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.     

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.     

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.     

Structure and properties of tussah silk fibers graft-copolymerized with methacrylamide and 2-hydroxyethyl methacrylate

Tussah 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 gain values were obtained with both grafting agents (up to 175%). The extent of homopolymerization was negligible for the MAA grafting system over the entire range of monomer–silk ratios examined, while polymer deposition on the fiber surface occurred when the HEMA–silk ratio exceeded 0.5% (w/w). The moisture content of poly(MAA)-grafted silk fibers was enhanced by grafting. Breaking load, elongation at break, and energy decreased at low weight gain (0–20%) and then remained rather constant. The DSC curves of poly(MAA)-grafted silk showed a new endotherm at about 280°C, due to the melting of poly(MAA) chains. The loss modulus peak of poly(HEMA)-grafted silk fibers broadened and shifted to a lower temperature, showing a tendency to split into two peaks at high weight gain. On the other hand, grafting with poly(MAA) induced a noticeable upward shift of the loss peak. The TMA curves showed that grafting with poly(MAA) resulted in a higher extent of fiber contraction from room temperature to about 250°C. Moreover, the intensity of the final contraction step at about 350°C decreased with increasing weight gain and shifted to a lower temperature. The Raman spectra of grafted fibers were characterized by overlapping of the characteristic lines of both silk fibroin and polymer, the latter showing an intensity proportional to the amount of weight gain. Among the conformationally sensitive vibrational modes of tussah silk fibroin, the amide III range was significantly modified by grafting with both poly(MAA) and poly(HEMA). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1393–1403, 1998     

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.     

Chemical modification of tussah silk fabrics with ethyleneglycol diglycidyl ether by a pad-batch method

Tussah silk fabrics have been chemically modified by pad-batch treatment with ethyleneglycol diglycidyl ether (EDGE). The maximum amount of weight gain attained was 5–6%. Epoxide adducts were formed with tyrosine and basic amino acid residues. The moisture regain of the fabric with 3% weight gain decreased slightly compared with that of the untreated sample. The crease recovery in the wet state improved significantly, while in dry state it remained unchanged. Mechanical and optical properties, and X-ray crystallinity did not exhibit noticeable changes. The position of the major DSC endothermic transition at 358d?C remained unchanged, regardless of the epoxide modification. Similar comments apply to the TMA contraction peak occurring at about 359d?C. The storage and loss modulus curves of EDGE-treated tussah silk fibres exhibited some changes, the most relevant consisting in a shift to higher temperature of the loss modulus peak.     

Mechanical properties of tussah silk fibers treated with methacrylamide

Tussah silk fibers were treated with methacrylamide (MAA). The polymerization of MAA onto tussah silk fibers and the mechanical properties of the MAA-treated tussah silk fibers were investigated. The tanning agent contained in tussah silk fibers acted as an inhibitor to the radical polymerization of MAA. The alkali treatment enhanced the swelling of noncrystalline regions of the tussah silk fibers and promoted the polymerization of MAA onto the tussah silk fibers. The cross-sectional area of the MAA-treated tussah silk fiber was given by the sum of the cross-sectional area of the original silk fiber and that of the MAA polymer. Breaking load of the fibers was almost unchanged by the MAA treatment, while rigidity was markedly increased. Young's modulus of the MAA-treated tussah silk fibers decreased with decreasing volume fractions of the fiber in the MAA-treated tussah silk fibers. Young's modulus of the MAA polymer in the MAA-treated tussah silk fibers was estimated by extrapolating the relation between Young's moduli and the volume fractions of the fiber to zero volume fraction. Young's modulus of the MAA polymer in the MAA-treated tussah silk fibers was significantly larger than the modulus of a MAA polymer plate. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2051–2057, 1997     

Characterization of microvoids in mulberry and tussah silk fibers using stannic acid treatment

To investigate the volume, size, and number of microvoids in mulberry and tussah silk fibers, stannic acid gel was used as a contrasting medium to the small-angle X-ray scattering (SAXS). The influence of the stannic acid treatment on the structure of silk fibers was first investigated by using the wide-angle X-ray diffraction prior to characterization of the microvoids. The changes in crystallite size and degree of orientation with increasing stannic acid gel fraction in fibers are investigated, and it was found that the stannic acid treatment does not cause serious changes in crystallite size and degree of orientation. The changes in crystallinity indices were observed when the volume fractions of stannic acid gel in the fibers exceeded about 10%. Thus, it was confirmed that the structure of silk fibers was retained in the region of the stannic acid gel fraction less than 10%. SAXS measurements revealed that the number and the fraction of the microvoids are larger, while the sizes of the microvoids are smaller, for the mulberry silk fibers compared with the tussah silk fibers. The fraction macrovoids, however, is considered to be larger for the tussah silk fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 363–367, 1999     

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.     

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.     

Characterization of methacrylonitrile-grafted silk fibers

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.     

Chemical modification of tussah silk with acid anhydrides

Tussah silk fibroin was chemically modified by acylation with aliphatic, aromatic, and hydrophobic acid anhydrides. The tussah silk fibers were pretreated by immersing them in a lithium thiocyanate (LiSCN) solution and then acylated in dimethylformamide (DMF) at elevated temperatures. Using this method, acylated tussah silk fibers with weight gains of 8–22% could be obtained. The pretreatment with LiSCN was necessary to promote the acylation. Without it, the reaction did not proceed. The optimum temperature and reaction time of the pretreatment was 55°C and 60 min, respectively. When examining the physical properties and the thermal behavior of both pretreated and acylated tussah silk, it was found that the mechanical properties and the position of the major DSC endothermic peak remained unchanged, regardless of pretreatment and acylation. The moisture regain of the pretreated tussah silk increased slightly while the moisture regain of the acylated silk decreased linearly with increasing weight gain. The chemical modification allows for a wide control of the tussah silk fiber's properties, making it possible to use tussah silk for the development and production of novel textile and biomaterials. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 382–391, 2000     

Structural changes and dyeability of silk fibroin fiber following shrinkage in neutral salt solution

The fine structural changes of Bombyx mori silk fibroin fibers, induced by shrinking with concentrated calcium chloride aqueous solution at elevated temperature were investigated as a function of shrinking rate. Tensile strength decreased and elongation at break increased in the shrinkage range 13–67%, the shape of the stress–strain curve changing from rubberlike to brittle at high shrinkage values (70–90%). The birefringence gradually decreased over the entire shrinking range examined, the curve becoming steep as the shrinkage exceeded about 67%. The behavior of isotropic refractive index (n_iso) closely resembled that of birefringence (Δn) in the shrinking range 13–67%. Beyond shrinkage of 67%, the n_iso showed a tendency to increase, especially for the sample with 80% shrinkage. Dichroism measurements showed that the molecular orientation within the amorphous regions decreased sharply at the beginning of the shrinking treatment, within the range 0–13%, then attained a saturation at about 55%. The position and intensity of the major X-ray diffraction peak at 20.5° remained essentially unchanged regardless of the shrinking treatment. The results of dyeing behavior showed that the saturation value attained by shrunk silk fibers was significantly larger than that of the untreated control sample. Both standard affinity and the heat of dyeing increased slightly for the shrunk silk fibroin fiber, suggesting that a larger number of reactive sites became available for the interaction between dye molecules and fibroin chains. A schematic model is proposed for explaining the relation between structural changes and enhanced dyeability of the silk fibers following shrinkage in neutral salt solution. © 1994 John Wiley & Sons, Inc.     

Structural characteristics of silk fibers treated with epoxides

Structural characteristics of the silk fibroin fiber-modified with epoxide treatment were elucidated by refractive index measurement, differential scanning calorimetry, and thermomechanical analysis and on the basis of strength–elongation measurements. The four epoxides used were glycidol (G), ethylene glycol diglycidyl ether (E), tolyl glycidyl ether (T), and resorcinol diglycidyl ether (R). The values of the isotropic refractive index of the silk fiber increased by the action of T or R. The position of the endothermic peak attributed to the thermal decomposition and the position of the onset of the contraction of each of the samples treated with epoxides shifted to higher temperature, suggesting the more thermal stability. However, the values of the molecular orientation and the crystallinity of the specimen evaluated from X-ray diffraction analysis remained unchanged regardless of the epoxide treatment. These experimental results have been interpreted in terms of the cross-links between the adjacent silk fibroin molecules and of the hydrogen bonds between the hydroxyl groups of the epoxide molecules attached to the side chains of the silk fibroin.     

Chemical composition and physical properties of Gonometa rufobrunnae silk

Chemical composition and physical properties of silk fibers from Gonometa rufobrunnae, a silkworm belonging to the family Lasiocampidae (order Lepidoptera, class Insecta) have been studied. G. rufobrunnae silk fibroin contains a large amount of glycine and alanine, as well as hydroxyl, acidic, and basic amino acids. The gly/ala ratio is 1.5, similar to that of Bombyx mori silk fibroin. The ratio between polar and nonpolar amino acids is higher than that of either domestic (family Bombycidae) or wild (family Saturniidae) silk fibroins. The sericin is characterized by a large amount of hydroxyl amino acids, mainly serine. The infrared spectrum of G. rufobrunnae silk fibroin showed characteristic absorptions at 1630, 1530, and 700 cm^?1 attributed to the β structure and at 1650 and 1540 cm^?1 due to the random-coil conformation. The birefringence and isotropic refractive index values were 0.027 and 1.559, respectively. The differential scanning calorimetry (DSC) curve showed two minor endothermic peaks at 222 and 288°C, together with a major endothermic peak at 344°C, attributed to the decomposition of the fibroin with β conformation. The fibers exhibited a maximum contraction peak (4.3%) at about 230°C. The dynamic storage modulus (E′) exhibited an abrupt drop at 190°C, while the loss modulus (E″) curve increased above 185°C with a sharp slope. The surface of degummed G. rufobrunnae silk fibers was very smooth. The shape of the cross section was triangular, round, or roundish shaped. Some fibers were very flat, showing a ribbonlike shape. © 1993 John Wiley & Sons, Inc.     

The preparation of poly[N(n-butoxymethyl) methacrylamide] grafted silk fibers by polymerization using a low pH system

The graft polymerizations of the N(n-butoxymethyl) methacrylamide (BMA) monomer onto silk fibers were effected after reducing the pH of the grafting system to 2.5 by the addition of a formic acid solution. We compared the grafting efficiencies, surface characteristics, and thermal behaviors, as well as the whiteness levels and the extent of reduction of the rate of yellowing following UV irradiation, with the equivalent features of poly(BMA)-grafted silk fibers, prepared under normal (pH 6) conditions. The grafting efficiency [as poly(BMA) weight gain] onto silk fiber that was attained was almost 100% through optimization of the pH environment in the polymerization system by the addition of formic acid. The stiffness of the silk fabrics observed, following the conventional grafting, was markedly higher than that of equivalent silks after the polymerization at pH 2.5. The rates of yellowness index increase, for these latter silk fabrics following UV irradiation were also reduced, specifically in the initial irradiation period (up to 60 h). The SEM of the grafted silk fabrics reveal the absence of granules on the surface of the grafted silk fiber, when the silk was grafted with poly(BMA), after reducing the pH of the grafting system to 2.5. These findings suggest that the BMA monomer was polymerized specifically within the silk fiber and not on the surface. It is suggested that the increase in the polymer weight gain, and the reduced adverse effect on the fabric handle, arise because of the modified polymer location. © 1993 John Wiley & Sons, Inc.     

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     

Structural analysis of methacrylamide-grafted silk fibers

The structural changes and the thermal behavior of silk fibers grafted with methacrylamide (MAA) were investigated as a function of the weight gain. The refractive index parallel to the fiber axis decreased with increasing weight gain, whereas that perpendicular remained almost unchanged. Accordingly, birefringence decreased with a steeper slope in the weight gain range 0–80%, suggesting a lower degree of average molecular orientation. Only small changes in the isotropic refractive index were detected, suggesting that the crystallinity of the fibers remained essentially unaffected by MAA grafting, as confirmed by the X-ray diffraction data. The molecular orientation in the crystalline regions remained unchanged in the weight gain range 0–60%, then sharply decreased. The strength and the initial tensile resistance of grafted silk fibers decreased both in the dry and wet states, while elongation at break increased in the dry state and remained almost constant in the wet state. The results of the thermal behavior, investigated by differential scanning calorimetry, thermomechanical and thermogravimetric analysis, and dynamic mechanical measurements, were consistent with an increased thermal stability conferred on silk fibers by MAA grafting. The cross-sectional area of MAA-grafted silk fibers increased. Moreover, ion-etched cross sections of the grafted silk fiber showed the presence of fibrils with a diameter larger than that of the untreated control. © 1993 John Wiley & Sons, Inc.     

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