淀粉接枝衣康酸/丙烯酸高吸水材料制备与性能

旨在为降低吸水材料成本、拓宽原料来源、提高生物降解性、减少对石油化工产品的依赖提供指导,以水溶液接枝共聚法制备了淀粉接枝衣康酸/丙烯酸高吸水材料（S/IA/AA）,讨论了淀粉糊化条件、中和度、单体含量、反应温度等因素对材料吸水性能的影响,采用FTIR、SEM、EDX等对吸水材料进行表征。研究表明：淀粉糊化最佳条件为糊化温度80℃,糊化比为10 g•g^-1,糊化时间30 min;吸水材料合成最佳条件为中和度50%,衣康酸40%,淀粉20%,引发剂为4×10^-3 mol•L^-1,交联剂0.075%,反应温度50℃;利用40％衣康酸替代丙烯酸所制S/IA/AA同S/AA相比,其吸水性能有一定提高且保水性能优良。     

Preparation and characterization of pH‐sensitive hydrogels based on chitosan,itaconic acid and methacrylic acid

Novel pH‐sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid were prepared in two steps. Chitosan was first ionically crosslinked with itaconic acid, after which a free radical polymerization and crosslinking of the chitosan/itaconic acid network was performed by adding methacrylic acid and a crosslinker in order to achieve better mechanical properties and tunable swelling. The samples were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, X‐ray diffraction, dynamic mechanical analysis and the swelling ratios of the hydrogels at various pH values (2.0–8.0). The hydrogel composition is found to have a great impact on the hydrogel structure, mechanical and thermal properties, morphology and swelling kinetics. The highly porous morphology of the gels is probably connected with the bulky chitosan/itaconic acid network which reduces the degree of crosslinking in the second step of the synthesis due to steric hindrances. The gels demonstrate substantial change in buffer absorbency with change of pH, low for acid buffers and the higher for pH values above 6 where the swelling is considerably slow, thus suggesting their strong candidature for use as oral drug‐delivery systems in the lower parts of the gastrointestinal tract and for drugs that require longer release times. Copyright © 2010 Society of Chemical Industry     

Preparation of chitosan‐coated magnetite nanoparticles and application for immobilization of laccase

In this study, immobilization of laccase (L) enzyme on magnetite (Fe₃O₄) nanoparticles was achieved, so that the immobilized enzyme could be used repeatedly. For this purpose, Fe₃O₄ nanoparticles were coated and functionalized with chitosan (CS) and laccase from Trametes versicolor was immobilized onto chitosan‐coated magnetic nanoparticles (Fe₃O₄‐CS) by adsorption or covalent binding after activating the hydroxyl groups of chitosan with carbodiimide (EDAC) or cyanuric chloride (CC). For chitosan‐coated magnetic nanoparticles, the thickness of CS layer was estimated as 1.0–4.8 nm by TEM, isoelectric point was detected as 6.86 by zeta (ζ)‐potential measurements, and the saturation magnetization was determined as 25.2 emu g^?1 by VSM, indicating that these nanoparticles were almost superparamagnetic. For free laccase and immobilized laccase systems, the optimum pH, temperature, and kinetic parameters were investigated; and the change of the activity against repeated use of the immobilized systems were examined. The results indicated that all immobilized systems retained more than 71% of their initial activity at the end of 30 batch uses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of poly(2‐acrylamido‐2‐methylpropane‐sulfonic acid) grafted chitosan using potassium persulfate as redox initiator

A grafted material based on chitosan and 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) has been successfully prepared in homogenous solution using potassium persulfate as a redox initiator. The grafted copolymer was precipitated during the reaction polymerization. The effects of the reaction temperature and chitosan–potassium persulfate contact time as well as concentrations of AMPS, potassium persulfate, and acetic acid on grafting yield were investigated. The percentage of grafting is gradually increased with the increasing of the AMPS concentration. The extent of grafting can be controlled by setting the appropriate reaction conditions. The maximum percentage of grafting was about 180% under the optimum conditions (1% v/v acetic acid, 50°C reaction temperature, 10 min chitosan–potassium persulfate mixing period, 0.37 mmol of potassium persulfate, and 28.96 mmol AMPS). The grafted chitosan was insoluble in the acid of the grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2314–2318, 2000     

多巴胺包埋磁性SiO2固定化漆酶催化去除4-氯酚

以磁性纳米颗粒为载体,通过多巴胺(dopamine,DA)聚合原位包埋制备了磁性SiO₂固定化漆酶(Fe₃O₄@SiO₂-PDA-Lac)。结果显示纳米颗粒尺寸均匀,并且保持较高的饱和磁性。通过最优条件制备出的固定化漆酶在50℃放置6 h后,活性保持在63%,而游离酶仅保留18%。将固定化酶用于催化降解4-氯酚(4-CP),探究了溶液pH、漆酶浓度和ABTS[2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸铵)]对4-CP去除率的影响。固定化漆酶在反应最适pH时,4-CP去除率为84.3%,而游离酶仅为65.7%。当漆酶浓度为1.2 U·ml^-1时,反应8 h后,4-CP去除率可达95%,而游离酶的4-CP去除率仅82%。ABTS可促进固定化漆酶降解4-CP,当体系中加入50 μmol·L^-1 的ABTS,反应10 min后,固定化酶对4-CP去除率可达99%。固定化漆酶在重复使用10次后,4-CP去除率仍可达67%。     

整体型大孔/介孔PDA/SiO2复合材料固定化漆酶及其在染料降解中的应用

用硬模板法制得具有三维连续贯通孔道结构的整体型大孔/介孔SiO₂，通过多巴胺（DA）在大孔/介孔SiO₂孔道表面的原位氧化聚合，制得聚多巴胺（PDA）功能化修饰的整体型大孔/介孔复合材料（PDA/SiO₂）。应用SEM、BET、FTIR和TG等技术对修饰前后的材料进行表征。以PDA/SiO₂为载体固定诺维信工业级漆酶，系统研究了pH、固定化时间、漆酶初始浓度及温度对漆酶固定化的影响；以偶氮荧光桃红作为模拟污染物，研究了固定化漆酶对染料的催化降解性能。结果显示，在漆酶浓度为80mg/mL、pH为4.0、固定化时间为6h及固定化温度为25℃时，固定化漆酶酶活达到最高（348.9U/g）。在偶氮荧光桃红浓度为10mg/L、pH为7.0、温度为30℃、降解时间为8h时，固定化漆酶对偶氮荧光桃红脱色率 ≥ 99.9%，且固定化漆酶易从反应体系中分离，重复使用性能良好。     

Preparation of methacrylic acid‐grafted chitin using cerium (IV) ion and its application in adsorbing paraquat

Chitin‐grafted‐poly(methacrylic acid) (chi‐g‐PMAA) was synthesized and characterized as an adsorbent of paraquat. Chi‐g‐PMAA copolymers were prepared using various concentrations of ammonium cerium(IV) nitrate (Ce⁺⁴) to determine the optimal concentration of Ce⁺⁴. Grafting was verified by differential scanning calorimeter thermograms, FTIR, and solid‐state ¹³C‐NMR spectra. A representative chi‐g‐PMAA copolymer was neutralized to a sodium salt (chi‐g‐PMANa) and used to adsorb paraquat. The adsorption equilibrium data are strongly related to both the Langmuir and the Freundlich isotherms. The maximal adsorption capacity is 147.0 mg/g‐adsorbent. This value exceeds those of Fuller's earth and activated carbon, which are the most common binding agents that are currently used for paraquat. The results suggest that chi‐g‐PMANa has potential as a paraquat adsorbent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Chitosan,itaconic acid and poly(vinyl alcohol) hybrid polymer networks of high degree of swelling and good mechanical strength

Chitosan is a biodegradable, non‐toxic, biocompatible polymer convenient for use in drug delivery. In this study, hybrid polymeric networks (HPNs) based on chitosan, itaconic acid and poly(vinyl alcohol) (PVA) were prepared and characterized. Chitosan was dissolved in itaconic acid in order to obtain ionic crosslinking with the dicarboxylic acid. In the second step, this chitosan/itaconic acid network was mixed with PVA and chemically crosslinked with glutaraldehyde. The chitosan/itaconic acid ratio was kept constant, while the concentrations of PVA and glutaraldehyde were varied. All samples were characterized using swelling studies, dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction and scanning electron microscopy. The equilibrium degrees of swelling obtained for the HPNs were higher than most of the values reported for chitosan hydrogels obtained by dissolving chitosan in acetic acid or HCl aqueous solutions. This method of synthesis also resulted in hydrogels with better mechanical properties and thermal stability. By changing the PVA content and the degree of crosslinking, it is possible to finely tune the properties of the HPNs, which could make them suitable as potential matrices in controlled drug delivery. Copyright © 2010 Society of Chemical Industry     

Determination of swelling behavior and morphological properties of poly(acrylamide‐co‐itaconic acid) and poly(acrylic acid‐co‐itaconic acid) copolymeric hydrogels

Poly(acrylamide‐co‐itaconic acid) (PAAmIA) and poly(acrylic acid‐co‐itaconic acid) (PAAIA) copolymeric hydrogels were prepared with different compositions via free‐radical polymerization. Ethylene glycol dimethacrylate (EGDMA) was used as an original crosslinker for these monomers. Gelation percentages of the monomers were studied in detail and it was found that addition of IA into the monomer mixture decreased the gelation percentage. The variation in swelling values (%) with time, temperature, and pH was determined for all hydrogels. PAA, which is the most swollen hydrogel, has the swelling percentage value of 2000% at pH = 7.4, 37°C. Swelling behaviors were explained with detailed SEM micrographs, which show the morphologic differences between dry and swollen hydrogels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5994–5999, 2006     

Synthesis and characterization of novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels

Novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels were prepared by free radical copolymerization of acrylamide and itaconic acid (IA) in chitosan solution. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and the swelling ratios of the hydrogels in water (pH 6.8) and pH 1.2. The influence of composition on the thermal properties of the hydrogels was assessed. The glass transition temperatures of the samples increased with IA content, ranging from 110 to 136 °C. Swelling of the hydrogels was found to obey second‐order kinetics with respect to the remnant swelling, indicating that diffusion is controlled by the relaxation of chains. The equilibrium swelling degree was strongly dependent on pH and composition. At both pH values the highest water uptake was obtained for the IA‐free sample M1. From the equilibrium swelling results the average molar mass between crosslinks, M_c, and the crosslink density of the chitosan‐poly(acrylamide‐co‐itaconic acid) samples were calculated. The results evidenced the reinforcing effect of IA on the hydrogel structure. It is concluded that these highly swellable pH‐sensitive hydrogels can be useful for applications in biomedicine and pharmacy. © 2013 Society of Chemical Industry     

Preparation of a Cu(II)-PVA/PA6 Composite Nanofibrous Membrane for Enzyme Immobilization

PVA/PA6 composite nanofibers were formed by electrospinning. Cu(II)-PVA/PA6 metal chelated nanofibers, prepared by the reaction between PVA/PA6 composite nanofibers and Cu²⁺ solution, were used as the support for catalase immobilization. The result of the experiments showed that PVA/PA6 composite nanofibers had an excellent chelation capacity for Cu²⁺ ions, and the structures of nanofibers were stable during the reaction with Cu²⁺ solution. The adsorption of Cu(II) onto PVA/PA6 composite nanofibers was studied by the Langmuir isothermal adsorption model. The maximum amount of coordinated Cu(II) (q_m) was 3.731 mmol/g (dry fiber), and the binding constant (K_l) was 0.0593 L/mmol. Kinetic parameters were analyzed for both immobilized and free catalases. The value of V_max (3774 μmol/mg·min) for the immobilized catalases was smaller than that of the free catalases (4878 μmol/mg·min), while the K_m for the immobilized catalases was larger. The immobilized catalases showed better resistance to pH and temperature than that of free form, and the storage stabilities, reusability of immobilized catalases were significantly improved. The half-lives of free and immobilized catalases were 8 days and 24 days, respectively.     

Interactions between poly(acrylamide)–poly(itaconic acid) and cerium(IV)–nitrilotriacetic acid redox pair in the synthesis of acrylamide and itaconic acid homo‐ and copolymers

Homopolymers of itaconic acid (PIA) and its copolymers with acrylamide (P(IA‐AAm) were synthesized using ceric ammonium nitrate (NH₄)₂Ce(NO₃)₆ in combination with nitrilotriacetic acid (NTA) as redox initiator, and potassium persulphate at pH 1. The chain structures of the resulting products have been studied by FTIR spectroscopy. It is concluded from a comparison of spectroscopic results with gravimetric and viscometric data that the depressions in the yields and viscosity numbers in the case of Ce(IV)–NTA redox pair result from interactions between the constituents of the redox initiator and IA. Spectra of the insoluble and pale yellow precipitates, which are formed during the first 4 h of the reaction, after addition of Ce(IV) solution to the NTA and NTA–IA homogeneous solutions, also indicate the presence of various oxidation products. Furthermore, it is observed that H‐bonded homopolymer complex obtained from PAAm–PIA blends, prepared from aqueous solutions containing equal unit moles of each polymer, contain both ordered and defective structures. © 2001 Society of Chemical Industry     

Polymeric multifunctional carboxylic acids as crosslinking agents for cotton cellulose: Poly(itaconic acid) and in situ polymerization of itaconic acid

Multifunctional carboxylic acids have been used as nonformaldehyde durable press finishing agents for cotton. In previous research we found that maleic acid (MA) and itaconic acid (IA) polymerize in situ on cotton fabric at elevated temperatures when both potassium persulfate (K₂S₂O₈) and sodium hypophosphite (NaH₂PO₂) are present, thus imparting wrinkle resistance to the treated cotton fabric. We also found that MA and IA polymerize in aqueous solutions in the presence of K₂S₂O₈ and NaH₂PO₂. In this research, we compared the effectiveness of poly(itaconic acid) (PIA) applied to cotton fabric as a polymer and IA applied as a monomer and allowed to polymerize in situ for crosslinking cotton cellulose. We found that IA is more effective in esterifying cotton cellulose and imparting a high level of wrinkle resistance to the fabric as it polymerizes in situ than PIA applied as a polymer. We also found that tensile strength loss of the cotton fabric crosslinked by IA polymerizing in situ as a function of fabric wrinkle recovery angle is practically the same as that crosslinked by PIA applied as a polymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 319–326, 2001     

Thermal crosslinking of collagen immobilized on poly(acrylic acid) grafted poly(ethylene terephthalate) films

Graft polymerization of acrylic acid onto plasma‐treated poly(ethylene terephthalate) (PET) films was used to prepare surfaces suitable for collagen immobilization by dip‐coating. Such surfaces could be used as matrices for smooth muscle cell cultures in tissue engineering. Contact angle measurements showed that plasma‐treated and grafted PET films undergo considerable surface reorganization during storage under ambient conditions. However, after collagen immobilization the contact angle remained relatively stable. The amount of collagen initially attached to the film surface increased with increasing poly(acrylic acid) graft density, but subsequent washing in water led to significant collagen loss. This loss could nevertheless be substantially reduced by thermal crosslinking of the collagen in the range 110–130 °C. Atomic force microscopy (AFM) observations suggested that the washed crosslinked collagen has a very similar structure to that of the un‐crosslinked collagen. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1874–1880, 2002     

Preparation and application of glycidyl methacrylate and methacrylic acid monomer mixture‐grafted poly(ethylene terephthalate) fibers for removal of methylene blue from aqueous solution

A novel fibrous adsorbent that grafts glycidyl methacrylate (GMA) and methacrylic acid (MAA) monomer mixture onto poly(ethylene terephthalate) (PET) fibers was used for removal of methylene blue (MB) in aqueous solutions by a batch equilibration technique. The operation parameters investigated included, pH of solution, removal time, graft yield, dye concentration, and reaction temperature. The adsorption rate of MB is much higher on the MAA/GMA‐grafted PET fibers than on the ungrafted PET fibers. MB was removed 99% the initial dye concentration at 10 mg L⁻¹ and 93% at 200 mg L⁻¹ by monomers mixture‐grafted PET fibers. Pseudofirst order and pseudosecond order kinetic equations were used to examine the experimental data of different graft yield. It was found that the pseudosecond order kinetic equation described the data of dye adsorption on fibrous adsorbent very well. The experimental isotherms data were analyzed using Langmuir and Freundlich isotherm models. The data was that Freundlich isotherm model fits the data very well for the dyes on the fibers adsorbent. The dye adsorbed was easily desorbed by treating with acetic acid/methanol mixture (50% V/V) at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The adsorption of Cu(II) ion from aqueous solution upon acrylic acid grafted poly(ethylene terephthalate) fibers

This study is concerned with the investigation of the adsorption properties of acrylic acid grafted poly(ethylene terephthalate) fibers by the use of Cu(II) ions in aqueous solutions. Influence of pH, graft yield, contact time, concentration of the ion, and reaction temperature on the amount of ion adsorbed upon reactive fiber were investigated. The time in which the adsorption reached to the equilibrium value was determined as 1 h. The adsorption isotherm of Cu(II) ion was found to be a Langmuir type and the heat of adsorption was calculated as ?10.1 kJ mol^?1. It was observed that the adsorbed Cu(II) ion upon acrylic acid grafted poly(ethylene terephthalate) fibers could be recovered in acidic media. The fiber could also readsorb Cu(II) ions without losing its activity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1216–1220, 2003     

Hemocompatibility evaluation of polyurethane film with surface‐grafted poly(ethylene glycol) and carboxymethyl‐chitosan

To improve the hemocompatibility and biocompatibility of polyurethanes (PUs), PU surface was firstly modified by poly(ethylene glycol) PEG through acryloyl chloride and subsequently grafted on carboxymethyl‐chitosan (CMCS). Attenuated total reflection Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analysis confirmed that carboxyl‐chitosan was grafted onto PUs surface. The surface properties of unmodified and modified PU films were determined and compared by water contact angle assessment. After PEG and CMCS grafting, the surface energy of the PU film was increased. Furthermore, the hemocompatibility of the modified PU films was systematically evaluated by bovine serum albumin (BSA) adsorption, the dynamic blood clotting test, the platelet adhesion test, and the hemolytic test. It appears that BSA adsorption and platelet adhesion were significantly curtailed for the modified PU films. Therefore, the obtained results showed the modified PU film has better hemocompatibility. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation,characterization, and drug‐release properties of poly(N‐isopropylacrylamide) microspheres having poly(itaconic acid) graft chains

An inverse suspension polymerization method for the preparation of thermoresponsive hydrogel microspheres based on N‐isopropylacrylamide was described in this article. The polymerization reaction was carried out at 200 rpm stirring rate and the microspheres obtained were in the size range of 71–500 μm in the swollen states. The particles were sieved by using ASTM sieves. The selected fraction (180–250 μm) of poly(N‐isopropylacrylamide) (PNIPAAm) microspheres was used for radiation‐induced modification with itaconic acid (IA) to obtain PNIPAAm/poly(itaconic acid) graft copolymer. Viagra and lidocaine were used as model drugs for the investigation of controlled‐release behavior of the microspheres. Incorporation of IA graft chains onto microspheres enhanced significantly the uptake of both drugs and further controlled release at specific pH values. The release studies showed that some of the basic parameters affecting the drug‐loading and ‐release behavior of the microspheres were pH, temperature, particle size, and chemical nature of drug. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1115–1124, 2005     

玉米淀粉接枝丙烯酸高吸水性树脂的制备及性能研究

以玉米淀粉为主要原料、丙烯酸(AA)为改性单体、过硫酸铵为引发剂和N,N-亚甲基双丙烯酰胺为交联剂,采用接枝共聚法制备淀粉接枝型高吸水性树脂。研究了糊化温度、糊化时间、引发剂和交联剂用量、单体浓度、接枝反应温度和反应时间等对树脂吸水性能的影响。确定其最佳工艺条件为:糊化温度为85℃、糊化时间为60min,w(引发剂)=3%(相对于淀粉而言)、w(交联剂)=0.8%(相对于淀粉而言)、AA单体浓度为4.5mol/L、反应温度为60℃和反应时间为4h。在最佳工艺条件下制备的树脂,其吸水性能最佳,吸水率达到730g/g。