A series of 2-hydroxyethylmethacrylate (HEMA)/methacrylamide (MAA)-grafted silk fibers obtained in various comonomer compositions was prepared and their structural characteristics were studied by X-ray diffractometry, differential scanning calorimetry, and scanning electron microscopy. HEMA/MAA-grafted silk fibers with a graft yield of about 60% obtained in a HEMA/MAA mixture system containing 20% of HEMA and 80% of MAA on a weight basis showed endothermic peaks at 280 and 420°C (shoulder form), which are attributed to the thermal decomposition of the MAA and HEMA polymers, respectively, in addition to the thermal decomposition peak of the silk fibroin fiber which appeared at 323°C. These DSC results suggest that the HEMA/MAA-grafted silk fiber showed a low compatibility in the relation between the silk fibroin molecules and HEMA and/or MAA polymers. The crystalline structure of the HEMA/MAA-grafted silk fiber remained unchanged regardless of the HEMA/MAA grafting ratio even when the graft yield value reached 120%. 相似文献
Structural characteristics of the methyl methacrylate (MMA)-grafted silk fibers using tri-n-butylborane as an initiator were analyzed by infrared spectroscopy and differential scanning calorimetry (DSC), and their refractive index and tensile properties were measured. Graft polymerization was promoted by FeCl3 pretreatment of the silk. The graft yield reached a maximum by the immersion in 4% FeCl3 solution for 1 min at 25°C. The infrared spectrum of poly(MMA)-grafted silk fibers showed overlapped absorption bands of silk fibroin with the β structure and of the grafted MMA polymer. A grafted silk fiber with graft yield of more than 140% exhibited two endothermic peaks at 321°C and 396°C on the DSC curve, attributed to the thermal decomposition of silk fibroin and grafted poly(MMA) chain, respectively. Refractive index measurements suggested that the molecular orientation and the crystallinity of the silk fiber decreased with increasing graft yield. Electron photomicrographs showed that silk was coated by grafted PMMA. The tensile strength of the grafted silk decreased rapidly by the grafting even at a lower level. 相似文献
Summary: By using DSC, 13C CP/MAS NMR and SEM, we studied the physical properties and chemical structure of silk fibers grafted with methacrylamide (MAA). At a given MAA concentration, the inverse of fiber weight gain linearly increased with increasing square root of the initiator concentration, and at a given initiator concentration the fiber weight gain increased with increasing MAA concentration. 13C CP/MAS NMR demonstrated that the primary and secondary structure remained unchanged, regardless of MAA grafting, implying the poor compatibility and the lack of new additional hydrogen bonding between the silk fiber and the MAA graft polymer. The degree of grafting in MAA‐grafted silk fiber (the accurate amount of actually loaded MAA polymer within the fiber matrix) can be evaluated from determination of the ratio of heat capacities calculated from two individual endothermic DSC peaks of silk fibroin and MAA polymer. The major endothermic peaks attributable to thermal degradation of the silk fiber and MAA graft polymer shifted to a higher temperature with increasing fiber weight gain by grafting. These findings are useful for the industrial production of grafted silk fiber with higher thermal stability.
CP/MAS spectra for poly(MAA) grafted silk and control silk fiber. 相似文献
Structural characteristics and physical properties of methyl methacrylate-grafted silk fiber from Bombyx mori were studied by X-ray diffractometry, differential scanning calorimetry (DSC), thermogravimetry, and scanning electron microscopy. Methyl methacrylate (MMA)-grafted silk fiber with a grafting yield of more than 30% showed two endothermic peaks at 320°C and 390–410°C, which are attributed to the thermal decomposition of silk fibroin and MMA polymer filled in the fiber, respectively. These DSC results indicate that MMA-grafted silk fiber showed a poor compatibility in the relation between the silk fibroin molecules and MMA polymer. The weight of the MMA-grafted silk fiber decreased as observed at 160°C on the thermogravimetric thermograms due to the evaporation of water from the sample with increasing graft yield. The crystalline structure of MMA-grafted silk fiber remained unchanged regardless of MMA grafting. Taking into account the X-ray diffraction patterns and the increasing graft yield with reaction time, it is assumed that the graft chains of MMA polymer have penetrated into a weak aggregate region and not in the crystalline region of silk fibroin. 相似文献
Bombyx mori silk fibers were chemically modified by acylation with itaconic anhydride. The reactivity of the modifying agent toward silk fibroin was investigated on the basis of the amino acid analysis. We examined the physical properties, the structural characteristics, and the thermal behavior of modified silk fibers as a function of the weight gain. Silk fibers with a weight gain of 9%, corresponding to an acyl content of 68.9 mol/105g, were obtained at the optimum reaction conditions for silk acylation (75°C for 3 h). The amount of basic amino acid residues (Lys, His, and Arg) decreased linearly as the weight gain increased. The alkali solubility increased proportionally with the weight gain, probably due to the dissolution of the modifying agent reacted with silk fibroin, and not to the degradation of the fibers induced by the chemical modification. The birefringence value, related to the molecular orientation, slightly decreased when the weight gain increased. The isotropic refractive index, associated with the crystallinity, increased when the weight gain ranged from about 5 to 7% and then remained unchanged. The moisture regain did not change regardless of the chemical modification, and the crease recovery behavior of modified silk fabrics did not show significant improvement. The thermal behavior of silk fibers was affected by the modification with itaconic anhydride. The decomposition temperature shifted up to 322°C, 10°C higher than the control silk fibers, suggesting a higher thermal stability induced by chemical modification. 相似文献
The structure and physical properties of silk fibroin fibers graft-polymerized with methacrylonitrile (MAN) were analyzed in relation to the weight gain on the basis of the results of tensile properties as well as of thermal analysis and X-ray diffractometry. The solubility of the specimen in NaOH solution and the moisture absorption decreased slightly with the duration of the MAN treatment. However, the polymerizing treatment with MAN did not affect significantly the tensile properties, i.e., strength and elongation at break of the original fibers. The position of the endothermic peak attributed to the thermal decomposition of the silk fibroin shifted to higher temperatures when the weight gain exceeded 25%, and a constant value at 328°C was obtained above a weight gain of 40%. Wide-range X-ray diffraction diagram of silk fibers with a weight gain of 10% showed diffraction maxima at the equator corresponding to the molecule oriented crystal structure of the silk fiber, in addition to the spots on a series of hyperbolic arcs arranged symmetrically at about the equator, which are associated with the crystalline form of the MAN polymer copolymerized in the specimen. Crystalline structure of the silk fiber remained unchanged essentially regardless of MAN treatment. 相似文献
The structural characteristics and physical properties of epoxide-treated tussah silk fibers from Antheraea pernyi silkworm are discussed in relation to the increasing weight gain values. Ethyleneglycol diglycidylether (E) and glycerin diglycidylether (G) were used as modifying agents. The noticeably high weight gain values (about 140%) obtained were attributed to the catalytic effect of SCN? anion absorbed by the fibers during the pretreatment under reduced pressure conditions. The amino acid analysis showed that epoxide G exhibited a slightly higher reactivity toward tyrosine, while arginine preferably reacted with epoxide E. The peak of loss modulus (E″) determined by dynamic viscoelastic measurements became broader and its position linearly shifted to lower temperature when the weight gain increased, and a minor peak appeared in the low-temperature region below 50°C. Differential scanning calorimetry (DSC) thermograms showed that the position of the decomposition peak of modified silk fibers shifted to lower temperature with increasing weight gain values. The minor and broad endothermic peaks, appearing in the reference sample at about 234 and 290°C, disappeared by epoxide treatment. X-ray diffraction patterns of tussah silk fibers suggested that the epoxide treatment does not affect directly the crystalline regions but causes a decrease of molecular orientation in the amorphous regions. Both briefringence (Δn) and isotropic refractive index (niso) of tussah silk fibers decreased by the reaction with epoxides, although with different rate and extent, confirming the decrease of average molecular orientation. The extent of decrease of strength and elongation depends on the kind of epoxide and on the weight gain value. Epoxide-treated tussah silk fibers did not show significant changes of surface characteristics as the weight gain values attained up to 60%. 相似文献