棉浆粕月桂酸酯的制备及其吸附有机废水污染物的研究

在氯化锂的N,N-二甲基乙酰胺（DMAc／LiCl）均相体系下,以棉浆粕为原料,月桂酰氯为酯化剂,吡啶为催化剂制备纤维素月桂酸酯,研究了月桂酰氯用量、反应温度、反应时间对纤维素酯的取代度（Ds）和得率的影响,确定了最佳的反应条件为月桂酰氯用量1．6～1．8mol／mol羟基、反应温度80℃、反应时间8h,此时产物得率为335％,产物DS=2．4。X射线衍射和接触角分析结果表明,纤维素月桂酸酯结晶结构发生了变化,疏水性随取代度增大而增强,DS=2．4时,接触角达118。,具有极强的疏水性。在25℃条件下,纤维素月桂酸酯吸附含氯代苯和吡啶的有机废水,达到吸附平衡所需时间为120min,吸附量随着取代度的增大而增大,DS=2．4的纤维素酯对1．0mmol／L的废水中氯代苯和吡啶的吸附量分别达0．82mmol／g和O．61mmol／g,表明纤维素酯对有机废水有较好的吸附能力。     

Water‐Soluble Amphiphilic O‐(Carboxymethyl)cellulose Derivatives – Synthesis and Properties

Summary: Water‐soluble, partially hydrophobized derivatives of O‐(carboxymethyl)cellulose (CMC) were prepared by esterification of CMC in its ‘gel suspension’ form. The classical esterification method (A) using stearoyl chloride/pyridine as well as two unconventional methods based on reaction with mixed anhydrides (B) and transesterification with vinyl laurate (C) respectively, were compared in terms of the structural, molecular and performance properties of the obtained derivatives. The classical esterification and method B yielded water‐soluble simple fatty acid esters, whereas mixed acetic‐fatty acid esters were obtained by method C. In all cases, molecular degradation of CMC was observed. ¹H and ¹³C NMR spectroscopy of the acetyl‐lauroyl derivatives of CMC with a degree of esterification DS_E of 0.20 indicated a prevalence of the lauroyl groups (DS_Ac:DS_La = 0.03:0.17). Most of the water‐soluble derivatives exhibited excellent emulsifying efficiency. They represent polysaccharide‐based surfactants with effective anti‐redeposition properties as well as good washing power. Suitable derivatives can be prepared under mild reaction conditions by both unconventional methods which implies that they have potential as substitutes for the expensive and invasive conventional method.

Preparation of CMC derivatives.     

Spinnability of SPPESK and its application in esterification

The electrospinning of sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) and its blend with polyether sulfone (PES) were investigated and the blend nanofibers were applied as a catalyst in esterification. Attempts to electrospin pure SPPESK resulted in electrospraying rather than electrospinning. However, a blend polymer solution of SPPESK and PES resulted in smooth electrospinning when SPPESK content was lower than 9 wt%. The geometrical properties such as fiber diameter and distribution, surface chemical properties such as inter-molecular interaction and crystalline, mechanical properties were investigated by SEM, FTIR, XRD, etc. The catalytic activities of SPPESK-PES nanofibers were measured by esterification of ethanol with acetic acid. A pseudo-homogeneous model was established to describe the kinetics of esterification with nanofiber as a catalyst. The results showed that the SPPESK-PES blend nanofiber had a high specific surface area (46.7–58.9 m²/g), good mechanical properties, good catalytic properties (ethanol conversion up to 80 % when reacted 8 h), and good forward rate constants (10.0?×?10^?3–14.6?×?10^?3 L/(mol?min)).     

Fabrication and characterization of electrospun PCL/Antheraea pernyi silk fibroin nanofibrous scaffolds

To engineer tissue restoration, it is necessary to provide a bioactive, mechanically robust scaffold. Electrospun poly(ε‐caprolactone) (PCL) nanofiber is a promising biomaterial candidate with excellent mechanical properties, but PCL scaffolds are inert and lack natural cell recognition sites. To overcome this problem we investigated the incorporation of Antheraea pernyi silk fibroin (ASF) containing inherent RGD tripeptides with PCL in electrospinning process. The mixing ratios showed remarkable impact on the properties of hybrid nanofibers. Increasing PCL content significantly enhanced the mechanical properties of nanofibers. In particular, the mechanical properties were remarkably enhanced when PCL content increased from 50 wt% to 70 wt%. Moreover, the biological assays based on endothelial cells showed promoted cell viability when ASF content reached to 30 wt%. The data demonstrated that the nanofiber containing 70% of PCL and 30% of ASF achieved the most balanced performances for integrating the mechanical properties of PCL and the bioactivity of ASF. Furthermore, biomimetic alignment of 70PCL/30ASF nanofibers was achieved, which could support PC12 neuron‐like cell growth and guide neurite outgrowth, providing a potentially useful option for the engineering of oriented tissues. The results show that the PCL/ASF hybrid nanofibers can be considered as a promising candidate for tissue engineering scaffolds. POLYM. ENG. SCI., 57:206–213, 2017. © 2016 Society of Plastics Engineers     

Electrospinning of polyacrylonitrile solutions containing diluted sodiumthiocyanate

The effect of NaSCN salt on the spinnability of polyacrylonitrile (PAN) solutions, its resulting morphology, mechanical property, and the flame resistance of the resulting electrospun nanofibers were studied. The intent was to develop a method to produce nanosized carbon fiber precursors with good properties. Electrospun PAN nanofibers from 9.7–9.9 wt% PAN/sodiumthiocyanate (NaSCN) (aq)/Dimethylformamide (DMF) solutions with 1.0–2.9 wt% NaSCN (aq), and 10–15 wt% PAN/DMF solutions without salt exhibited good spinnability and morphology with no beading in the range of applied voltage (18–20 kV) and take‐up velocity (9.8–12.3 m/s). The relatively high take‐up velocity produced good yarn alignment. The diameter distributions of the PAN nanofibers containing the NaSCN salt were narrower than those of the PAN/DMF nanofibers without the salt. It was determined that the maximum content of salt for production of electrospun PAN nanofibers with good morphology was below 3.8 wt% (40 wt% based on PAN). The salt concentration can positively influence on the narrow diameter distributions of the resulting electrospun fibers. Also, it could be confirmed that the salt effect on mechanical property and flame resistance of electrospun PAN nanofibers. In particular, the elongation of the PAN nanofiber with 2.9 wt% NaSCN (aq) was significantly increased as much as 186% compared with that of 10 wt% PAN nanofiber without the salt. The flame resistance and mechanical properties of the stabilized PAN nanofibers with NaSCN (aq) increased after oxidization process. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Single‐wall carbon nanotubes dispersion behavior and its effects on the morphological and mechanical properties of the electrospun nanofibers

The dispersion behavior of single‐walled carbon nanotube (SWCNT) has important effects on morphological and mechanical properties of SWCNT composite nanofibers. The relationship of the dispersion conditions with morphological and mechanical characteristics for SWCNT / polyacrylonitrile (PAN) / polyvinylpyrrolidone (PVP) composite nanofibers have been examined. The SEM and TEM analyses of the nanofibers revealed that the deformation in the nanofiber structures increases with increasing concentration of SWCNTs. Tensile results showed that only 2 wt% SWCNT loading to the electrospun composite nanofibers gave rise to 10‐fold and 3‐fold increase in the tensile modulus and tenacity of nanofiber layers, respectively. Essentially, high mechanical properties and uniform morphology of the composite nanofibers were found at SWCNT concentration of ∼2 wt% due to their stable and individual dispersion. POLYM. COMPOS., 33:1951–1959, 2012. © 2012 Society of Plastics Engineers     

Au/PANA/PVAc and Au/P(ANA-co-CNTA)/PVAc electrospun nanofibers as tyrosinase immobilization supports

Au/poly anthranilic acid/poly vinyl acetate and Au/poly(anthranilic acid-co-3-carboxy-N-(2-thenylidene)aniline)/poly vinyl acetate nanofibers through electrospinning and their modification with covalent tyrosinase (Ty) immobilization was performed. It was realized by surface activation using N-(3-dimetylaminopropyl)-N-ethylcarbodimide hydrochloride/N-hydroxysuccinimide chemistry. Electrochemical impedance spectroscopy (EIS), FTIR–ATR, Raman spectroscopy, and bicinchoninic acid assay analyses demonstrated that Ty was stably and covalently bonded onto the nanofibers. Increase in surface roughness [atomic force microscopy (AFM)] and the presence of Cu atoms in the nanofiber composition after enzyme immobilization confirmed the Ty immobilization. The charge transfer resistances of the nanofibers decreased due to changes in the nanofiber surfaces after attachment of enzyme.     

Continuous production of acyl <Emphasis Type="SmallCaps">l</Emphasis>-ascorbates using a packed-bed reactor with immobilized lipase

Saturated acyl (6-O-caproyl, lauroyl, and myristoyl) and unsaturated acyl (6-O-oleoyl, linoleoyl, and arachidonoyl) l-ascorbates were continuously synthesized at 50°C using a system where a column packed with ascorbic acid powder and a packed-bed reactor with an immobilized lipase from Candida antarctica were connected in series. A productivity of 1.6–1.9 kg/L reactor·d was achieved for at least 11 d. The surface tension of the caproyl or lauroyl l-ascorbate in aqueous solution was measured at various temperatures and pH to estimate the critical micelle concentration (CMC) of the acyl l-ascorbate. The CMC values were independent of temperature but dependent on the pH. The value of the caproyl ascorbate increased with an increase in pH.     

Physicochemical modifications of partially esterified cellulose evidenced by inverse gas chromatography

Partial esterification of cellulose using acyl chlorides having 5 and 16 carbon atoms was performed in a swelling medium to produce cellulosic esters with two different degrees of substitution (DS = 0.15 and 0.45). The effects of this treatment on the surface energy, on the water uptake, and on the acido-basic character of the cellulose were studied by inverse gas chromatography and thermogravimetric analysis. The attaching of alkyl chains to the surface of cellulose reduces its acidic character and its hydrophilicity and the DS required for such an effect depends on the chain length. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2195–2203, 1998     

Acrylonitrile/vinyl acetate copolymer nanofibers with different vinylacetate content

In this study, free radical copolymerization of acrylonitrile (AN)–vinyl acetate (VAc) was performed for five different feed ratio of VAc (wt %) by using ammonium persulfate (APS) in the aqueous medium. The effect of VAc content on the spectrophotometric and thermal properties of AN–VAc copolymers was investigated by Fourier Transform Infrared–Attenuated Total Reflectance spectrophotometer (FTIR–ATR), differential scanning calorimeter (DSC), and thermal gravimetric analyzer (TGA). Thermal stability of homopolymer of AN is improved after being copolymerized. The electrospun P(AN‐co‐VAc) nanofibers were fabricated and the effect of VAc content on the morphologic properties of nanofibers was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The viscosity of the solution had a significant effect on P(AN‐co‐VAc) electrospinning and the nanofiber morphology. The average diameters of P(AN‐co‐VAc) nanofibers decreased 3.4 times with increasing feed ratio of VAc wt %. The P(AN‐co‐VAc) electrospun nanofiber mats, with the feed ratio of 30 wt % VAc, can be used as a nanofiber membrane in filtration and as a carbon nanofiber precursor for energy storage applications due to high surface to volume ratio, high thermal stability, homogeneous, and thinner nanofiber distribution. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Graphitic carbon nanofiber (GCNF)/polymer materials. II. GCNF/epoxy monoliths using reactive oxydianiline linker molecules and the effect of nanofiber reinforcement on curing conditions

Reactive (r‐) graphitic carbon nanofibers (GCNFs) with 3,4'‐oxydianiline (ODA), r‐GCNF‐ODA, capable of covalent binding to an epoxy resin during thermal curing, are prepared by reaction of GCNFs surface‐derivatized with ODA linker molecules (GCNF‐ODA) with butyl glycidyl ether. The thermal curing characteristics of r‐GCNF‐ODA/epoxy resin mixtures having nanofiber loadings of 0.3 wt% and 1.3 wt% are analyzed by differential scanning calorimetry (DSC). The quality of the cured GCNF/epoxy nanocomposites is assessed through bending tests and scanning electron microscopy (SEM). These results indicate that the presence of r‐GCNF‐ODA nanofibers affects the thermal curing process, and that additional heating is required to achieve cured nanocomposites at higher nanofiber loadings. Reaction of GCNF‐ODA nanofibers with butyl glycidyl ether prior to mixing with an epoxy resin gives more well‐dispersed r‐GCNF‐ODA/epoxy resin mixtures and r‐GCNF‐ODA/epoxy nanocomposites having better flexural strength than the corresponding GCNF‐ODA/epoxy materials. POLYM. COMPOS., 26:128–135, 2005. © 2005 Society of Plastics Engineers     

Enhancement of heavy metal ion adsorption using electrospun polyacrylonitrile nanofibers loaded with ZnO nanoparticles

This article describes the adsorption and tensile behavior of electrospun polyacrylonitrile (PAN) nanofiber mats loaded with different amounts of ZnO [0.5, 1.0, 2.0, and 5.0 wt%] nanoparticles. X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transforminfrared (FTIR) spectroscopy, and thermal gravimetric analysis (TGA) were utilized to characterize the resulting composite nanofibers. Microscopic investigations revealed that the increase in surface roughness and diameter of the electrospun PAN nanofibers was due to the addition of ZnO nanoparticles. Adsorption results indicated that the fabricated PAN/ZnO (2.0 wt%) composite nanofiber mats showed the best adsorption performance with 261% and 167% increase in adsorption capacities for Pb(II) and Cd(II) from aqueous solutions, respectively, compared to pristine PAN nanofibers. The adsorption equilibrium was reached within 60 min, and the process could be described using the nonlinear pseudo-second-order kinetic model. The adsorption isotherm study was better represented by the Langmuir model, which suggested a homogeneous distribution of the monolayer adsorptive sites on the surface of the composite nanofibers. Mechanical testing revealed that the decrease in tensile strength and elongation at breakof the PAN/ZnO composite nanofiber mats was due to the formation of some bead defects and agglomerates within the structure of the PAN nanofibers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47209.     

Preparation of higher aliphatic acid esters of wood in an N2O4–DMF cellulose solvent medium

Esterification of wood meal with a series of aliphatic acid anhydrides and acid chlorides in a nonaqueous cellulose solvent, an N₂O₄–DMF solvent, has been studied. The N₂O₄–DMF–pyridine solution used as the reaction medium plays a role in destroying the molecular order of the cellulose within the wood, enabling the cellulose to be uniformly substituted by acyl groups along its chain. These uniformly distributed blocking groups result in the permanent decrystallization of the wood. The acyl blocking groups are best achieved by esterification using acid chlorides in the nonaqueous solvent. Acid chlorides, from caproyl to stearoyl chloride, were found to be much more effective as acylating agents than acid anhydrides, from propionic to caproic anhydride. Although no difference in reactivity can be recognized among the acid chlorides, the reactivity decreases with increase in the number of carbon atoms in the acyl group among the acid anhydrides.     

Determination of the Z 1H NMR chemical shift substituent parameters for the sulfinyl chloride and sulfinate ester functionalities

Using established and new ¹H NMR data for sulfinate esters and sulfinyl chlorides, the parameters required for predicting position-dependent alkene ¹H NMR chemical shifts of vinylic sulfinate esters and vinylic sulfinyl chlorides have been obtained. Standard deviations of the new Z parameters lie in the range 0.08 to 0.15?ppm. Sulfinyl chloride and cyclohexyl sulfinate derivatives of (E) and (Z)-2-cyanoethenesulfinic acids have been prepared for the first time.     

A comprehensive study on Plantago ovata/PVA biocompatible nanofibers: Fabrication,characterization, and biological assessment

In this study, a biocompatible nanofiber is fabricated using Plantago ovata mucilage (POM) combined with polyvinyl alcohol (PVA), which is considered as a non-toxic polymer. High quality nanofibers were produced by controlling the electrospinning parameters after selecting an appropriate solvent for the POM/PVA combination (12% PVA and 3% POM). Electrospinning parameters, including high voltage, distance from collector to tip, feed rate and POM to PVA proportion were optimized following preparation of an aqueous POM/PVA solution. Using the results of scanning electron microscopy, the optimized electrospinning conditions for producing POM/PVA nanofibers were determined (high voltage = 18 kV, distance = 15 cm, feed rate = 0.125 ml/hr, PMM/PVA = 50/50) and uniform nanofibers with an average diameter of 250 nm were produced. The POM/PVA nanofiber sample was evaluated by determining the mechanical strength, characterization of produced nanofiber morphology, and investigating the cell viability by applying MTT assay. The bands for both POM and PVA from FTIR results showed that the samples remained stable. The tensile strength results showed that blending POM with PVA solution enhanced the Young's modulus by factor of 3.2 (0.2 MPa to 0.64 MPa). The MTT analysis on POM/PVA cell lines proved that the produced nanofiber considerably enabled the cellular proliferation. Enhancement in these analysis indicated how POM-based nanofibers is a promising scaffold for cell culture, drug delivery systems and food additives.     

Preparation of polyester nanofibers and nanofiber yarns from polyester/cellulose acetate butyrate immiscible polymer blends

Development of high throughput production processes for making thermoplastic nanofiber and nanofiber yarns are urgently needed. PET, PTT, and PBT nanofibers were prepared from PET/CAB, PTT/CAB, PBT/CAB immiscible polymer blends by in situ microfibrillar formation during the melt extruding process. The diameter distribution and crystallization properties of PET, PTT, and PBT nanofibers were analyzed. After removing the CAB matrix phase, the nanofibers could be collected in the forms of random or aligned nanofibers and nanofiber bundles or yarns. To understand the formation mechanism of the nanofibers, the morphology development of three different polyesters in the dispersed phase were studied with samples collected at different zones in a twin‐screw extruder. The morphological development mechanism of the dispersed phases involved the formation of sheets, holes and network structures, then the size reduction and formation of nanofibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhancing water swelling ability and mechanical properties of water‐swellable rubber by PAA/SBS nanofiber mats

Investigation of the potential use of nanofibers to reinforce composites has gained significance in many applications. In this article, the nanofiber mats of poly(acrylic acid) (PAA) and styrene–butadiene–styrene (SBS) triblock copolymer with composites structure were interweaved by double needle electrospinning process. The multiple nanofiber mats were added to conventional water‐swellable rubber (WSR). Improved mechanical and physical properties of WSR were obtained. Enhancement of the swellability of WSR + PAA/SBS nanofiber mats was derived from the PAA constituent absorbing water from the surface into the bulk and introducing random internal water channels between discontinuous superabsorbent polymers. The role of SBS nanofibers in the composite of WSR + PAA/SBS nanofiber mats was more related to the mechanical properties, where the breaking force of the composite increased to twice that of the conventional WSR. Interestingly, after immersion of the WSR + PAA/SBS nanofiber mats in water for 1 week, there was only a slight decrease in their mechanical properties of less than 5% compared to the dry state. The mechanisms and effects of the nanofiber mats in enhancing the mechanical and water swelling properties of WSR are also discussed. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44213.     

Synthesis of (Z)‐3‐hexen‐1‐yl acetate by lipase immobilized in polyvinyl alcohol nanofibers

Polyvinyl alcohol (PVA)‐nanofibers‐immobilized lipase were formed by electrospinning. The specific surface area of the nanofiber (5.96 m²/g) was about 250 times larger than that of PVA‐film‐immobilized lipase (0.024 m²/g). The PVA‐nanofibers‐immobilized lipase were used as the catalyst for the esterification of (Z)‐3‐hexen‐1‐ol (leaf alcohol) with acetic acid in hexane. The activity of the nanofiber is equivalent to that of commercially available immobilized lipase (Novozym‐435). The ester conversions of the nanofibers, Novozym‐435, the film and lipase powder reached 99.5% at 5 h, 100% at 5 h, 11.5% at 6 h, and 81.1% at 5.75 h, respectively. The nanofibers‐immobilized lipase showed higher activity for the esterification than the film‐immobilized lipase and lipase powder, probably because it has high specific surface area and high dispersion state of lipase molecules in PVA matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Aligned electrospun sulfonated polyetheretherketone nanofiber based proton exchange membranes for fuel cell applications

In this study, electrospinning of sulfonated poly(ether ether ketone) (SPEEK) at different degrees of sulfonation (DS) was investigated. The polymer solution concentration of 22 wt% was obtained to collect smooth fiber in nanoscale range of 112 to 131 nm at various conditions. SEM observations of SPEEK nanofibers showed the decrease of diameter with increasing DS from 74% to 81%, mainly due to the increase of electrical conductivity of polymer solution at higher DS. The increase of collecting speed from 20 to 305 m/min decreased the diameter of nanofibers slightly and improved their alignment. The presence of SO₃H groups in collected nanofibers was demonstrated with FT‐IR analysis. WAXD patterns of SPEEK nanofibers indicated featureless amorphous peak with no crystalline regions that was broaden at higher DS and aligned nanofibers. The electrochemical impedance spectroscopy of SPEEK nanofibers showed the through‐plane proton conductivity of fully hydrated nanofibrous membranes measured at room temperature were improved with DS. The proton conductivity of randomly oriented and aligned nanofibers were measured from 0.0098 to 0.0722 S/cm and from 0.0592 to 0.0907 S/cm, respectively. Aligned nanofibers exhibited more proton conductivity than randomly collected nanofibers. POLYM. ENG. SCI., 57:789–796, 2017. © 2016 Society of Plastics Engineers     

Preparation and antibacterial activity of PET/chitosan nanofibrous mats using an electrospinning technique

The nanofiber deposition method, by electrospinning, was employed to introduce antibacterial activity and biocompatibility to the surface of poly (ethylene terephthalate) (PET) textiles. The polymer blends of PET and chitosan were electrospun on to the PET micro‐nonwoven mats for biomedical applications. The PET/chitosan nanofibers were evenly deposited on to the surface, and the diameter of the nanofibers was in the range between 500 and 800 nm. The surface of the nanofibers was characterized using SEM, ESCA, AFM, and ATR‐FTIR. The wettability of the PET nanofibers was significantly enhanced by the incorporation of chitosan. The antibacterial activity of the samples was evaluated utilizing the colony counting method against Staphylococcus aureus and Klebsiella pneumoniae. The results indicated that the PET/chitosan nanofiber mats showed a significantly higher growth inhibition rate compared with the PET nanofiber control. In addition, the fibroblast cells adhered better to the PET/chitosan nanofibers than to the PET nanofibers mats, suggesting better tissue compatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007