热塑性魔芋葡甘聚糖/聚己内酯共混物制备及表征

以资源丰富的天然可降解高分子材料魔芋葡甘聚糖(KGM)为原料, 以甲基丙烯酸甲酯和丙烯酸甲酯为单体,过硫酸铵为引发剂,合成了热塑性魔芋葡甘聚糖。将热塑性魔芋葡甘聚糖(TDKGM)和聚己内酯(PCL)熔融共混制备热塑性魔芋葡甘聚糖/聚己内酯共混物(TDKGM/PCL)。通过热重分析、扫描电镜、差示扫描量热仪(DSC)、XRD和万能力学试验机等对TDKGM/PCL共混物的结构和性能进行了分析表征。结果表明：共混物中热塑性魔芋葡甘聚糖对聚己内酯的结晶起到了成核剂的作用,使聚己内酯能在较高温度下开始结晶,并可明显提高共混物中聚己内酯相的结晶速度。TDKGM/PCL复合材料(20/80)的最大扭矩值为48.7 N·m,塑化时间在300 s以上,平衡扭矩在10.7 N·m,与PE相当接近,并且具有高达256.48%的断裂伸长率。     

Preparation and characterization of carboxymethyl konjac glucomannan/sodium montmorillonite hybrid films

Carboxymethyl konjac glucomannan (CKGM)/ sodium montmorillonite (MMT) hybrid films of various compositions were prepared by casting from a polymer/silicate water suspension. The structure and properties of the hybrid films were investigated by wide angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM), attenuated total reflection infrared spectroscopy (ATR‐IR), differential scanning calorimetry (DSC), and tensile tests. The results from WXRD and TEM indicated that an intercalated CKGM/MMT nanocomposite film was obtained by polymer solution intercalation. WXRD and DSC showed that the high‐T_m crystal phase was induced by the presence of lower MMT loading, but the T_m of the hybrid films became weak with the increase of MMT content due to the polymer confinement. The hybrid films showed higher thermal stability and mechanical properties than that of the neat polysaccharide due to the strong interaction between hydroxyl and carbonyl group of CKGM and the silicate layer of MMT. Furthermore, the degree of swelling of the hybrid films was investigated in acidic buffer solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2954–2961, 2007     

Binary and ternary blends of polylactide, polycaprolactone and thermoplastic starch

In this study binary and ternary blends of polylactide (PLA), polycaprolactone (PCL) and thermoplastic starch (TPS) are prepared using a one-step extrusion process and the morphology, rheology and physical properties are examined. The morphology and quantitative image analysis of the 50/50 PLA/TPS blend transverse phase size demonstrate a bimodal distribution and the addition of PCL to form a ternary blend results in a substantial number of fine dispersed particles present in the system. Focused ion beam irradiation, followed by atomic force microscopy (AFM) shows that dispersed PCL forms particles with a size of 370 nm in PLA. The TPS phase in the ternary blends shows some low level coalescence after a subsequent shaping operation. Dynamic mechanical analysis indicates that the temperature of the tan δ peak for the PLA is independent of TPS blend composition and that the addition of PCL in the ternary blend has little influence on the blend transitions. Both the α and β transitions for the thermoplastic starch are highly sensitive to glycerol content. When TPS of high glycerol content is blended with PLA, an increase in the ductility of the samples is achieved and this effect increases with increasing volume fraction of TPS. The ternary blend results in an even greater ductility with an elongation at break of 55% as compared to 5% for the pure PLA. A substantial increase in the notched Izod impact energy is also observed with some blends demonstrating three times the impact energy of pure PLA. The mechanical properties for the ternary blend clearly indicate a synergistic effect that exceeds the results obtained for any of the binary pairs. Overall, the ternary blend approach with PLA/TPS/PCL is an interesting technique to expand the property range of PLA materials.     

Preparation and characterization of konjac glucomannan and sodium carboxymethylcellulose blend films

The novel blend films of konjac glucomannan (KGM) and sodium carboxymethylcellulose (NaCMC) were prepared by casting the mixed polymer aqueous solutions. The physical properties of the blend films from konjac glucomannan and sodium carboxymethylcellulose were investigated by using FT‐infrared (FTIR), wide‐angle X‐ray diffraction (WAXD), differential thermal analysis (DTA), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and measurements of mechanical properties. The experimental results showed that the occurrence of the interactions between KGM and NaCMC molecular chains through hydrogen bond formation, and the physical properties of the films largely depend on the blending ratio. The thermal stability, mechanical properties of both tensile strength, and elongation at break of the blend films were improved by blending KGM with NaCMC. The surface morphology of the films observed by SEM was consistent with the results mentioned above. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 26–31, 2001     

一种改性魔芋葡甘露聚糖的合成与表征

以三乙胺为催化剂,用没食子酸对魔芋葡甘露聚糖（KGM）进行酯化改性,反应条件为：m（KGM）∶m（三乙酰没食子酰氯）=1∶2,反应温度50℃,时间3 h,用饱和乙酸钠的无水乙醇溶液进行脱除乙酰基,得改性KGM,总收率为57.9%。     

魔芋葡甘露聚糖的研究进展

综述了国内外对于魔芋葡甘露聚糖的结构、化学改性及应用的研究，提出了存在的问题，展望了发展前景。     

魔芋葡甘聚糖材料疏水改性的研究进展

介绍了魔芋葡甘聚糖与高分子材料共混疏水改性的方法,评述了化学改性中魔芋葡甘聚糖脱乙酰基化、交联、接枝共聚、互穿聚合物网络、羧甲基化等疏水改性的最新研究进展,探讨了其今后的研究方向,并提出了开发热塑性KGM材料这一前沿性课题。     

Preparation of konjac glucomannan ester of palmitic acid and its emulsification

Various degrees of palmitoylated konjac glucomannan (PKGM) are prepared by a heterogeneous method. Differential thermal analysis thermographs show PKGM having 0.51 degrees of substitution (DS) gave a new crystalline peak at higher temperature. With the increase of DS, the former crystalline state of konjac glucomannan will disappear; PKGM only shows the new crystalline state. Furthermore, the effect of the DS of PKGM on its emulsifying ability has been investigated in the water in oil and oil in water systems. It is demonstrated that it is a kind of good water in oil emulsifier, with the DS ranged between 1.00 and 1.70, whereas DS < 0.50. It is a kind of good oil in water emulsifier and an interesting phenomenon appears in the water in oil system. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1035–1038, 1998     

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。     

魔芋葡甘聚糖及其衍生物的应用研究进展

综述了魔芋葡甘聚糖(KGM)及其衍生物在食品、医药及环保等领域的应用,表明KGM具有较高的学术研究价值及广阔的应用前景。     

Synthesis and characterization of konjac glucomannan/poly(vinyl alcohol) interpenetrating polymer networks

Novel interpenetrating polymer networks (IPNs) coded as KP were synthesized successfully from poly(vinyl alcohol) (PVA) and konjac glucomannan (KGM) in the presence of glutaraldehyde as a crosslink agent. The transparent IPN films that were 40 μm thick were prepared by means of conventional solvent‐casting technique and dried at room temperature for 2 days. The structure and miscibility of the KP films were studied by Fourier transformed infrared spectra, scanning electron microscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, and ultraviolet visible spectroscopy (UV–Vis). The results indicated that strong intermolecular interaction caused by crosslink bonding between PVA and KGM occurred in the IPN films, resulting in wonderful miscibility when the reaction time is 4 h. The tensile strength, elongation at break, and moisture uptake was much higher than that of the pure PVA film, KGM film, and uncrosslinked blend films. In other words, the structure of IPN endowed the films with excellent performance, so the new material has promising applications to food package film and agricultural film because of its biodegradability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2775–2780, 2004     

具有吸水保水功能的改性魔芋共聚物包膜缓释尿素的制备及其性能研究

以烯丙基硫脲改性魔芋葡甘聚糖为包膜剂制备包膜缓释尿素。对包膜缓释材料进行扫描电子显微镜(SEM)表征,并分析其吸水性能;评价温度及土壤水含量对包膜缓释尿素氮素溶出率的影响,利用土柱淋溶法检测包膜缓释尿素的缓释效果,并分析缓释尿素对白菜的生长影响。结果表明,烯丙基硫脲接枝魔芋葡甘聚糖在接枝率为35%~45%时,吸水性能最好,吸水量高达794 g/g;随着温度和土壤水含量的升高,包膜缓释尿素氮素溶出率逐渐增加;氮素溶出具有典型的缓释肥溶出特征,表现出良好的缓释效果;白菜对缓释尿素中氮素的利用率提高。     

Blend films from chitosan and konjac glucomannan solutions

Blend films were prepared by blending 7 wt % konjac glucomannan (KGM) aqueous solution with 2 wt % chitosan (CH) in acetate solution and dried at 40°C for 4 h to obtain the transparent films. Their structure and properties were studied by infrared (IR), wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential thermal analysis (DTA). Crystallinities of the blend films decreased with the increase of konjac glucomannan. The thermostability, tensile strength, and breaking elongation of the blend films in dry state were obviously higher than those of both konjac glucomannan and chitosan films. Tensile strength of the dry blend film achieved 73.0MPa when the weight ratio of chitosan to konjac glucomannan was 7:3. The structure analysis indicated that there is a strong interaction between konjac glucomannan and chitosan resulted from intermolecular hydrogen bonds. The water solubility of the blend films was improved by blending with konjac glucomannan, so they have promising applications to soluble antiseptic coating of pills. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 509–515, 2000     

魔芋粉-丙烯酸-丙烯酰胺接枝共聚合成高吸水树脂

以魔芋粉,丙烯酸和丙烯酰胺等为原料,经接枝聚合合成了魔芋粉－丙烯酸－丙烯酰胺类超强吸水性树脂。讨论了引发剂,交联剂,丙烯酸,丙烯酰胺等用量以及反应时间和反应温度等因素对树脂吸水性能的影响。结果表明: 在魔芋粉与单体质量比为1:4,引发剂用量为0.35%（占单体的质量）,丙烯酸/丙烯酰胺（质量）为1:1,丙烯酸中和度为80% ,反应温度为55～65℃,交联剂用量为0.75%（占单体的质量）的条件下,制得的SAP吸去离子水可达720g/g,吸0.9%的NaCl溶液为110g/g。     

Lipase‐catalyzed acylation of konjac glucomannan in ionic liquids

A comparative study was made of lipase‐catalyzed acylation of konjac glucomannan (KGM) with vinyl acetate as the acyl donor in five ionic liquids (ILs) and also in the presence of the organic solvent tert‐butanol (t‐BuOH). An obvious enhancement in enzyme activity and stability was observed using ILs as the reaction media when compared with t‐BuOH. The maximum degree of substitution (DS) of the modified KGM in ILs and t‐BuOH under the conditions employed is 0.71 and 0.54, respectively. The water activity (a_w) of the reaction system affected the acylation of KGM to some extent. 1‐Butyl‐3‐methylimidazolium tetrafluoroborate (C₄MIm.BF₄) was the best IL medium for the reaction, and an a_w of 0.75 was optimum. It was also found that the nature of both the cation and the anion of ILs had an effect on the reaction. Candida antarctica lipase B immobilized on an acrylic resin (Novozym 435) displayed no acylation activity to KGM in 1‐butyl‐3‐methylimidazolium chloride (C₄MIm.Cl). The optimum reaction temperature for enzymatic acylation in ILs was shown to be 45‐55 °C. Enzymatic acylation of KGM in IL‐t‐BuOH co‐solvent systems was also investigated. When an appropriate amount of t‐BuOH was added to ILs, the DS of the modified KGM was enhanced. Additionally, the enzymatic acylation of KGM in all the media examined was shown to be regioselective, with acylation occurring predominantly at the C‐6‐OH. Copyright © 2006 Society of Chemical Industry     

Silk nanofibrous scaffolds assembled by natural polysaccharide konjac glucomannan

Natural silk fibroin nanofibers (SNF) have recently attracted great attention in the field of biomaterials due to their excellent biocompatibility, outstanding mechanical properties, and biomimetic nanostructures. However, the poor structural stability of SNF assembly in aqueous conditions remains a major obstacle to their biomedical application. In this work, SNF scaffolds with extracellular matrix-mimicking architecture and tunable properties were developed by using a small amount of konjac glucomannan (KGM) as a physical adhesive. Fourier transform infrared spectroscopy (FTIR) results revealed that KGM facilitated the formation of hydrogen bond networks between SNF as well as nanofibers/polysaccharide molecules, thereby reinforcing the interconnectivity between SNF. The water stability test showed that SNF scaffolds exhibited good structural stability in water when the mass ratio of KGM/SNF reached 2.5/100. Raising KGM content significantly enhanced the compression strength, modulus, and swelling ratio of the porous scaffold. Whereas, the nanofibrous morphology and porosity of the scaffolds were significantly sacrificed as KGM content exceeded 10% as evidenced by scanning electron microscopy (SEM) results. In vitro, cytocompatibility results also demonstrated the excellent biocompatibility of the biomimetic nanofibrous scaffolds, and the high porosity significantly enhanced cell viability. These results suggest that KGM-reinforced SNF scaffolds may serve as promising candidates for biomaterial applications.     

Synergistic interaction of konjac glucomannan and gellan gum investigated by rheology and texture analysis

The rheological kinetics of konjac glucomannan and gellan gum mixed sols were studied using rotational concentric cylinder viscometer. The effects of polymers weight ratio, shear rate, and temperature were systematically investigated. The curves showed a Newtonian plateau followed by strong shear thinning that can be described by a power law dependence on the shear rate. The dynamic viscoelastic character was evaluated by measurements of small-deformation oscillatory. After adding some cations, the mixed sols turned into mixed gels. The contribution of Na⁺, K⁺, Ca²⁺, and Zn²⁺ at different concentration was also evaluated by texture analysis. The results reveal a strong dependence of the structural properties of different samples on their preparation conditions. A fine turning of the properties of the mixed sols is possible through the change of the temperature preparation and/or the polymer weight ratio. The texture properties of the mixed gels were also possibly influenced significantly by the cations. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on in situ synthesis of konjac glucomannan/silver nanocomposites via photochemical reduction

Konjac glucomannan (KGM)/Silver nanocomposites have been prepared directly in the dilute hydrosol of KGM using photochemical reduction of Ag⁺. The KGM/Ag nanocomposites have been characterized by means of Fourier transform infrared (FTIR) spectra, transmission electron microscopy (TEM), and thermalgravimetry (TG). The results of FTIR showed that the wavenumbers and the strengths of some characteristic peaks of KGM treated by silver nanoparticles were changed obviously, the characteristic peaks of the O? H stretching and the C? O? (H) stretching became wider with increasing concentrations of the reactants, and the characteristic peaks of the O? H stretching and the C? O? (H) stretching shifted to high wavenumbers with increasing time of photochemical reduction. The images of TEM indicated that Ag nanoparticles were finely dispersed inside the KGM films with different shapes, such as sphere‐like (average diameters of 9 ± 4 nm) and star‐like (edge lengths of about 20 nm), respectively. These suggested that the morphology and the agglomerated state of Ag nanoparticles in the composites changed with the conditions of the preparation, especially with the concentrations of Ag⁺ and KGM as well as the time of photochemical reduction. The KGM and KGM/Ag films had remarkably different thermal properties from the TG curves. The mechanism of interaction between the polysaccharide and the silver nanoparticles has also been generally discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1323–1327, 2006     

Improvement of physical properties of crosslinked alginate and carboxymethyl konjac glucomannan blend films

Blend films from carboxymethyl konjac glucomannan and sodium alginate in different ratios were prepared by blending 4 wt % sodium alginate aqueous solution with 2 wt % konjac glucomannan aqueous solution. After crosslinking with 5 wt % calcium chloride aqueous solution, the blend films formed a structure of semi‐interpenetrating networks. The structure and physical properties of both uncrosslinked and crosslinked films were characterized by Fourier transformed infrared spectra (FTIR), differential thermal analysis (DTA), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and tensile tests. The results indicated that the mechanical properties and the thermal stability of the films were improved by blending sodium alginate with carboxymethyl konjac glucomannan due to the intermolecular hydrogen bonds between sodium alginate and carboxymethyl konjac glucomannan. The crosslinked blend films with Ca²⁺, compared with uncrosslinked blend films, exhibited further improved physical properties due to the formation of a semi‐IPN structure. Furthermore, the degree of swelling of the crosslinked films was also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2554–2560, 2002     

Effect of aggregate size on liquid absorption characteristics of konjac glucomannan superabsorbent

In this article, four kinds of konjac glucomannan based superabsorbent polymers (KSAPs) with different aggregate sizes were obtained by sieving the KSAP powders manually. They were characterized by scanning electronic microscopy (SEM), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and optical contact angle (OCA), and the effects of aggregate size on liquid absorption characteristics of KSAP were studied in detail. The results show that the coarse KSAP particles were aggregated by many microspheres, while the fine particles were well dispersed with 50–150 µm particle size. OCA dynamic images showed the enhanced hydrophilicity for the finer particles. The liquid absorption measurements demonstrated that water and physiological saline absorption velocity of KSAP increased for the finer particles, while their ultimate water holding capacity decreased accordingly. The liquid absorption capacity of the finest sample (75 µm) could reach its maximum value (332.5 ± 5.6 g/g) in 0.5 min, while the coarsest sample (850 µm) reached the maximum value (532.5 ± 1.2 g/g) in 16 min. The reason for this phenomenon was discussed, and a new model was proposed to explain it. We believe that the results of this article would be meaningful in application of KSAP as superabsorbent materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45416.