Synthesis and fluorescence properties of a waterborne polyurethane–acrylic hybrid polymeric dye

A waterborne polyurethane–acrylic hybrid polymeric dye was prepared depending on soap-free emulsion polymerization method. The resulting polymeric dye composed of methyl methacrylate (MMA) monomer which was polymerized into polymethyl methacrylate (PMMA) as cores and waterborne polyurethane-based dye was synthesized by anchoring dye monomers (6-amino-2-cyclohexyl-benz[de]isoquinone-1,3-dione) to polyurethane chains as shells. The average particle sizes of the hybrid polymeric dye emulsions were found to be increased with the increase in MMA contents for MMA monomers. Compared with dye monomers, the absorption intensities and fluorescence intensities of the hybrid polymeric dye were enhanced with the increase of particle sizes. This study revealed that enhanced fluorescence intensity of the hybrid polymeric dye was mainly attributed to the hindered formation of exciplexes among dye monomers and an augmented light absorption area. It was found that the fluorescence intensity of the hybrid polymeric dye was increased with increasing temperature and the trend first increased and then decreased with increase in concentration. Furthermore, the fluorescence of the hybrid polymeric dye emulsions was found to be very stable and not sensitive to the fluorescence quencher.     

Synthesis and characterization of potassium humate–acrylic acid–acrylamide hydrogel

A novel potassium humate–acrylic acid–acrylamide (KHA–AA–AM) superabsorbent polymer was prepared from the reaction among leonardite potassium humate, acrylic acid and acrylamide by free radical initiating process using ammonium persulfate as the initiator and N, N′-methylene bisacrylamide as the crosslinker. Various effects of synthesis conditions on superabsorbent polymer were studied and the optimal reaction condition was obtained with crosslinker concentration 0.44–0.74 wt%, initiator concentration 1.12–2.22 wt%, n(KOH)/n(AA) 0.51–0.70, monomer concentration 10.95–12.59 wt%, graft reaction temperature 83 ± 1°C, monomer mole ratio of acrylic acid to acrylamide 1.42–2.30, and potassium humate content 17.54 wt%. Under the optimal conditions, the solution absorbency of KHA–AA–AM superabsorbent polymer to deionized water, tap water, 0.5% carbamide solution and 0.9% NaCl solution were 733–756, 161–284, 786–825, and 76–83 g/g, respectively.     

Grafting of sulfamethoxazole on acrylic acid−vinyl methyl ketone copolymer using the schiff base reaction−application as a drug delivery system

A series of poly(acrylic acid-co-methylvinylketone–graft–sulfamethoxazole)(AVMDS) species was synthesized for drug carrier applications. The synthesis involved two steps: copolymerization of acrylic acid(AA) with methyl vinyl ketone(MVK) through the free radical route and subsequent grafting of the sulfamethoxazole (SMX) onto the copolymer via the Schiff base reaction of the primary amine of SMX with the carbonyl groups of the MVK units. The structures and properties of the materials were characterized by nuclear magnetic resonance(NMR), X-ray diffraction(XRD), differential scanning calorimetry(DSC), and scanning electronic microscopy (SEM). An in-vitro cytotoxicity test of the drug-carrier systems via MTT assay revealed no significant cytotoxic effect at concentrations up to 100?µg?·?ml^?1. The dynamic release of SMX from these systems through a retro-imidation reaction (inverse Schiff base reaction) was investigated in depth, where the diffusion through the polymer matrix, the enhancement of the water solubility of SMX, the influence of the initial drug concentration, the pH of the medium, and the effect of the degree of swelling of the polymer matrix on the release dynamics were evaluated. The AVMGS4 and AVMGS1 drug carrier systems containing 3.58 and 1.18?wt% of SMX were the best performing systems.     

Synthesis and performance of alkyd–acrylic hybrid binders

Preparation and properties of alkyd–acrylic hybrids have been studied. Hybrids with different alkyd–acrylic ratios and acrylic parts were prepared via free radical polymerization of acrylic monomers in a presence of an unsaturated alkyd resin using emulsion polymerization technique. The binders were characterized according to their solid content, conversion, viscosity, pH and particle size. Evidence on formation of true copolymer was obtained via NMR spectroscopy and molecular weight and glass transition temperature measurements, as well as via performance studies. The performance evaluation was focused on investigation of drying, penetration and water repellency ability, as well as on film formation and surface topography studies. The binders were compared to references of an alkyd emulsion, acrylic latex and a blend made of them. The results showed that alkyd–acrylic hybrids with synergistic and improved properties can be prepared.     

Waterborne acrylic–casein latexes as eco-friendly binders for coatings

The use of casein as renewable resource to produce eco-friendly hybrid latexes has an increasing importance in industrial applications especially for high performance waterborne coatings. This work describes the synthesis of hybrid acrylic–casein latexes by emulsion polymerization of acrylic monomers in presence of varied casein concentration, and in absence of emulsifier which is usually a challenge for preparing stable nanocomposite latexes. The production and microstructure characterization of the casein–acrylic nanoparticles, as well as the properties of the films obtained from the hybrid latexes are here reported. The synthesized acrylic–casein latexes are able to form films with promising properties for a potential application as waterborne bio-based coatings.     

Model bulk Mo–V–Te–O catalysts for selective oxidation of propane to acrylic acid

The crystal structures and chemical compositions of the M1 and M2 phases proposed as active and selective in propane oxidation to acrylic acid over the bulk mixed Mo–V–Te–O catalysts were investigated by the transmission electron microscopy, coupled with energy dispersive analysis of X-rays. The results revealed that the crystal structure of the M1 phase is orthorhombic with space group Pbca, lattice parameters a=21.25 Å, b=27.14 Å, c=4.03 Å and composition Mo_0.64V_0.32Te_0.1O_3.05 (Mo/V ∼2), whereas M2 is hexagonal with space group P6mm, lattice parameters a=7.10 Å, c=4.05 Å and composition Mo_1.79V_1.85Te_0.1O_11.36 (Mo/V ∼1). The M1 phase was dominant in the Mo–V–Te–O catalyst. The results obtained indicated that the bulk Mo–V–Te oxides represent a well-defined model catalytic system for the studies of the surface molecular structure-activity/selectivity relationships in propane oxidation to acrylic acid.     

pH-Sensitive performance of dextran–poly(acrylic acid) copolymer and its application in controlled in vitro release of ibuprofen

Dextran–poly(acrylic acid) copolymers (D-A) are prepared through copolymerizing of acrylic acid (AA) with dextran. Their structural properties and performances are characterized using various methods. The results indicate that the carboxyl groups of poly(acrylic acid) strongly interact with the proton acceptors of glucose units in dextran, and the effects of AA/dextran molar ratio on the pH sensitivity of obtained copolymers are remarkable. The D-A copolymer shows a smart pH response, specifically, shrinkage in a low pH medium and swelling at high pH. The potential application of D-A copolymer as a drug delivery matrix is explored using ibuprofen as a model drug.     

Physical properties and biodegradation of acrylic acid grafted poly(ε-caprolactone)/chitosan blends

We blended films of acrylic acid grafted polycaprolactone (PCLgAA) and citosan (CS) with different compositions from aqueous acetic acid solution. DSC measurements showed that the melting temperatures and enthalpies of the blends decreased with increasing CS content. From FTIR results, we observe that the amino groups of CS form covalent bonds with the carboxylic groups of PCLgAA in addition to hydrogen bonds between the constituents in the blends. Though the crystal structure of the PCLgAA component was not changed, as proved by WAXD results, blending CS suppressed the crystallinity of the blends. Furthermore, the ductility of CS was increased during tensile testing in PCLgAA/CS blends due to enhanced affinity between the two components. However, PCLgAA/CS blends show greater resistance than PCL/CS blends to biodegradation in an enzymatic environment.     

Biodegradable depsipeptide–PDO–PEG-based block copolymer micelles as nanocarriers for controlled release of doxorubicin

Nowadays, biodegradable amphiphilic block copolymers with stable performance and adjustable structure have attracted the interests of researchers in the field of drug delivery. In this work, the triblock copolymer, P(SBMD-co-PDO)-b-PEG-b-P(SBMD-co-PDO), was successfully synthesized by ring-opening polymerization of 3(S)-sec-butyl-morpholine-2,5-dione (SBMD) and p-dioxanone (PDO) with poly(ethylene glycol) (PEG) as the initiator. In phosphate buffered solution (PBS), these copolymers could self-assemble into nano-sized micelles that have a hydrophobic P(SBMD-co-PDO) core surrounded by a hydrophilic PEG shell. Because of the strong hydrogen bonding and hydrophobic interactions, doxorubicin (DOX) was loaded into the micelles with high loading capacity (LC, up to 28.4%) and encapsulation efficiency (EE, up to 62.5%). The drug-loaded micelles showed sustained-release of DOX along with the hydrolytic degradation of the micelles in PBS. Therefore, these amphiphilic triblock copolymers have potential as drug matrix for controlled release.     

Synthesis and application of nanocomposite Fe3O4@SiO2@CTAB–SiO2 as a novel adsorbent for removal of cyclophosphamide from water samples

ABSTRACT

We present a way of synthesizing nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ by employing simple sol–gel technique with selective etching for extreme selectivity adsorption of cyclophosphamide (CP). The transmission electron microscopy (TEM); scanning electron microscopy (SEM); X-ray diffraction (XRD); Fourier transform infrared (FT-IR); vibrating sample magnetometer (VSM); pH_PZC; and Brunauer, Emmett and Teller (BET) techniques were used for nanocomposite characterization. These nanoparticles have an S_BET of 157.8 m² g^?1 and a high saturation magnetization of 67.5 emu g^?1. First, the adsorption system was examined as a function of contact time under various initial CP contents, ionic strength, initial solution pH, adsorbent dose and temperature in batch test. The optimum dose, pH and contact time were obtained to be 0.01 g, 7.0 and 30 min, respectively. Ultimately, experimental isotherm and kinetics data of adsorption of CP onto nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ were fitted to classical models. Additionally, it was found that the maximum adsorption process capacity of CP on adsorbent was 342.8 mg g^?1.     

Effects of different silane coupling agents on structure and properties of starch–chitosan–kaolin composites

Effects of different silane coupling agents on clay surface modification were studied. Herein, functionalized superfine kaolin was compounded with starch–chitosan (SCS) to prepare starch–chitosan-functionalized superfine kaolin composite. The characterization results showed that kaolin (K) was successfully modified; the composite formed a dense intercalated structure. The glass-transition temperature (T _g) was measured by differential scanning calorimetry and dynamic mechanical analysis. It decreased by 60 °C which attested the crystallinity of SCS. The results of thermogravimetric analysis showed that the fastest weight-loss temperature (T_max) was elevated by over 50 °C for composites. Mechanical properties of the composites were explored by electronic universal testing machine. Tensile strength and elongation of composites were improved by 4.7 and 10.9 times. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48050.     

Syntheses and self-assembly of novel polyurethane–itaconic acid copolymer hydrogels

Novel physically crosslinked polyurethane–itaconic acid (PU–I) copolymer hydrogels were synthesized by the macroiniferter-controlled radical polymerization method. The structures of the PU–I copolymer hydrogels were characterized by ¹H NMR, FTIR, GPC, and DSC. The water contact angles and self-assembly of the PU–I copolymer hydrogels have been investigated. The results revealed that PU–I copolymer hydrogels have good hydrophilicity, so the water contact angles of polyurethane could be easily adjusted by controlling the content of the hydrophilic vinyl monomers. The PU–I copolymer hydrogels were subjected to solvent-induced self-assembly in THF + water to construct a variety of morphologies. The morphology of the PU–I copolymer hydrogels’ self-assembly was observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the mechanism of self-assembly was investigated.     

Sulfuric acid–methanol electrolytes as an alternative to sulfuric–hydrofluoric acid mixtures for electropolishing of niobium

Attainment of the greatest possible interior surface smoothness is critical to meeting the performance demands placed upon niobium superconducting radiofrequency (SRF) accelerator cavities by next generation projects. Electropolishing with HF–H₂SO₄ electrolytes yields cavities that meet SRF performance goals, but a less-hazardous, more environmentally-friendly process is desirable. Reported studies of EP on chemically-similar tantalum describe the use of sulfuric acid–methanol electrolytes as an HF-free alternative. Reported here are the results of experiments on niobium samples with this electrolyte. Voltammetry experiments indicate a current plateau whose voltage range expands with increasing acid concentration and decreasing temperature. Impedance spectroscopy indicates that a compact salt film is responsible for the current plateau. Equivalent findings in electropolishing chemically-similar tantalum with this electrolyte were interpreted due to as mass transfer limitation by diffusion of Ta ions away from the anode surface. We infer that a similar mechanism is at work here. Conditions were found that yield leveling and brightening comparable to that obtained with HF–H₂SO₄ mixtures.     

Acrylamide–formaldehyde–urea copolymer as a novel compatibilizer for high density polyethylene/plant fiber composite

In the present work, a terpolymer of acrylamide–formaldehyde–urea (AMFU) which could interact with both plant fiber and high density polyethylene (HDPE) was synthesized, and which as novel compatibilizer for HDPE/plant fiber was also investigated. The result of SEM demonstrated that interfacial adhesion was observed in the presence of AMFU compatibilizer but void at the interface of HDPE/plant fiber without compatibilizer. Evident improvements on both static and dynamic mechanical property of WPC in the presence of AMFU compatibilizer were observed. Water uptake indicated that WPC with AMFU compatibilizer shown a lower water uptake. This research gives a new way in the design of new compatibilizer for WPC in the future.     

Fabrication of magnetic β-CD/chitosan nanocomposite as an efficient and recyclable dye adsorbent

ABSTRACT

In this work, novel magnetic nanocomposite adsorbents were prepared by crosslinking β-cyclodextrin (β-CD) onto chitosan backbones by using epichlorohydrin as a crosslinker and in the presence of Fe₃O₄ nanoparticles. The composition of β-CD-chitosan nanocomposites was characterized via FTIR, XRD, TEM, SEM, and VSM. Then, the as-prepared nanocomposites were treated for elimination of methyl orange (MO). The results indicated that the adsorption of MO exhibited a maximum adsorption capacity of 314 mg g^?1 at 25°C. Moreover, the rates and isotherm data of adsorption matched excellent at different MO concentrations (10, 60, and 120 mg/L) using second-order and Langmuir models with the regression coefficient (R²) of 0.9993 and 9990, respectively. Besides, the thermodynamic data confirmed MO adsorption as an endothermic process. The adsorbent was also confirmed as good materials for re-use and maintained 88% of its initial adsorption capacity for MO after the fifth regeneration cycles. In conclusion, the synthesized magnetic nanocomposites can be applied as cost-effective dye adsorbents with high regeneration efficiency.     

Synthesis and characterization of (poly (N-vinyl formamide)—pregelled starch—graft copolymer

Bromate / cyclohexanone redox system was investigated as a novel initiator for graft copolymerization of N-vinyl formamide onto pregelled starch. A number of variables in the grafting reaction were investigated including N-vinyl formamide, cyclohexanone, bromate ion, sulphuric acid and pregelled starch concentrations, material to liquor ratio along with polymerization time and temperature. The graft copolymers were evaluated in terms of graft yield, graft reaction efficiency and homopolymer formation (%). The optimum conditions for grafting of N-vinyl formamide onto pregelled starch are: N-vinyl formamide 50% based on weight of substrate, cyclohexanone 15 mmol / l, bromate ion, 30 mmol / l, liquor ratio 10, pH 6, time 120 min., and temperature 40°C. On the other hand, characterizations of the resultant copolymers with respect to swelling capacity, solubility %, metal ion up-take and suitability as a sizing agent for cotton textiles were investigated. The results obtained reflect that, the resultant copolymer shows better results for the aforementioned properties in comparison with that obtained from native pregelled starch as a starting substrate.     

Adsorption mechanism of copper ions in aqueous solution by chitosan–carboxymethyl starch composites

Based on the structural characteristics of chitosan (CTS) and carboxymethyl starch (CMS), CTS–CMS composites were prepared by crosslinking. The composites had a plurality of reactive functional groups such as  NH₂,  NH₃⁺,  COOH, and  OH and are applied to the adsorption of Cu²⁺ in aqueous solution. The adsorption capacity and stability in acidic solution of the composites were preferable to that of raw material. The effects of temperature, contact time, initial concentration, and pH on the adsorption of Cu²⁺ were investigated. Infrared spectroscopy, scanning electron microscope–energy dispersive spectrometer, X-ray diffraction, and X-ray photoelectron spectroscopy were used to explore the adsorption mechanism. The experiment showed that chemisorption and physisorption coexisted in the adsorption process. It is promising to apply this adsorbent to remove the metal ions in wastewater. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48636.     

Synthesis of end group functionalized styrene-butadiene-styrene three block copolymer using lithumamide as initiator

用氮锂引发剂合成端基官能化苯乙烯-丁二烯-苯乙烯三嵌段共聚物王强,廖明义,王玉荣,张雪涛,张春庆(大连理工大学化工学院,辽宁大连116012)研究了六亚甲基亚胺基锂、氮锂和正丁基锂引发剂引发苯乙烯的聚合速率,合成了端基官能化苯乙烯-丁二烯-苯乙烯三嵌段聚合物(SBS)。结果表明,在设计相对分子质量相同的情况下,随着四氢呋喃加入量的增加,端基官能化SBS的1,2-结构质量分数增加,顺式-1,4-结构和反式-1,4-结构质量分数下降,但两者比值基本不变。相同条件下,用氮锂引发剂制备的端基官能化SBS的1,2-结构质量分数要略高于用正丁基锂引发剂制备的SBS。     

Porous Mn–Co mixed oxide nanorod as a novel catalyst with enhanced catalytic activity for removal of VOCs

Mn–Co mixed oxide nanorod with porous structure and high surface area was fabricated by an oxalate route and further used for deep oxidation of VOCs. Compared to the single MnO_x or Co₃O₄, the Mn–Co mixed oxide showed an enhanced activity for ethyl acetate and n-hexane oxidation with T_90% was low to 194 and 210 °C at a high space velocity, respectively. The formation of solid solution with spinel structure inhibits the growth of nanoparticles which leads to its higher surface area, and the strong synergistic effect of Mn–Co species in the oxide makes a great contribution to its low temperature reducibility which plays a key role in VOCs' oxidation.