Synthesis and characterization of novel swelling tunable oligomeric poly(styrene‐co‐acrylamide) modified clays

The oligomeric poly(styrene‐acrylamide‐vinylbenzylchloride) (P(St‐AM‐VBC)) quaternary ammonium salts have been prepared from the reactions of trimethylamine with the corresponding P(St‐AM‐VBC)s, which were synthesized by free‐radical polymerization of a mixture of styrene, acrylamide, and vinylbenzylchloride. Then the swelling tunable oligomeric poly(styrene‐co‐acrylamide) modified clays have been prepared through cation exchange of the sodium ions in the clay with the corresponding P(St‐AM‐VBC) quaternary ammonium salts. The P(St‐AM‐VBC) and its modified clays have been characterized by infrared spectra (IR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), proton nuclear magnetic resonance (¹H NMR), X‐ray diffraction (XRD), and transmission electron microscopy (TEM). The solvent‐swelling capacity of poly(styrene‐co‐acrylamide) modified clays have also been tested, and the experimental results have indicated that these clays are novel swelling tunable organic clays. XRD and TEM studies have shown that these novel swelling tunable clays are well‐intercalated or exfoliated. Furthermore, TGA analysis shows that these polymerically modified clays have high thermal stability for nanocomposites by melt blending. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Application of quaternary ammonium salt as catalyst in the reaction of glycidyl methacrylate with CO2

This study is related to the investigation of the characteristics of quaternary ammonium salt catalyst on the addition reaction of carbon dioxide and glycidyl methacrylate (GMA) to form (2-oxo-l,3-dioxolan-4-yl) methyl methacrylate (DOMA). Among the salts tested, the ones with higher alkyl chain length and with more nucleophilic counter anion showed a higher catalytic activity. The DOMA monomer was obtained in non polar solvent like toluene and cyclohexane, while poly (DOMA) could be directly obtained in aprotic dipolar solvent such as DMF. In order to facilitate recovery of catalyst, polymer-immobilized quaternary ammonium salt was prepared by copolymerization of styrene (ST), divinylbenzene (DVB) and vinyl benzene chloride (VBC). The catalyst with 2 wt% of DVB, 25 wt% of VBC and quaternized tributyl amine showed the highest catalytic activity, and its activity was maintained even up to 10 successive experimental runs.     

Antibacterial activity of novel insoluble bead‐shaped polymer‐supported multiquaternary ammonium salts

This study describes the effect of antibacterial activity of newly reported five different novel insoluble bead‐shaped polymer‐supported multiquaternary ammonium salts (PM quats) viz., bis‐quat, tris‐quat (2 Nos.), tetrakis‐quat, hexakis‐quat containing two, three, four, and six quaternary ammonium groups, respectively. The presence of number of quaternary ammonium groups in each salt was established already through Fourier‐transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and chloride ion analyzes. The antibacterial activities of these five different PM quats against three different bacteria viz., Staphylococcus aureus, Klebsiella pneumoniae, and Pseudomonas aeruginosa were investigated by serial dilution and spread plate method and compared the same with a monoquat containing single quaternary ammonium group. The extent of antibacterial activity has been measured in terms of colony forming units (CFU) at different time intervals. The observed results show that all the PM quats exhibited excellent‐antibacterial activity against each bacterium. On the basis of the CFU values, the antibacterial activity was found to increase from bis‐quat to hexakis‐quat, which reveals that the activity of PM quats increases with increase in the number of quaternary ammonium groups. The mechanism of interaction of quats with bacterial cytoplasmic membrane has been explained as an adsorption‐like phenomenon. The reusability of highly active hexakis‐quat against Staphylococcus aureus was studied and the activity was found to reduce after first cycle. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of polymer-supported catalysts containing phosphorus palladium complexes and quaternary onium groups,and their application to the vinylation reaction

Micron-sized crosslinked polystyrene [poly(ST-DVB)] particles prepared by the concentrated emulsion polymerization method were coated with nonuniform layers of the following functionalized polymers: (I) poly(3- and 4-vinylbenzyl chloride) [poly(VBC)]; (II) a copolymer of VBC and 4-chlorosytrene [poly(VBC)-(CST)] and; (III) a composite of poly(VBC) and poly(3,4-dichloro-1-butene) [poly(VBC)-poly (DCB)]. A fine powder composed of small aggregates of such particles was obtained by grinding. The polymers thus prepared were converted to three types of reactive substrates containing both organophosphorus ligands and quaternary onium groups: (1) (m-sulfonate phenyl) diphenyl phosphine and poly(vinylbenzyl tributyl ammonium chloride) bound to poly(ST-DVB); (2) diphenyl ethylene phosphite and benzyl methyl diethanol ammonium groups bound to poly(ST-DVB); and (3) phosphine oxide and quaternary benzyl tributyl ammonium or phosphonium groups bound to poly(ST-DVB). The polymer-supported catalysts containing phosphorus palladium complexes and quaternary onium groups were then employed in the vinylation reaction of iodobenzene with methyl acrylate. These supported bicatalysts displayed a cooperative effect that increased the yield of vinylation by a factor greater than two when compared to its homogeneous counterpart. The relative locations of palladium complexes and quaternary onium groups are found to influence the yield.     

Polymeric phosphonium salts as a novel class of cationic biocides. VII. Synthesis and antibacterial activity of polymeric phosphonium salts and their model compounds containing long alkyl chains

Various polymeric phosphonium salts containing long alkyl chains (C₁₀? C₁₈) and their corresponding model compounds were prepared, which possess the same hydrophobic structure as that of the common disinfectants (quaternary ammonium salts), and their antibacterial activities were evaluated by means of the viable cell counting method against Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative). The polymer with the decyl group exhibited a higher activity than that of the corresponding model compound, particularly against the Gram-positive strain. Furthermore, antibacterial activity of the polymers was found to decrease as the chain length increased. In contrast with the polymers, the antibacterial activity of the corresponding model compounds increased as hydrophobicity of the substituents increased. The antibacterial activity was strongly dependent on the structure, particularly on the length of the alkyl chain. © 1994 John Wiley & Sons, Inc.     

Preparation and antibacterial properties of waterborne UV cured coating modified by quaternary ammonium compounds

In this article, the antibacterial properties and mechanism of waterborne UV cured acrylic coatings (WUV) modified by quaternary ammonium compounds (QAC) is discussed, as well as the changes in the antibacterial properties of QAC under the action of different additives. (60 wt% methanol, 60 wt% ethanol, and 75 wt% ethanol). And the chemical cross-linking method is used to combine WUV with QAC. The scanning electron microscopy (SEM), Fourier transforms infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS) was employed to characterize the modified WUV. The antibacterial properties of three antibacterial agents in liquid coatings (WUV-L) and cured coating films (WUV-C) are investigated. The SEM images showed many irregular wrinkles appeared on the surface of modified coating films. The FTIR result showed the hydroxyl groups promoted the binding ability of the antibacterial agents and coating, and the XPS result revealed that the increase of −NR₄⁺ concentration enhanced the antibacterial properties of coating films. The antibacterial properties of WUV-L and WUV-C improved with the increase of QAC. Theoretical antibacterial agents mass fraction of 5% or higher was found to have the highest antibacterial rate (>90.00%) for WUV modification, among, the WUV modified by QAC-m60 is the best with the antibacterial rate reaching to 99.73% in WUV-L and 99.67% in WUV-C.     

Quaternarized cationic poly[(vinyl chloride)-co-(vinyl chloroacetate)] binary copolymer as non-migration antibacterial additive in PVC matrix

Antibacterial polyvinyl chloride (PVC) materials have drawn considerable attention since their wide application in medical devices. The objective of this study is to develop a novel quaternary ammonium cationic vinyl chloride copolymer, which can be potentially used as antibacterial additive in PVC matrix. Initially, the low average-number molecular weight poly[(vinyl chloride)-co-(vinyl chloroacetate)] (PVC-co-PVCA) is synthesized by precipitation copolymerization. Subsequently, quaternary ammonium cationic moieties with different lengths of alkyl chains are introduced into the copolymers via quaternization reaction between alkyl-dimethyl tertiary amines with acyl chloride groups. The successful synthesis of PVC-co-PVCA and quaternarized copolymers are carefully confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H NMR), and x-ray photoelectron spectroscopy. The antibacterial behaviors of the quaternarized copolymers and its blends with PVC are investigated. The results reveal that all the PVC blends containing at least 5% by weight of quaternarized copolymer have superior bacteriostasis ratio (>99.6%) against both Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus) due to the incorporation of quaternary ammonium groups. Meanwhile, the cationic copolymer exhibits excellent antifouling and much lower migration rate (<0.4%). These interesting consequences endow the quaternarized copolymers as alternative antibacterial agents possess a great deal of potential for use in PVC materials.     

Biocidal polymers active by contact. II. Biological evaluation of polyurethane coatings with pendant quaternary ammonium salts

Films of polyurethane were prepared by reaction of hydroxytelechelic polybutadienes carrying covalently bound quaternary ammonium salts with an aliphatic triisocyanate. These coatings exhibited high biocidal activity against Gram-positive and Gram-negative bacteria, yeasts, and moulds. It was found that many parameters controlled the bioactivity such as the time of contact between films and bacteria, the [NCO]/[OH] ratio used to prepare the cured polyurethane, the concentration of quaternary ammonium salts in the coating, and the length of the alkyl chain from C₈ to C₁₆ linked to the quaternary nitrogen atom. A secondary phenomenon of diffusion only observed with the shorter alkyl chains (C₈ and C₁₀) was shown to be due to synthesis residues. After these water-soluble impurities are eliminated, the biocidal activity remains excellent: then it is due only to a contact polymer bacteria. © 1993 John Wiley & Sons, Inc.     

Antibacterial and Bacterium Adsorbing Macromolecules

Currently studies on antibacterial macromolecules, i. e., bactericidal and bacteriostatic ones, have been made to develop a new utilization field of polymeric materials. In these studies, there are immobilizations of iodine to quaternary ammonium salts, antibiotics, antibacterial groups to macromolecular substances, as well as syntheses of polymers with quaternary ammonium salts, biguanide groups, quaternary pyridinium salts, sulphonium salts, phosphonium salts, and other antibacterial groups. On the other hand, studies have been made of bacterium adsorbing macromolecules, which can remove by adsorbing bacterial cells in water. The macromolecules are the ones based on poly(4‐vinylpyridine‐co‐divinylbenzene), crosslinked poly(3‐ and 4‐chloromethylated styrene‐g‐amine), and poly(glycidyl methacrylate‐g‐amine), as well as filters and microporous membranes are covered with a macromolecule based on quaternized poly(4‐vinylpyridine‐co‐styrene). Here, a review is made of the syntheses and preparation of the respective macromolecules, as well as of their antibacterial activities and the bacterium adsorbing activities.     

新型蓖麻油基季铵盐的合成及其抑菌性能研究

以蓖麻油酸甲酯为起始原料,与N,N-二甲基-1,3-丙二胺和溴化苄、溴乙烷通过酰胺化反应和季铵化反应生成了新型蓖麻油基季铵盐,其结构经FTIR、1HNMR、13CNMR及ESI-MS进行了确证。采用抑菌圈直径法对目标产物的抑菌性能进行了测试,结果表明,两种季铵盐均有一定的抑菌活性,N,N-二甲基-N-乙基-蓖麻油酸酰胺丙基溴化铵的抑菌活性略强于N,N-二甲基-N-苄基-蓖麻油酸酰胺丙基溴化铵。     

Biocidal polymers active by contact. V. Synthesis of polysiloxanes with biocidal activity

Polysiloxanes with 3‐(alkyldimethylammonio)propyl pendant groups were synthesized by quaternization of n‐octyldimethylamine or n‐dodecyldimethylamine with linear polysiloxanes containing 3‐chloropropyl groups and/or 3‐bromopropyl groups attached to silicon atoms. The precursor polysiloxanes, poly[(3‐chloropropyl)methylsiloxane] homopolymer and various copolymers containing (3‐halogenopropyl)methylsiloxane and dimethylsiloxane units, were obtained by equilibrium cationic polymerization of linear and cyclic siloxanes with (3‐halogenopropyl)methylsiloxane units. The polysiloxanes bearing quaternary ammonium salts (QAS) showed bactericidal activity against bacteria such as Escherichia coli and Aeromonas hydrophila when incorporated in a polysiloxane network. The activity was retained after 66 days of immersion in water. The QAS‐containing polysiloxanes are also active in aqueous solution. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1005–1012, 2000     

Antibacterial activity of copolymers of trialkyl(4-vinylbenzyl)ammonium chlorides with acrylonitrile

Homopolymers of cetyldimethyl(4-vinylbenzyl)ammonium chloride (VB16), lauryl-dimethyl(4-vinylbenzyl)ammonium chloride (VB12), and trimethyl (4-vinylbenzyl)ammonium chloride (VB1), and copolymers of these compounds with acrylonitrile were examined for antibacterial activity using B. subtilis, S. aureus, E. coli, and P. aeruginosa. All homopolymers and copolymers showed germicidal action to the bacterias, especially strong action to gram-positive B. subtilis and S. aureus. The strength of the germicidal action of the quaternary ammonium branches was in the order: VB16 > VB12 ? VB1.     

Preparation of cationic water-absorbent resin from PEI and PEO

Hydrophilic network copolymers containing poly(ethylene oxide) and polyethyleneimine blocks were prepared by cross-linking polyethyleneimine with poly(ethylene oxide) terminated at both ends with Br atoms in DMSO. The experimental results show that the network density of the copolymer and the water absorption power thereupon can be efficiently controlled by the change of the amount of DMSO in the reaction system. Further modification was obtained by converting these copolymers into quaternary ammonium salts. The resulting quaternary ammonium salts exhibit enormously enhanced water absorption power. The absorption power of these quaternary ammonium salts in several organic solvents and in aqueous solutions containing Na⁺, Ca²⁺, Mg²⁺, or Fe³⁺ was also examined.     

Biologically active polymers. IV. Synthesis and antimicrobial activity of tartaric acid polyamides

New bactericidal polyamides with quaternary ammonium or phosphonium salts were prepared, and their antimicrobial activities were explored. The polyamides were synthesized by the polycondensation of diethyl‐l‐tartrate or chloromethylated diethyl‐l‐tartrate with ethylenediamine in dry absolute ethanol. The polyamides were modified to yield polymers with either quaternary ammonium or phosphonium salts. The polymers were characterized with elemental microanalysis and ¹H‐NMR and IR spectra. The antimicrobial activity of the polymers bearing onium salts was studied against Gram‐negative bacteria (Escherichia coli, Pseudomones aeruginosa, Shigella sp., and Salmonella typhae), Gram‐positive bacteria (Bacillus subtilis and Bacillus cereus), and a fungus (Trichophytum rubrum) by the cut‐plug and viable‐cell‐count methods. Although all the polymers showed high antibacterial activity, some had no antifungal activity. The tributyl phosphonium salt of the polyamide was more effective against both Gram‐negative and Gram‐positive bacteria than the triethyl ammonium and triphenyl phosphonium salts of the polyamide. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4780–4790, 2006     

Preparation of iodine containing quaternary amine methacrylate copolymers and their contact killing antimicrobial properties

A novel quaternary amine methacrylate monomer (QAMA) was synthesized by amination of dimethacrylate with piperazine followed by its quaternization using an alkyl iodide. Copolymerization of QAMA with 2‐hydroxyethyl methacrylate was carried out by free radical bulk polymerization technique at room temperature using ammonium persulfate and N,N,N′,N′‐tetramethyl ethylenediamine as a redox initiator. The monomer as well as copolymers was characterized by FTIR and ¹H NMR spectral studies. Thermal and physical characteristics of copolymers of varying compositions of QAMA were evaluated by thermogravimetric analysis, differential calorimetry, contact angle and scanning electron microscopy. The antibacterial activity of the synthesized quaternary amine dimethacrylate copolymers against Escherichia coli and Staphylococcus aureus was studied by zone of inhibition and colony count method. QAMA copolymers showed broad‐spectrum contact killing antibacterial properties without releasing any active agent as checked by iodide‐selective ion meter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1038–1044, 2006     

Emulsifier‐free cationic latexes based on vinylbenzyl chloride and 2‐(dimethylamino)ethyl methacrylate with adjusted hydrophilic–hydrophobic properties

Functional emulsifier‐free cationic latexes based on styrenic monomer vinylbenzyl chloride (VBC) and acrylic monomer 2‐(dimethylamino)ethyl methacrylate (DMA) were successfully prepared with dual quaternary ammonium ions (36–63 mol %) on both monomer moieties in two‐stages. First, [2‐(methacryloyloxy)ethyl]dimethylhexadecylammonium bromide monomer (DMA(C₁₆)), prepared via quaternization of DMA with 1‐bromohexadecane, was utilized as a comonomer (5–20%) as well as a surfactant in the emulsion polymerization of VBC. Next, the quaternization of chloromethyl groups in the VBC moiety in latex particles with trimethylamine and N,N‐dimethylhexadecylamine created a second type of quaternized sites on the latex particles. The percentages of the quaternary ammonium ions of the first‐stage latexes (P[VBC‐DMA(C₁₆‐x)]) and the second‐stage latexes (P[VBC(R)‐DMA(C₁₆‐x)]) were determined using bromide and chloride ion‐selective electrodes. The particles were characterized with a scanning electron microscope, Zetasizer, measuring water contact angles of their pellets. The polymer structure and the alkyl group length in their quaternary ammonium ions played an important role on the sizes, zeta potentials and hydrophilic–hydrophobic balances of the latexes. The water contact angles of the pellets of the latex particles varied from 50.3 to 109.6° depending on both the polymer structure and the alkyl group length. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42775.     

Keggin型磷钨钒杂多酸季铵盐的合成、表征及抑菌效果的研究

以不同钒原子数取代Keggin型磷钨杂多酸并与十六烷基三甲基溴化铵反应合成了3种杂多酸季铵盐.通过红外光谱(IR)、X-射线衍射(XRD)、紫外(UV)等表征手段确定了杂多酸以及杂多酸季铵盐的结构.结果表明,在红外光谱中,引入钒原子后阴离子负电荷增加,导致相应的特征峰出现红移现象;从X-射线衍射谱图中确定了杂多酸季铵盐的二级结构,最后通过热重分析(TG)得出杂多酸季铵盐所含结晶水的数目.通过杯碟法测试了目标产物对大肠杆菌、金黄色葡萄球菌、枯草芽孢杆菌、蜡样芽孢杆菌的抑菌性能,结果表明杂多酸季铵盐对枯草芽孢杆菌的抑菌能力最好,并且钒原子所占比例越高,抑菌效果越好.     

Synthesis and Properties of Organosilicon Quaternary Salts Surfactants

Diethyl-benzyl-[3-methyldimethoxyl)]silpropyl ammonium chloride (DEBSAC) was synthesized from N,N-diethyl-aminopropyl-methyldimethoxysilane (DEAPMDES) and benzyl chloride. Diethyl-2,3-epoxypropyl-[3-methyldimethoxyl)] silpropyl ammonium chloride (DEEPSAC) was synthesized from DEAPMDES and epoxy chloropropane. Trimethyl-[3-methyldimethoxyl)] silpropyl ammonium chloride (TMSAC) was synthesized from trimethylamine and γ-chloropropylmethyldimethoxysilane (CPMDMS). The products were characterized by ¹H NMR, ¹³C NMR, and IR. The surface tension measurements showed that the organosilicon quaternary salts exhibit a lower surface tension and a lower critical micelle concentration (CMC) than the hydrocarbon counterparts. The plate count method experiments illustrated that DEEPSAC has a better degree of antibacterial activity against Escherichia coli than DEBSAC. The solubilizing effects of the organosilicon quaternary salts on organosilicone were studied by pseudo-ternary phase diagrams of synthesized products/cosurfactant(n-butanol)/water/octamethylcyclotetrasiloxane. The solubilizing activities decreased in the order of TMSAC > DEBSAC > DEEPSAC.     

Amphiphilic macromolecular nanostructure materials derived from 5-(octanoate methyl)bicyclo[2.2.1]hept-2-ene and 5-(phthalimide methyl)bicyclo[2.2.1]hept-2-ene via ring-opening metathesis copolymerization

Novel highly stable polynorbornenes with self-assembling amphiphilic architecture containing hydrophilic ammonium salt and hydrophobic alkyl ester group were obtained via ring-opening metathesis polymerization (ROMP) of 5-(octanoate methyl)bicyclo[2.2.1]hept-2-ene (NBMO) and 5-(phthalimide methyl)bicyclo[2.2.1]hept-2-ene (NBMPI), hydrogenation, hydrazinolysis, and subsequent quaternization. Polymeric micelles of such amphiphilic random and block polynorbornenes formed in solvents by varying the content of ammonium salts were investigated. Amphiphilic block copolymers exhibited perfect spherical morphology. Nanoscale polymeric micelles of random copolymers with 50-75 mol% of ammonium salts were roughly spherical in shape, while the morphologies of micelles transferred into network-like aggregates as hydrophilic contents of the random copolymers are higher than 80 mol%. The formation and fine structures of micelles were investigated by dynamic light scattering (DLS), TEM, and fluorescence technique using pyrene as fluorescence probe.     

Synthesis and antibacterial activity of immobilized quaternary ammonium salts

Quaternary ammonium salts were immobilized on hydrophilic gels based on sucrose methacrylates (SM) and tested for their antibacterial properties. The cross-linked polymers were prepared by copolymerization of monomer–SM mixtures with 4-vinylpyridine and subsequent quaternization with 1-bromoctane and 1-bromoctadecan and by esterification of SM gels with 3-pyridine carboxylic acid chloride and quaternization. In addition, immobilized quaternary salts bonded by hydrophobic as well as by hydrophilic spacers were synthesized by esterification of SM gels with 11-bromundecanoic acid chloride and the tetraethylene glycol-based acid chloride 13c , respectively, and subsequent reaction of the halogen-substituted gels with tertiary amines. Suspension tests for antibacterial properties of the immobilized bactericides against Escherichia coli, Staphylococcus aureus, and Micrococcus luteus demonstrated high activity of the quaternary salts bonded by the hydrophobic spacer. Advantageously, these insoluble bactericides can be applicated without contamination of the substrate; they can be removed easily and used repeatedly. © 1994 John Wiley & Sons, Inc.