Preparation of a C6 quaternary ammonium chitosan derivative through a chitosan schiff base with click chemistry

In this study, we explored a new method for preparing C₆ quaternary ammonium chitosan (CTS) derivatives. The C₂? NH₂ of CTS was first protected by benzaldehyde. The C₆? OH of CTS was then transformed into a sulfonyl ester, which was then reacted with NaN₃ through nucleophilic substitution to introduce the ? N₃ group at the CTS C₆ position. This intermediate was reacted in a click chemistry reaction with a terminal alkynyl quaternary ammonium salt; this was followed by the deprotection of C₂? NH₂ with acid to furnish the C₆ quaternary ammonium CTS derivative. The structures and properties of synthesized products in the reactions were characterized by Fourier transform infrared spectroscopy, NMR, X‐ray diffraction, and thermogravimetric analysis, respectively. The effects of the reaction conditions on the degree of Schiff‐base CTS quaternization were evaluated by elemental analysis. The largest inhibition zone test and the minimum inhibitory concentration test showed that compared with CTS, the prepared CTS derivative had significantly improved antibacterial activity toward Staphylococcus aureus and Escherichia coli. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of cationic starch containing quaternary ammonium substituents by reactive twin-screw extrusion processing

Cationic starch, an important additive for papermaking and other uses, was prepared from native cornstarch and 3-chloro-2-hydroxypropyltrimethylammonium chloride in aqueous sodium hydroxide using a twin-screw extruder as the reactor. The effects of physical and chemical reaction variables on reaction efficiency (RE) and degree of substitution (DS) of up to 0.05 were studied. RE was based on nitrogen content contributed by cationization of the starch after the products were exhaustively washed to remove unreacted monomer. Under certain reaction conditions, exceptionally high RE (90%+) was achieved, exceeding maximum values previously reported using laboratory-batch reaction procedures. The combined effects of high reaction temperature (90°C), intense mixing, high-starch solids (65%), and appropriate levels of catalyst contributed to the unusually high RE values achieved by the reactive extrusion process. © 1994 John Wiley & Sons, Inc.^?     

Synthesis,characterization, and drug‐release behavior of amphiphilic quaternary ammonium chitosan derivatives

A new type of amphiphilic quaternary ammonium chitosan derivative, 2‐N‐carboxymethyl‐6‐O‐diethylaminoethyl chitosan (DEAE–CMC), was synthesized through a two‐step Schiff base reaction process and applied to drug delivery. In the first step, benzaldehyde was used as a protective agent for the incorporation of diethylaminoethyl groups to form the intermediate (6‐O‐diethylaminoethyl chitosan). On the other hand, NaBH₄ was used as a reducing agent to reduce the Schiff base, which was generated by glyoxylic acid, for the further incorporation of carboxymethyl groups to produce DEAE–CMC. The structure, thermal properties, surface morphology, and diameter distribution of the resulting chitosan graft copolymers were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, thermogravimetric analysis, differential scanning calorimetry, X‐ray powder diffraction, scanning electron microscopy, and laser particle size analysis. Benefiting from the amphiphilic structure, DEAE–CMC was able to be formed into microspheres in aqueous solution with an average diameter of 4.52 ± 1.21 μm. An in vitro evaluation of these microspheres demonstrated their efficient controlled release behavior of a drug. The accumulated release ratio of vitamin B₁₂ loaded DEAE–CMC microspheres were up to 93%, and the duration was up to 15 h. The grafted polymers of DEAE–CMC were found to be blood‐compatible, and no cytotoxic effect was shown in human SiHa cells in an MTT [3‐(4, 5‐dimethyl‐thiazol‐2‐yl)‐2, 5‐diphenyltetrazolium bromide] cytotoxicity assay. These results indicate that the DEAE–CMC microspheres could be used as safe, promising drug‐delivery systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39890.     

Preparation of superabsorbent based on the graft copolymerization of acrylic acid and acrylamide onto konjac glucomannan and its application in the water retention in soils

A new konjac glucomannan (KGM)-based superabsorbent polymer, KGM-g-poly(acrylic acid-co-acrylamide), was prepared by the free radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto KGM in the presence of N,N′-methylenebisacrylamide as a crosslinker with potassium persulfate as an initiator. The effects of reaction parameters, including the amount of crosslinking agent and initiator, the weight ratio of both (AA + AM) to KGM and AM to (AA + AM), neutralization degree of AA, bath temperature, and reaction time, on the water absorbency of the superabsorbent were investigated. The Fourier transform infrared spectroscopy was used to characterize the structures of the copolymer. The maximum water absorbency of the optimized product was 650 g/g for distilled water and 70 g/g for a 0.9 wt % aqueous NaCl solution. Furthermore, the water retention of the copolymer in soils was studied. The effect of the copolymers on the aggregate distribution of soils was also evaluated. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Water‐soluble grafted polysaccharides containing sulfobetaine groups: Synthesis and characterization of graft copolymers of hydroxyethyl cellulose with 3‐dimethyl(methacryloyloxyethyl)ammonium propane sulfonate

New water‐soluble grafted polysaccharides containing sulfobetaine groups were synthesized by the grafting of the sulfobetaine‐type zwitterionic monomer 3‐dimethyl‐(methacryloyloxyethyl)ammonium propane sulfonate (DMAPS) onto hydroxyethyl cellulose (HEC) in the presence of a ceric ammonium nitrate (CAN)/ethylenediaminetetraacetic acid (EDTA) initiation system. The effects of the concentrations of CAN, EDTA, DMAPS, and HEC, as well as the polymerization time and temperature, on the grafting reactions were investigated in terms of the grafting percentage (%GP) and grafting conversion (%GC) of the monomer. The %GP and %GC increased and then decreased with increasing concentrations of CAN, EDTA, and HEC. The %GP and %GC increased with increasing DMAPS concentration up to a certain value, beyond which the %GP did not significantly increase and the %GC decreased. The appropriate polymerization time and temperature were favorable for the grafting reactions. With infrared, thermogravimetric analysis, and viscosity measurements, the resulting grafted polysaccharides were characterized. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2755–2761, 2002; DOI 10.1002/app.10191     

Polyurethane‐functionalized starch nanoparticles for the purification of biodiesel

Polyurethane‐functionalized starch nanoparticles (PUFSNPs) have been synthesized by chemical modification of polyhydroxylated starch nanocrystals (SNC) with aliphatic and aromatic diisocyanates. The covalent attachment of the diisocyanates to the backbone of SNC for the formation of starch‐derived nanopolyurethane polymers was unambiguously determined by FTIR and NMR spectroscopy. PUFSNPs were entirely obtained from SNC with yields ranging from 41.5 to 86.0 wt % and their size distribution, size, porosity and morphology were determined by dynamic light scattering (DLS), high resolution transmission electron microscopy (HRTEM) and Brunauer–Emmett–Teller (BET) adsorption techniques. The size and surface area of the cyclic aliphatic‐based PUFSNP (NPU4) is 27 nm and 52.64 m² g^?1, respectively, indicating one of the potential and promising biodegradable materials for the adsorption of acid impurities and contaminants that are found in crude biodiesel. The acid content of the biodiesel is remarkably reduced by 32–39% with PUFSNPs while 7–18% with their corresponding bulk materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44463.     

Preparation of cationic modified collagen extracted from leather wastes and their application in dye flocculation

A series of novel cationic flocculants are designed and synthesized successfully by grafting two monomers onto the collagen backbone, namely acrylamide (AM) and 2‐methacryloyloxyethyltrimethyl ammonium chloride (DMC). Apparently, these effective grafting modifications are well demonstrated by adopting FTIR and H¹ NMR measurements, which could be used to estimate grafting ratios of corresponding monomers approximately. Additionally, significant improvements in positive charge densities and amorphous aggregation structures are also definitely confirmed by Zeta and XRD measurements, respectively. Moreover, thermogravimetric analysis clearly proves the formation of cationic branched chain architectures, whose maximum thermal degradation temperature would significantly decrease with the introduction of AM. In addition, much more porous and rougher surface structures could be visibly observed after successful grafting modifications. Furthermore, when the feeding weight ratio between collagen and DMC is controlled at 1:3, or the equal amounts of AM and DMC are introduced meanwhile the mass ratio between collagen and mixed monomers (DMC + AM) is fixed at 1:4, the samples acquired could both perform the best in decolorizing the model wastewater containing methyl orange (MO) dyes in their groups, and hereby, a corresponding flocculation mechanism is also proposed based on the structural analysis of the formed flocs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45363.     

Preparation of chitosan and carboxymethylcellulose-based polyelectrolyte complex hydrogel via SD-A-SGT method and its adsorption of anionic and cationic dye

The excellent properties of the polyelectrolyte complex hydrogels (PECHs) prepared with polysaccharides only, including polyampholyte, low toxicity, green, and clean production, have endowed them great application potentials as the adsorbents for dye-containing wastewater treatments. In the current study, the PECH of chitosan (CTS) and carboxymethylcellulose (CMC) was prepared by semi-dissolution acidification sol–gel transition (SD-A-SGT) method. The hydrogel was formed by the strong electrostatic interaction of cationic  NH₃⁺ groups of CTS and the anionic  COO⁻ groups of CMC. This simple but efficient means exhibited great potentials in constructing PECHs with uniform composition and controllable sol–gel transitions. Molecular dynamics simulation was first employed to predict the formation process and the microstructure of PECHs prepared by SD-A-SGT method. The structure and properties of the CTS-CMC PECHs were also characterized by Fourier transform infrared spectroscopy, SS ¹³C-NMR, scanning electron microscopy, mechanical tests, and rheological measurements, respectively. Taking the advantage of amphoteric polyelectrolyte properties, adsorption properties of anionic and cationic dyes were investigated using sunset yellow FCF and methylene blue as model dyes, respectively. The PECHs prepared in the present work had good adsorption capacity for both cationic and anionic dyes with maximum adsorption capacity of 212.83 mg/g for sunset yellow FCF and 167.35 mg/g for methylene blue. Therefore, this PECH would be a promising environmentally friendly adsorbent for the treatment of functional molecules with different charges.     

Synthesis of cationic hemicellulosic derivatives with a low degree of substitution in dimethyl sulfoxide media

A series of water‐soluble cationic 2‐hydroxylpropyltrimethylammonium hemicellulosic derivatives with low average degrees of substitution (DS's) were prepared by the incorporation of the cationic moiety 2,3‐epoxypropyltrimethylammonium chloride (ETA) onto the backbone of hemicelluloses in the presence of NaOH as a nucleophilic catalyst in homogeneous dimethyl sulfoxide (DMSO) media. The dependence of the homogeneous reaction on the different affecting factors was investigated. The average DS was calculated from the N/C ratio in the products and from the weight gain. The degree of substitution determined by the nitrogen content (DS_N) values up to 0.25 in a one‐step synthesis of the etherified hemicelluloses could be controlled by the adjustment of the amount of solvent used and the molar ratio of NaOH or ETA to the anhydromonomer units in the hemicelluloses. The structure of the cationic hemicellulosic derivatives formed was determined by Fourier transform infrared spectroscopy and further confirmed with solution‐state ¹³C‐NMR spectroscopy. In comparison, no significant degradation of the hemicellulosic derivatives occurred during the etherification of the polymers in the homogeneous DMSO system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and antimicrobial activities of new water‐soluble bis‐quaternary ammonium methacrylate polymers

New methacrylate monomers containing pendant quaternary ammonium moieties based on 1,4‐diazabicyclo‐[2.2.2]‐octane (DABCO) were synthesized. The DABCO group contains either a butyl or a hexyl pendant group comprising the hydrophobic segment of the monomers and one tether group to the methacrylate moiety. The monomers were homopolymerized in water by using 2,2′‐azobis(2‐methylpropionamide) dihydrochloride (V‐50) as an initiator. The monomers and polymers were characterized by elemental analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), FTIR, and ¹³C‐NMR. The antimicrobial activities of the corresponding small molecules (bis‐quaternary ammonium monocarboxylates) and polymers were investigated against Staphylococcus aureus and Escherichia coli. Although the small molecules did not show any antimicrobial activity, the polymers were moderately effective against both Gram‐positive and Gram‐negative bacteria. The minimum inhibitory concentration (MIC) values of the polymers with butyl and hexyl hydrocarbon chains against S. aureus and E. coli were found to be 250 and 62.5 μg/mL, respectively. The minimum bactericidal concentration (MBC) value for the polymer with the butyl group was higher than 1 mg/mL, whereas the MBC value for the polymer with hexyl group was found to be 62.5 μg/mL. Thus, an increase of the alkyl chain length from 4 to 6 significantly increased the antimicrobial activity of the polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 635–642, 2004     

In situ pH-decrease-induced gelation of sodium alginate/carboxymethylated konjac glucomannan

The gelation kinetics and rheological properties of a mixture system containing two anionic polysaccharides, sodium alginate and carboxymethylated konjac glucomannan, in the presence of glucono-delta-lactone were investigated with dynamic viscoelastic measurements. The slow release of protons induced by glucono-delta-lactone gave birth to partly uncharged polymer chains and partly shielded electrostatic repulsion, resulting in an interpolymer association. This segregative interaction brought about a significant improvement in the elastic modulus of the resultant gel. The strongest synergism occurred at a carboxymethylated konjac glucomannan concentration of 29.9 wt %, exhibiting the highest gel strength. Increasing the content or the degree of substitution of carboxymethylated konjac glucomannan resulted in slower gelation kinetics. The fractal dimension of the incipient gel, which was not greatly affected by the mixing ratio or the degree of substitution of carboxymethylated konjac glucomannan, reflected a rather compact gel structure network. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of lignin–poly(acrylamide)–poly(2‐methacryloyloxyethyl) trimethyl ammonium chloride copolymer

In this work, two monomers, acrylamide (AM) and [2‐(methacryloyloxy)ethyl]trimethylammonium chloride (DMC) were copolymerized from kraft lignin (KL) in an aqueous suspension initiated by free radical copolymerization in the presence of potassium persulfate. The impact of copolymerization conditions on the charge density and molecular weight of the copolymers was investigated. The molecular weight and mass balance analyses confirmed that the homopolymer [polyDMC (PDMC) and polyAM (PAM)] and undesired copolymer (AM–DMC) productions dominated as time, initiator, and DMC dosage increased more than the optimum values. The activation energy of the polymerization of KL and AM (43.02 kJ mol^?1), KL and DMC (21.99 kJ mol^?1), AM (14.54 kJ mol^?1), DMC (10.34 kJ mol^?1), and AM and DMC (18.13 kJ mol^?1) was determined. Proton nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, and elemental analysis confirmed the production of KL–AM–DMC copolymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46338.     

Conjugation of a phenanthrene-imidazole fluorophore with the chondroitin sulfate generated from Escherichia coli K4 polysaccharide

Escherichia coli K4 expressed a fructosylated chondroitin (K4), which had a chondroitin structure after the defructosylation treatment. Polysaccharide K4 as a preferred precursor was modified to produce chondroitin sulfate A (CSA). Here, glycosaminoglycans including K4, defructosylated K4, and CSA were conjugated with fluorophore A, which were optimized under three reaction conditions to give the maximum DS of 2.9, 6.5, and 8.5%, respectively. All of conjugates displayed luminescence response linearly to concentration. And they exhibited good storage stability in luminescence and dispersion within 24 h. The conjugate CSA-A with substituted degree of 6.4% was chosen for the bioimaging study in vitro. CSA-A showed nontoxic to astrocytes with concentrations lower than 100 μg/ml. It was internalized effectively by astrocytes after incubation for 24 h.     

琥珀酰壳聚糖季铵盐的合成及絮凝性能

壳聚糖由于水溶性差、电荷密度低等缺点,使其在絮凝应用方面受到限制。对壳聚糖进行化学改性,可以改善其水溶性和絮凝性能。本文采用苯甲醛保护壳聚糖氨基,然后与丁二酸酐反应合成琥珀酰壳聚糖（SACTS）,进一步与二甲基二烯丙基氯化铵（DMDAAC）反应合成琥珀酰壳聚糖季铵盐（SAQCS）。采用FTIR、¹H NMR、XRD、ESEM等方法对SAQCS的结构和形貌进行表征。探讨了引发剂用量、单体配比、反应温度、反应时间对SAQCS阳离子度的影响。结果表明,SAQCS较优合成工艺条件为：引发剂用量（占单体的质量分数） 2%,m（DMDAAC）/m（SACTS）=5.4,反应温度70℃,反应时间7h。此工艺条件下合成的SAQCS的阳离子度为42.26%。将SAQCS、壳聚糖、聚丙烯酰胺与配制的高岭土模拟废水进行絮凝实验,考察了pH、投加量、温度对絮凝效果的影响。结果表明,当絮凝条件为pH=2～5、投加量3~9mg/L、温度25～50℃范围内,使用SAQCS絮凝后上清液浊度去除率均在96%以上。     

季铵盐型阳离子沥青乳化剂的合成方法

介绍了乳化沥青的分类及发展现状，就目前我国主要的季铵盐型沥青乳化剂的品种对其合成方法进行了总结。指出阳离子乳化沥青发展前景广阔，应大力发展阴阳离子复合乳化沥青和聚合物改性阳离子乳化沥青。     

Graft copolymerization of 4‐vinyl pyridine onto konjac glucomannan initiated by ammonium persulfate

The grafting of 4‐vinyl pyridine (4‐VP) onto konjac glucomannan (KGM) by ammonium persulfate (APS) as the initiator was studied in an acid aqueous solution under an inert atmosphere. The grafting ratio (G%) and grafting efficiency (E%) were evaluated comparatively. The dependence of these parameters on the initiator concentration, sulfuric acid concentration, ratio of monomer to KGM, temperature, and reaction time was also investigated. Under conditions of [KGM] = 1.00 g/L, [APS] = 1.00 × 10^?2 mol/L, [4‐VP] = 9.32 × 10^?2 mol/L, [H⁺] = 5.00 × 10^?2 mol/L, temperature = 35°C, and time = 120 min, the optimum G% and E% were 307.27 and 52.75%, respectively. The proof of grafting was obtained from thermogravimetric analysis and infrared spectra. Preliminary research of the graft's adsorption capacity for heavy‐metal ions [Cr(VI), Cu(II), Pb(II), and Cd(II)] was done. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of sustainable polyurethane modified by cyclic polysiloxane

In this article, a series of sustainable polyurethanes are prepared by introducing different content of cyclic polysilanol, which may act as a chain extender to replace 1, 4‐butanediol (BDO). Consequently, cyclic polysiloxanes are successfully incorporated into the molecular chains to afford organic–inorganic polyurethanes and then their effects on polyurethanes thermal properties and surface hydrophilicity are fully characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and contact angle testing. Results show that the hybrid polyurethanes display enhanced glass transition temperatures (T_g). While in terms of TGA, the effects of cyclic polysilanol on thermal properties seem complex, which would reduce the thermal stability in the first degradation process but enhance in the second process. The morphology observed by scanning electron microscopy (SEM) show that the inorganic constitutions, namely, cyclic polysilanol, may occur to self‐condensation or aggregation, which can help to explain the uncommon thermal phenomenon above. Thus, an opportunity of future applicability in the areas of sustainable polymer with improved properties can be envisioned in our research method of hybrid polyurethanes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41277.     

Synthesis and properties of cationic polyacrylamide containing pyridine quaternary salt

The copolymer P(AM‐co‐4VP) of acrylamide (AM) and 4‐vinylpyridine (4VP) was synthesized by radical copolymerization in solution, and then the copolymer was quaternarized using dimethyl sulfate to produce cationic P(AM‐co‐4VP) (CPAV), a cationic polyacrylamide containing quaternary pyridine salt. Two series of CPAV have been synthesized. The structure and composition of the copolymer and the cationic copolymer were characterized by their FTIR, ¹H NMR and ultraviolet spectra Flocculation and corrosion inhibition properties of the cationic copolymer were studied in detail and effects of cationic degree and molecular weight on the flocculation and corrosion inhibition properties were discussed. The results showed that cationic polyacrylamide containing quaternary pyridine salt possesses excellent flocculation, corrosion inhibition and other functions. The higher the degree of cationization, the better are these functions, and the molecular weight also effects the functions significantly. Copyright © 2003 Society of Chemical Industry     

柠檬酸三酯三季铵盐阳离子表面活性剂的合成

采用柠檬酸、环氧氯丙烷和十二烷基二甲基叔胺合成三烷基三季铵盐阳离子表面活性剂。得到较佳工艺条件:n(柠檬酸)∶n(十二烷基二甲基叔胺)∶n(环氧氯丙烷)为1∶3∶3,于85℃下反应12 h,得到产率大于90%的目的产物。测定了产物的cmc为3.3×10-4mol/L。研究了反应条件对目的产物产率的影响。结果表明:随反应温度的升高,产率逐渐增加,当升温到一定程度后,产率略有下降;反应12 h后产率基本不再变;十二烷基二甲基叔胺及环氧氯丙烷与柠檬酸的投料比大于3时,对三烷基三季铵盐阳离子表面活性剂产率的增加影响不大;异丙醇溶剂有利于反应产率的提高,但随着溶剂量的增多,反应产率会下降。     

魔芋葡甘聚糖复合凝胶的制备及其溶胀性能研究

通过在水中复配魔芋葡甘聚糖(KGM)、黄原胶(XG)和β-环糊精(β-CD),制备了KGM/XG/β-CD复合水凝胶。探讨了β-CD含量对凝胶平衡溶胀度的影响,并探讨了介质pH和温度对凝胶溶胀度的影响。结果表明,当m(KGM):m(XG):m(β-CD)=1:1:1时,复合凝胶的平衡溶胀度最大;复合凝胶的溶胀度在溶胀初期增加很快,随着溶胀时间的延长,溶胀度增加变慢,约7 h内基本达到平衡;随着介质pH的增大或体系温度从25℃增加至37℃,KGM/XG/β-CD复合凝胶的溶胀度随之增大。