyl‐6‐(2‐amino‐ethylamino)‐benzo[de]isoquinoline‐1,3‐dione, and 2‐chloro‐N′‐(2‐methyl)‐1,3‐dioxo‐2,3‐dihydro‐1H‐benzo[de] isoquinoline‐6‐yl) acetohydrazide were dyed, and materials with an intense yellow color and fluorescence were obtained. Cotton fabrics were whitened with 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐methoxy‐benzo[de]isoquinoline‐1,3‐dione, 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐allyloxybenzo[de]isoquinoline‐1, 3‐dione, and 2‐[2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐1,3‐dioxo‐2,3‐dihidro‐1H benzo [de]isoquinoline‐6‐oxy]ethyl‐2‐methacrylate, and materials with bright whiteness and intense bluish fluorescence were obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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 refreshable N‐halamine polymeric biocides: Grafting hydantoin‐containing monomers onto high performance fibers by a continuous process

In this study, a continuous “pad‐dry‐cure” process was developed for the first time to graft a cycloamine monomer, 3‐allyl‐5,5‐dimethylhydantoin (ADMH), onto several high performance fibers, including Nomex, Kermel, and a PBI/Kevlar blend. The influence of reaction conditions on the grafting copolymerizaiton was studied. It was found that in the presence of a difunctional monomer, poly(ethylene glycol)–diacrylate (PEG–DIA), ADMH could be readily grafted onto these fibers. After exposure to chlorine, the hydantoin structures in the grafted samples could be transformed into N‐halamines, which provided powerful, durable, and regenerable antibacterial activities against both gram‐negative and gram‐positive bacteria. The influence of hydrophobic/rigid properties of the fabrics on grafting reactions as well as on their antibacterial activities was discussed, and the importance of full contact was emphasized. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1032–1039, 2003     

Durable and regenerable antimicrobial textile materials prepared by a continuous grafting process

A cyclic‐amine monomer, 3‐allyl‐5,5‐dimethylhydantoin (ADMH), was grafted onto various textile materials in a continuous finishing process to prepare durable and regenerable antibacterial textiles. Highly efficient radical grafting polymerizations occurred inside or on the surfaces of fibers with the assistance of different initiators. In the finishing process, particular factors such as types and concentrations of radical initiators, drying, and curing conditions were rather important in effecting the final grafts of ADMH on fabrics and were studied carefully. After exposure to chlorine, the grafted hydantoin structures in the samples could be transformed into N‐halamines, which provided powerful, durable, and regenerable antibacterial activities. The influence of hydrophilic/hydrophobic properties of the fabrics on the antibacterial activities was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1592–1599, 2002; DOI 10.1002/app.10456     

Synthesis and properties of polycarbonate copolymers of trimethylene carbonate and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate

The polycarbonate copolymers poly[trimethylene carbonate‐co‐2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate] [P(TMC‐co‐PTC)] were synthesized by the ring‐opening polymerization of trimethylene carbonate (TMC) and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as the catalysts. These copolymers were further reduced by a palladium/carbonate (Pd/C; 10%) catalyst to produce partly deprotected copolymers. These two types of copolymers were characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, UV spectroscopy, gel permeation chromatography, differential scanning calorimetry, and an automatic contact angle meter. The influences of the feed molar ratio of the monomers, the catalyst concentration, the reaction time, and the reaction temperature on the copolymerization process were also studied. The copolymerization of the TMC and PTC monomers was a nonideal copolymerization, and the copolymerization reactivity ratio of TMC was higher than that of PTC. In vitro degradation tests indicated that the partly deprotected copolymers possessed faster degradation rates and more hydrophilicity than the corresponding unreduced copolymers. Moreover, the degradation of these two type copolymers increased when the pH value of the buffer solutions decreased. In vitro drug‐release experiments showed that these two types of copolymers had steady drug‐release rates and good controlled release properties. Moreover, the partly deprotected copolymers had faster drug‐release rates than the corresponding unreduced copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Water‐soluble allyl and diallyl camphor sulfonamides‐based polyacrylamide copolymers for enhanced oil recovery

The monomers N‐allyl camphor sulfonamide (CSAP) and N,N‐diallyl camphor sulfonamide (CSDAP) were copolymerized with acrylamide (AM), acrylic acid (AA) for EOR, respectively. The effect of the synthesis conditions on apparent viscosity was investigated, and the copolymers were characterized by Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance (¹H NMR), environmental scanning electron microscope (ESEM), and thermogravimetric analysis (TGA). Increasing mass ratio of diallyl CSDAP could lead to the water‐insoluble of copolymer, and competition of free radicals could make polymerization of AM/AA/CSDAP more difficult than AM/AA/CSAP. The thickening function and temperature resistance of two copolymers were remarkably improved in comparison with similar molecular weight partially hydrolyzed polyacrylamide (HPAM). In addition, the pronounced temperature resistance of the copolymers has been also demonstrated by temperature resistance test. It has also found that copolymers AM/AA/CSAP and AM/AA/CSDAP brine solutions could obtain significant enhanced oil recovery at 70°C suggesting their potential being applied in chemical enhanced oil recovery. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41238.     

Synthesis and characterization of novel fluorine‐containing methacrylate copolymers: Reactivity ratios,thermal properties,and antimicrobial activity

The free‐radical‐initiated copolymerization of 2‐(4‐acetylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (AOEMA) and 2‐(4‐benzoylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (BOEMA) with 2‐[(4‐fluorophenyoxy]‐2‐oxoethyl‐2‐methylacrylate (FPEMA) were carried out in 1,4‐dioxane solution at 65°C using 2,2′‐azobisisobutyronitrile as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR and ¹H‐ and ¹³C‐NMR spectral studies. ¹H‐NMR analysis was used to determine the molar fractions of AOEMA, BOEMA, and FPEMA in the copolymers. The reactivity ratios of the monomers were determined by the application of Fineman‐Ross and Kelen‐Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPEMA, and copolymers formed are statistically in nature. The molecular weights (M _w and M _n) and polydispersity index of the polymers were determined using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of FPEMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPEMA in the copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Evaluation of the diethylene glycol bis(allyl carbonate)/acrylic acid copolymer behavior by solid‐state 13C‐NMR

The dynamic behavior of diethylene glycol bis(allyl carbonate) (CR‐39)/acrylic acid (AA) copolymers was evaluated by ¹³C high‐resolution solid‐state nuclear magnetic resonance (NMR). The NMR data showed that the copolymerization of CR‐39 and AA generated copolymers with different molecular behaviors as a function of AA content, which promoted changes in the crosslinking of CR‐39 chains and in the intramolecular forces. The copolymerization process influenced the sequence distribution and domain formation of the monomers, which is a consequence of the dispersion of comonomers along the macromolecular chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 740–745, 2005     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

Use of allyl‐functional benzoxazine monomers as replacement for styrene in vinyl ester resins

New vinyl ester systems are prepared using allyl‐functional benzoxazine monomers, 3‐allyl‐6‐methyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazine (pC‐ala) or bis(3‐allyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazin‐6‐yl)methane (BF‐ala), as reactive diluents for vinyl ester resins derived from an epoxy resin, diglycidyl ether of bisphenol A, instead of using styrene. Different initiators are used to investigate the copolymerization of allyl function from pC‐ala with vinyl function from vinyl ester resin prepolymer. The temperature dependence of viscosity is studied to demonstrate the retention of processability of the new vinyl ester resins. Dynamic mechanical and thermogravimetric analyses are used to investigate the dynamic mechanical properties and thermal stability of the new resins. Copyright © 2012 Society of Chemical Industry     

Synthesis and characterization of new polybenzoxazines from renewable resources for bio‐composite applications

Renewable natural resources such as eugenol, furfurylamine, stearylamine, and jute fiber were used to prepare polybenzoxazine composites. The purity of eugenol which is extracted from clove was confirmed by gas chromatography. FTIR, ¹H, and ¹³C NMR spectroscopic analysis were used to determine the structure of eugenol and the benzoxazine monomers namely 6‐allyl‐3‐furfuryl‐8‐methoxy‐3,4‐dihydro‐2H‐1,3‐benzoxazine (EF‐Bz) and 6‐allyl‐3‐octadecyl‐8‐methoxy‐3,4 dihydro‐2H‐1,3‐benzoxazine (ES‐Bz) synthesized from it. The curing analysis from differential scanning calorimetric analysis shows that the onset of curing is shifted to lower temperature (161°C) for EF‐Bz, when compared with ES‐Bz (174°C). The thermal stability analyzed from thermogravimetric analysis shows that the polybenzoxazine EF‐Pbz has higher thermal stability (T_5% = 361°C) with that of ES‐Pbz (T_5% = 313°C). The storage modulus, tensile, and flexural strength of the EF‐Bz/Jute fiber composite show high value when compared with ES‐Bz/Jute fiber composites. POLYM. COMPOS., 37:1821–1829, 2016. © 2014 Society of Plastics Engineers     

Synthesis and biodegradability evaluation of 2‐methylene‐1,3‐dioxepane and styrene copolymers

Biodegradable copolymers of 2‐methylene‐1,3‐dioxepane (MDO) and styrene (ST) were synthesized by free‐radical copolymerization using di‐t‐butyl peroxide (DTBP) as the initiator. The copolymers containing ester units were characterized by Fourier transform infrared (FTIR), ¹H‐NMR, and ¹³C‐NMR spectroscopy. Their molecular weight and polydispersity index were determined by gel permeation chromatography (GPC). In vitro enzymatic degradation of poly(MDO‐co‐ST) was performed at 37°C in phosphate buffer solution (PBS, pH = 7.4) in the presence of Pseudomonas lipase or crude enzyme extracted from earthworm. The experiment showed that incorporating ester units into C? C backbone chain of polystyrene would result in a biodegradable copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1146–1151, 2007     

Synthesis,characterization, and antimicrobial properties of novel quaternary amine methacrylate copolymers

A novel amine methacrylate monomer trimethylolpropane trimethacrylate–piperazine–ethyleneglycol dimethacrylate (TMPTMA‐PPZ‐EGDMA) was synthesized by amination of trimethylolpropane trimethacrylate (TMPTMA) with excess of piperazine (PPZ) followed by reaction with ethyleneglycol dimethacrylate (EGDMA). Copolymerization of TMPTMA‐PPZ‐EGDMA with 2‐hydroxyethyl methacrylate (HEMA) was carried out by free radical polymerization using ammonium persulfate (APS) and N,N,N′,N′‐tetramethyl ethylenediamine (TEMED) as a redox initiator. The copolymers obtained were then quaternized with 1‐iodooctane. The monomers were characterized by FTIR and ¹H NMR spectral studies. The molecular weights and polydispersity values of the monomers were determined with gel permeation chromatography. Quaternized copolymers containing more than 20% amine methacrylate monomer showed microporosity in the range of 9.9–10.4 μm. The antibacterial activity of the quaternized copolymers against Escherichia coli and Staphylococcus aureus was studied using UV–vis spectrophotometer and scanning electron microscopy. Quaternized copolymers showed broad‐spectrum contact‐killing antibacterial properties without releasing any active agent as checked by iodide selective ion meter. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Antimicrobial coatings based on hydantoin‐containing polymer networks for textiles

An advanced method with an initiator pretreatment was developed for the coating of nylon/cotton fabrics with the hydantoin‐containing monomer 3‐allyl‐5,5‐dimethylhydantoin and two water‐soluble crosslinkers N,N′‐methylene bisacrylamide and poly(ethylene glycol) 200 diacrylate. The formulations were applied to textiles by either batch coating or dip coating. In the dip‐coating process, the influence of individual parameters on the fabric modification was investigated and evaluated. After treatment with chlorine, the hydantoin structure was transformed into antimicrobial active N‐halamines. The modified fabrics exhibited potent antibacterial properties against Staphylococcus aureus and Escherichia coli. Our method, based on an initiator pretreatment and water‐soluble crosslinkers, outperformed current technologies in the degree of fabric modification. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Non‐catalyst synthesis and in vitro drug release property of poly(5,5‐dimethyl‐1,3‐dioxan‐2‐one)‐block‐methoxy poly(ethylene glycol) copolymers

A series of poly(5,5‐dimethyl‐1,3‐dioxan‐2‐one)‐block‐methoxy poly(ethylene glycol) (PDTC‐b‐mPEG) copolymers were synthesized by the ring‐opening polymerization of 5,5‐dimethyl‐1,3‐dioxan‐2‐one (DTC) in bulk, using methoxy poly(ethylene glycol) (mPEG) as initiator without adding any catalysts. The resulting copolymers were characterized by Fourier transform infrared spectra, ¹H NMR and gel permeation chromatography. The influences of some factors such as the DTC/mPEG molar feed ratio, reaction time and reaction temperature on the copolymerization were investigated. The experimental results showed that mPEG could effectively initiate the ring‐opening polymerization of DTC in the absence of catalyst, and that the copolymerization conditions had a significant effect on the molecular weight of PDTC‐b‐mPEG copolymer. In vitro drug release study demonstrated that the amount of indomethacin released from PDTC‐b‐mPEG copolymer decreased with increase in the DTC content in the copolymer. © 2013 Society of Chemical Industry     

Ring‐opening copolymerization and properties of polycarbonate copolymers

A series of polycarbonate copolymers were synthesized by the ring‐opening bulk polymerization of 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) and 5,5‐dimethyl trimethylene carbonate (DTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as initiators. The copolymers obtained were characterized by ¹H‐NMR, Fourier transform infrared, and ultraviolet. The influence of the molar ratio of the monomers, the initiators, and their concentrations, the reaction time, and the reaction temperature on the copolymerization was also studied. The copolymerization of monomers DTC and PTC was a nonideal copolymerization, and the copolymerization reactivity ratio of the monomer DTC was higher than that of PTC in the copolymerization process. In vitro release profiles of fluorouracil from the copolymers showed that the copolymer had a steady drug‐release rate and good controlled‐release property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Antibacterial N‐halamine coating on cotton fabric fabricated using mist polymerization

3‐Methylallyloxy‐5,5‐dimethylhydantoin (MH), an methacrylate monomer containing N‐halamine moiety, was synthesized by 5,5‐dimethylhydantoin (DMH) and methacryloyl chloride. Antimicrobial coating of poly[1‐methyl‐1‐(4,4‐dimethyl‐2,5‐dioxoimidazolidin‐carbonyl)ethylene] (PMH) was prepared on cotton fabrics via “mist polymerization” using MH as monomer. The coating gave the cotton fabric with efficient antibacterial function with remarkable durability. In the antibacterial tests, the bacteriostatic reduction rate is greater than 99.78%, and can be maintained over 99.00% even after 30 washing cycles. Compared with other antimicrobial technologies, mist polymerization offers advantages such as achieving antimicrobial function by small consumption of monomer, forming coatings on single‐side of the fabrics, and minimizing the damages on the original properties of cotton during the finishing process. It can be applied in a wide variety of textile products such as sportswear, underwear, socks, and medical textiles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44897.     

Hydrosoluble copolymers of acrylamide‐(2‐acrylamido‐2‐methylpropanesulfonic acid). Synthesis and characterization by spectroscopy and viscometry

Hydrosoluble copolymers containing sulfonic acid groups incorporated into a macromolecule were synthesized. The group of polymers studied was obtained by free radical solution polymerization, using potassium persulfate as an initiator. The copolymerization of the monomers 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) and acrylamide (AA) was carried out at different pH values of the reaction medium of the monomer mix. The copolymers were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR) and Fourier transform infrared spectroscopy (FTIR). The viscosity behavior of the copolymers in NaCl solution showed a dependency on the pH of the reaction medium, with higher pH leading to lower viscosities. The acidic conditions of this medium affect the initiator decomposition rate, which is a probable cause of the viscosity variation, and the extent of decomposition increases with increasing pH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 192–198, 2003