Preparation of water‐repellent silks by a reaction with octadecenylsuccinic anhydride

Silk fibers and membranes were acylated with octadecenylsuccinic anhydride (ODSA) at 75°C for different times. Swelling [N,N‐dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)] and nonswelling (xylene) solvent media were used for the reaction. Silk membranes that reacted in DMF or DMSO displayed faster reaction kinetics and attained higher weight‐gain values than fibers. The effect of the solvent on the reaction yield was in the following order: DMSO > DMF ? xylene. The Fourier transform infrared spectra of acylated silk samples showed the characteristic absorption bands of the anhydride at 2990, 2852, 1780–1700, and 1170 cm^?1. The intensity of the latter band, which increased linearly with the weight gain, was used as a marker for evaluating the reaction kinetics of the samples acylated in the nonswelling medium. The moisture regain and water retention of silk fibers acylated with ODSA decreased significantly, regardless of the solvent system used. Accordingly, the water repellency increased. Acylation induced an increase in the thermal stability of the silk fibers and membranes. Fine particles adhering to the surfaces of the silk fibers acylated in xylene were detected by scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 324–332, 2003     

Chemical modification of silk with itaconic anhydride

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.     

Chemical modification of silk with aromatic acid anhydrides

Bombyx mori silk fibers were chemically modified by acylation with aromatic acid anhydrides, such as phthalic and o-sulfobenzoic anhydrides. We examined the reactivity of these modifying agents toward silk fibers, the physical and thermal properties, and the dyeing behavior with acid and cationic dyes. The o-sulfobenzoic anhydride was more reactive toward silk fibroin than phthalic anhydride. The amount of both basic and acidic amino acid residues decreased after modification with aromatic acid anhydrides. The moisture regain of silk treated with phthalic anhydride remained almost unchanged, while that of the samples modified with o-sulfobenzoic anhydride increased linearly as the weight gain increased. Chemically modified silk fabrics showed improved crease recovery behavior, even though phthalic anhydride seemed more effective at comparatively low weight gain. The modification of silk with o-sulfobenzoic anhydride caused a drastic a reduction of acid dye uptake and enhanced the affinity of silk for cationic dye. Silk fibers did not show any significant change in thermal behavior, regardless of the modification with o-sulfobenzoic anhydride. Silk fibers modified with phthalic anhydride showed on differential scanning calorimetry (DSC) curves a minor and broad endothermic peak at around 210°C, attributed probably to the breaking of the crosslinks formed between adjacent fibroin molecules.     

Acylation of silk and wool with acid anhydrides and preparation of water-repellent fibers

Silk and wool fibers were acylated with two acid anhydrides, dodecenylsuccinic anhydride (DDSA) and octadecenylsuccinic anhydride (ODSA), at 75°C with N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) as the solvent, the latter of which allowed higher weight gains to be reached. The weight gain and acyl content of wool was always higher than that of silk. Tensile properties of silk remained unchanged regardless of weight gain, whereas wool displayed a noticeably higher extensibility at high weight gain. Fine structural changes of acylated wool were detected by DSC analysis. Moisture regain and water retention of acylated silk and wool decreased significantly, whereas water repellency increased. SEM analysis showed the presence of foreign material firmly adherent to the surface of both silk and wool, whose amount increased with increasing weight gain. These deposits were attributed to the presence of the modifying agents at the fiber surface on the basis of the characteristic IR bands. The possible application of silk and wool fibers acylated with DDSA or ODSA for the preparation of water-repellent textile materials is discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2832–2841, 2001     

Chemical structure and dynamic mechanical behavior of silk fibers modified with different kinds of epoxides

The chemical reactivity of epoxide molecules toward silk fibroin was investigated by determining the rate of conversion of reactive amino acid residues. Significant differences were found between two different bifunctional epoxides, diglycidyl ethers of ethylene glycol (E) and resorcinol (R), the former reacting at a higher extent with arginine and tyrosine. The moisture regain decreased by reaction with epoxides, at a variable rate and extent, according to the hydrophobic/hydrophilic properties of epoxides. A two-step behavior was observed when moisture regain values relating to the silk content in modified silk, fibers were plotted as a function of the weight gain. Dynamic mechanical data showed that the major loss peak became broader and its temperature shifted to lower values following the increase of weight gain. The loss peak temperatures showed a linear relationship with the amount of weight gain. The fine structural changes induced by reaction with eposides will be discussed in terms of chemical and steric factors of the epoxides, as well as of epoxide location within the different structural domains of silk fibers. © 1994 John Wiley & Sons, Inc.     

Absorption of metal cations by modified B. mori silk and preparation of fabrics with antimicrobial activity

Silk fabrics were modified by treatment with tannic acid (TA) solution or by acylation with ethylenediaminetetraacetic (EDTA) dianhydride. Kinetics of modification with TA and acylation with EDTA–dianhydride was investigated. The physico‐mechanical properties of silk fabrics acylated with EDTA–dianhydride remained unchanged regardless of chemical modification. The absorption of metal cations (Ag⁺, Cu²⁺) by untreated and modified silk fabrics was studied as a function of the kind of modifying agent, weight gain, and pH of the metal solution. The absorption of Cu²⁺ at alkaline pH was not significantly influenced by chemical modification of the silk substrate. The absorption of Ag⁺ by acylated silk remained at a level as low as untreated silk, while was enhanced by TA. The higher the content of TA, the higher the absorption of Ag⁺. With respect to the pH of the metal solution, the acylation with EDTA–dianhydride enabled silk to absorb and bind metal cations even in the acidic and neutral pH range, where tannic acid had no effect. Medium to high levels of metal desorption were exhibited by untreated and modified silk fabrics towards the metal cations, with the only exception of the silk–tannic acid–Ag complex, which displayed an extraordinary stability. All metal‐containing silks exhibited significant antibacterial activity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 297–303, 2001     

Physical properties and dyeability of NaOH-treated silk fibers

Domestic (Bombyx mori) and wild (tussah, Antheraea pernyi) silk fabrics were treated with diluted NaOH solutions by the pad/batch method. The equillbrium moisture regain of tussah silk fibers increased steadily with alkaline treatment, while that of B. mori did not change. B. mori tensile strenght and elongation at break were slightly impaired. The average molecular orientation and crystallinity of both kinds of silk remained unchanged. Differential scanning calorimetry (DSC) and thermomechanical analysis(TMA) showed that the thermal behavior of B. mori silk was almost unaffected, while that of tussah exhibited slight changes in the temperature range 250–300°C. By dynamic mechanical measurements (DMA) it was elucidated that both storage and loss moduli of B. mori silk fibers decreased following NaOH treatment. On the other hand, tussah silk exhibited a noticeable upward shift of the major loss peak. Alkali-treated tussah silk fibers, dyed with an acid dyestuff, attained a lower degree of dye-bath exhaustion. © 1995 John Wiley & Sons, Inc.     

Preparation of metal‐containing protein fibers and their antimicrobial properties

Bombyx mori silk, Antheraea pernyi silk, and wool fibers were chemically modified by treatment with tannic acid (TA) or by acylation with ethylenediaminetetraacetic (EDTA) dianhydride. Kinetics of TA loading or acylation with EDTA‐dianhydride varied from fiber to fiber. B. mori silk and wool displayed the highest weight gains with TA and EDTA‐dianhydride, respectively. The uptake of different metal ions (Ag⁺, Cu²⁺, Co²⁺) by protein fibers, either untreated or chemically modified, was studied as a function of weight gain and pH of the aqueous metal solution. Below pH 7, absorption of metal ions by untreated and TA‐treated fibers was negligible. Acylation with EDTA‐dianhydride enabled protein fibers to absorb and bind significant amounts of metal ions in the acidic and neutral pH range. The levels of metal desorption at acidic pH depended on the fiber‐metal combination. Untreated protein fibers usually displayed the lowest stability of the metal complex. Metal complexes with protein fibers exhibited prominent antimicrobial activity against the plant pathogen Cornebacterium. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 638–644, 2003     

Studies of mechanical and moisture regain properties of methyl methacrylate grafted silk fibers

The mechanical properties such as the tenacity, breaking extension, initial modulus, elastic and work recovery, and stress relaxation behavior of methyl methacrylate (MMA) grafted silk fibers prepared under different conditions were measured and explained in terms of the relative dominance of the stress concentration, reduction in the interchain cohesion, and fiber matrix stiffening at different grafting percentages. The moisture regain characteristics of fibers grafted in the presence of different solvents were also studied and compared. The grafting of MMA on silk was found to improve the recovery properties significantly without affecting the stress relaxation behavior. The moisture regain studies indicate that moisture regain is reduced with increasing length of the grafted poly(MMA) chains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 969–974, 2002; DOI 10.1002/app.10202     

Structure and physical properties of epoxide-treated tussah silk fibers

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 (n_iso) 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%.     

Physical characteristics of silk fibers modified with dibasic acid anhydrides

The objective of this study was to investigate the physical properties of silk fibers modified with dibasic acid anhydrides. These are potentially attractive modifying agents to reduce the rate of photoyellowing of silk during and following UV irradiation. Several analytical techniques were employed, which included the measurement of the basic mechanical properties (tensile strength and elongation at break), equilibrium regain, amino acid analysis, dynamic viscoelastic measurements, X-ray diffractometry, and scanning electron microscopy (SEM). The succinylated silk fibers, which have been conditioned under different relative humidity atmospheres, always exhibited slightly higher equilibrium regain values than those of equivalently conditioned glutarylated silks. The amount of the basic amino acid residues slightly decreased following modification with both succinic and glutaric anhydrides. The birefringence values and the isotropic refractive indices decreased only slightly, which suggests that the fine structure of the treated silk fibers was not significantly altered. The X-ray diffraction curves demonstrated that no changes in the crystalline structure were induced by reaction with dibasic acid anhydrides. The tensile properties of the modified silks remained more or less unchanged. Only the initial tensile resistance of glutarylated silks in the dry state significantly decreased. The dynamic viscoelastic behavior of modified silk fibers was characterized by a reduced thermal stability. In fact, the onset temperature of the prominent E peak corresponding to the molecular movement shifted to lower values. The surfaces of modified silk fibers were as smooth as that of the untreated control sample. © 1994 John Wiley & Sons, Inc.     

Chemical modification of Bombyx mori silk with calcium‐salt treatment and subsequent glycerin triglycidyl ether crosslinking

In this article, we propose a new modification method for obtaining porous silk fibers with excellent wet elastic resilience and flexibility. Bombyx mori silks were modified by calcium‐salt treatment and subsequent epoxy crosslinking with glycerin triglycidyl ether. The effects of temperature, time, and catalyst (sodium carbonate) on the crosslinking reaction of the silk fibers were investigated, and the best conditions of reaction were determined as a temperature of 120°C, a crosslinking agent concentration of 7%, and immersion for 1 h with 2% Na₂CO₃ solution before the crosslinking reaction. The change in the structure and the physical properties of the silk fibers after calcium‐salt treatment and epoxy crosslinking was studied. Separating behavior of the microfibers occurred on the surface of the silk fiber after calcium‐salt treatment, and a porous structure formed in the interior of the silk. This porous structure of the silk was enlarged by subsequent epoxy crosslinking, and accordingly, the moisture conduction of the silk fibers improved remarkably. The breaking strength, breaking elongation, and wet elastic resilience of the silk fibers increased evidently after modification, and the modified silks exhibited a better flexibility. The conformation of silk fibroin fibers changed from β sheet to random coil after calcium‐salt treatment, whereas the β‐sheet content in the silk fibers increased after subsequent epoxy crosslinking. The significant reductions in the crystallinity and crystalline sizes in the silk fibers after the crosslinking reaction indicated that the crosslinking reaction occurred within the crystalline region because the calcium‐salt treatment increased the reaction accessibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure and properties of bombyx mori silk fibers grafted with methacrylamide (MAA) and 2-hydroxyethyl methacrylate (HEMA)

Silk fibers were graft-copolymerized with methacrylamide (MAA) and 2-hydroxyethyl methacrylate (HEMA) in aqueous media, using a chemical redox system as an initiator. High weight gains (300%) were obtained with both monomers, the weight gain being linearly related to the amount of monomer contained in the reaction system. The reaction efficiency attained 95–100%. The extent of homopolymerization was negligible for the MAA grafting system, while large amounts of poly-HEMA covered the surface of silk fibers beyond 70% weight gain. The fiber size increased linearly with the weight gain. The moisture content of MAA-grafted silk fibers was highly enhanced by grafting. The severe grafting conditions caused a partial degradation of the tensile properties of silk fibers, as well as of the degree of fiber whiteness. Following grafting, the breaking load slightly increased, while elongation at break and energy decreased. The decomposition temperature of grafted silk fibers shifted upwards. The Raman spectra of untreated silk fibers showed strong lines at 1667 (amide I), 1451, 1227 (amide III), 1172 and 1083 cm⁻¹. Overlapping of the lines characteristic of both silk fibroin and grafted polymer was observed in the spectra of grafted silk samples. The vibrational mode of the amide III lines of silk fibroin was significantly modified by grafting. © 1996 John Wiley & Sons, Inc.     

Physical properties of silk fibers treated with ethylene glycol diglycidyl ether by the pad/batch method

This paper deals with the epoxide treatment of silk fabrics by the pad/batch method. The optimum reaction conditions, i.e., NaOH concentration, and reaction temperature were 2.5 g/L and 30°C, respectively. A weight gain of 8.5% was attained at a reaction time of 6 h. This value slightly increased to 10% after 24 h. The reactivity of tyrosine and basic amino acid residues was dependent on the reaction time and did not significantly differ from the results of epoxide-treated silk fiber by the conventional method in tetrachloroethylene. The moisture regain slightly decreased at 4% weight gain and then increased with the epoxide content, exceeding the value of the untreated control. The crease recovery of the epoxide-treated silk fabrics measured in the wet state was significantly improved, whereas that in the dry state was almost unchanged. The rate of photoyellowing of the epoxide-treated silk fabrics by the pad/batch method was reduced significantly compared with that of the untreated control. Among the mechanical properties, elongation at break and tensile modulus remained unchanged, whereas the tensile strength slightly increased following the epoxide reaction. The thermal properties were evaluated by DSC and TGA and on the basis of the dynamic viscoelastic measurements. The DSC curve of the epoxide-treated sample showed a slight increase of the decomposition temperature of silk fibroin. The rate of weight loss determined by TGA remained unchanged regardless of the chemical modification, whereas the peak of loss modulus became broader and shifted to lower temperature. The X-ray diffractograms showed that the crystalline structure of silk fibers was not affected by the reaction with epoxides. © 1993 John Wiley & Sons, Inc.     

Structural changes in Tencel by enzymatic hydrolysis

The NaOH‐, fibrillation‐, and cellulase‐ treated Tencel fabrics were characterized by weight loss, tensile strength, scanning electron microscopy (SEM) analysis, X‐ray diffraction analysis, measurements of moisture regain and dye adsorption (K/S value), degree of polymerization (DP), and copper number. Weight loss increased and tensile strength decreased with increase in cellulase concentration and treatment time. At a similar weight loss, tensile strength retentions of the NaOH‐pretreated samples were better than those of the NaOH‐nontreated samples because of more uniform enzymatic hydrolysis. SEM photographs showed more surface peeling and interfibrillar splitting as enzymatic hydrolysis progressed. Crystalline structure and degree of crystallinity were not much changed by cellulase treatment. As enzymatic hydrolysis progressed, moisture regain and K/S value increased slightly due to increase of specific surface area by fibrils. DP initially decreased as enzymatic hydrolysis progressed and then leveled off. Copper number increased largely at an initial stage of degradation and then decreased gradually. The NaOH‐pretreated samples showed higher degree of crystallinity, DP, moisture regain, and K/S value, but lower copper number than the NaOH‐nontreated ones. These results were attributed to extraction of short chain molecules in the amorphous region during NaOH pretreatment and change of amorphous region into the open‐up structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1644–1651, 2000     

Changes in physical properties of methacrylonitrile (MAN)-grafted silk fibers

Changes in physical properties of silk fibers, grafted with methacrylonitrile (MAN), were investigated as a function of the weight gain. The weight gain increased steadily during the first 60 min of reaction and gradually attained an equilibrium value (60%) after about 4 h. The initial tensile resistance of silk fibers decreased by MAN grafting. The crystalline structure of silk fibers remained unchanged, regardless of MAN grafting, however. a minor and broad peak appeared in the X-ray diffraction curves of MAN-grafted silk fibers with a weight gain of 60%, corresponding to the unoriented MAN polymer attached inside the fibers. Molecular orientation of silk fibroin chains in the crystalline regions, evaluated from X-ray diffraction curves, did not change significantly, while both birefringence and isotropic refractive index decreased as the weight gain increased, implying that MAN polymer attached preferentially to the amorphous and not to the crystalline regions. Dynamic vis-coelastic measurements showed that the position at which the E′ value began to decrease shifted to a lower temperature as the weight gain increased. These findings suggest that the thermal movement of silk fibroin molecules was accelerated by the presence of the poly-MAN chains attached to the amorphous regions of silk fibroin fibers. © 1993 John Wiley & Sons, Inc.     

Effects of ethylene content of poly(ethylene‐co‐vinyl alcohol) on diameter of fibers produced by melt‐electrospinning

Rodlike samples were made from four kinds of poly(ethylene‐co‐vinyl alcohol) (EVAL) pellets with different ethylene contents. From these rodlike samples, fibers were produced using a melt‐electrospinning system equipped with a CO₂‐laser melting device. The effects on the fiber diameter of the ethylene content and the moisture regain of the rodlike samples were investigated. Furthermore, the physical properties of the fibers were investigated. The following conclusions were reached: (i) EVAL fibers having an average fiber diameter smaller than 1 μm can be obtained using the system developed; (ii) the diameter of EVAL fiber is influenced by the ethylene content and the moisture regain of the starting rods; (iii) the laser heating does not greatly decrease the melting point and the molecular weight of EVAL; and (iv) preferred crystal orientation can be seen in electrospun EVAL fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1368–1375, 2007     

生物质胶原蛋白纤维性能测试及对纺纱的影响分析

测试了生物质胶原蛋白纤维的力学性能、卷曲性、回潮率、质量比电阻等,并和棉、毛、丝等纤维进行对比。实验结果表明,胶原蛋白纤维拉伸强度较大,卷曲弹性较好,回潮率略低于棉,含油率适中,纺纱性能优良。     

The in situ polymerization of vinyl monomers in polyester yarns

The effects of a pretreatment of polyester (PET) yarns with a strongly interacting solvent such as dimethylformamide (DMF) on vinyl monomer incorporation were investigated. When the DMF pretreatment is carried out at high temperatures (above 120°C), the swollen PET structure is stabilized by solvent-induced secondary crystallization. This substrate is highly suitable for the incorporation of vinyl monomers. In situ polymerization of vinyl monomers in DMF-treated PET was investigated using chemical and γ-irradiation polymerization techniques, both in the presence and in the absence of excess monomer outside the PET fibers. When polymerization was carried out in a system in which a constant supply of free radicals was available from the outside of the PET fibers, lower initiator concentrations and smaller γ-irradiation doses were necessary. These results are attributed to a low efficiency of the initiator inside the PET fiber due to mobility restrictions. Water uptake and moisture regain of PET yarns containing poly(hydroxyethyl methacrylate) and poly(acrylic acid) were also investigated. When most of the vinyl polymer was inside the PET fiber, water absorption was limited. The changes in mechanical properties of the PET yarns resulting from the DMF pretreatment were partially reversed by in situ polymerization of vinyl monomers.     

Chemical modification of Bombyx mori silk with epoxide EPSIB

Bombyx mori silk fabrics were chemically modified by EPSIB (a multifunctional silicone‐containing epoxy crosslinking agent). The reactivity of the epoxy groups with silk fibroin was studied by using amino acid analysis. The physical properties of the modified silks such as resiliency (both wet and dry), moisture regain, dyeing behaviors, and solubility in a mixture solvent (C₂H₅OH × CaCl₂ : H₂O = 2 : 1 : 8, molar ratio) were examined. The modified silk fabrics exhibited a significantly improved resiliency, a small increase in moisture regain and whiteness, and a slightly decreased tensile strength. The contents of Serine, Trosine, Lysine, and Histidine decreased linearly as the wet crease recovery angle (CRA) increased. The solubility in the mixture solvent also decreased as the wet CRA increased. The changes of physical properties, especially the wet CRA, were mainly due to the presence of stable cross‐links between silk fibroin and epoxy groups. The DSC and TGA analyses showed that EPSIB‐modified silk fibroin had a higher thermal stability compared with the control. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3579–3586, 2004