Durable press finish of cotton/polyester fabrics with 1,2,3,4‐butanetetracarboxylic acid and sodium propionate

Sodium hypophosphite (SHP) is widely used as an effective catalyst for the esterification reaction of cellulose with 1,2,3,4‐butanetetracarboxylic acid (BTCA). However, catalysts containing phosphorus cause significant shade changes in dyed fabrics because of their reductive nature, and the effluents containing phosphorus cause eutrophication in rivers and lakes. Hence, their commercial application as catalysts in textile processing is limited. In this study sodium propionate and its catalytic activities as a nonphosphorous catalyst were investigated. The evidence for esterification and crosslinking of cellulose with BTCA in the presence of sodium propionate was shown by an improved wrinkle recovery angle and durable press rating of treated fabrics. The presence of ester groups in the treated fabrics was confirmed by FTIR analysis. The performance of sodium propionate as a catalyst for BTCA was comparable to that of SHP. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 654–661, 2001     

Characterization of ramie yarn treated with sodium hydroxide and crosslinked by 1,2,3,4‐butanetetracarboxylic acid

Ramie yarns were treated with various concentrations of NaOH at room temperature and subsequently crosslinked with 1,2,3,4‐butanetetracarboxylic acid (BTCA). The microstructure and tensile properties of the treated yarns were characterized. X‐ray diffraction (XRD) and FTIR were used to study the crystalline structure of the resultant ramie yarns. The results showed that the maximum change in the structure of the alkali‐modified ramie took place at 16% NaOH, which would completely transform cellulose I to cellulose II. At the same time, the crystallinity index and fiber orientation decreased to the minimum value while the absorption properties were enhanced. The average degree of polymerization (DP ) of the treated ramie yarns slightly decreased after NaOH treatment. Tensile properties including tenacity, breaking elongation, and modulus of the treated yarns were also investigated. Scanning electron microscopy (SEM) was used to investigate the breakage of the treated yarns. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1857–1864, 2004     

Relationship between water absorbency and reaction conditions in aqueous solution polymerization of polyacrylate superabsorbents

Polyacrylate superabsorbents were prepared by in situ aqueous solution polymerization in a polyethylene bag, which was submerged in a water bath. The influence of the initiator content, bath temperature, isopropanol content, initial monomer concentration, and crosslinker content (Cc) on water absorbency (Q) were investigated. The temperature change of the monomer mixture during polymerization was also analyzed. Increase of the chain ends in networks resulting from decrease of the molecular weight in free‐radical polymerization causes an increase of the water absorbency of superabsorbents and also reduces the crosslinking efficiency. The results are in conformity with the classical network theory. An empirical relation of Q = 2.45 Cc^−0.600 was obtained and the validity of Flory's swelling equation was confirmed indirectly. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 808–814, 2000     

Improving the antibacterial activity of cotton fabrics finished with triclosan by the use of 1,2,3,4‐butanetetracarboxylic acid and citric acid

For producing antibacterial textiles, the conventional finishing processes have high productivity and low processing costs, but textiles finished in these ways exhibit low durability against laundering. Therefore, cotton fabrics were bleached with hydrogen peroxide, finished with triclosan, and then treated with polycarboxylic acids such as 1,2,3,4‐butanetetracarboxylic acid (BTCA) and citric acid (CA) as crosslinking agents to provide durable antibacterial properties. The surface of fibers treated with BTCA had a greater crosslinked area, and the surfaces of fabrics treated with CA were exposed to greater amounts of deformation due to the mechanical and chemical influences after 50 launderings. The bleaching and finishing treatments did not dramatically affect the breaking strength. However, the polycarboxylic acid treatment (both BTCA and CA) alone showed reductions in the breaking strength when the acid concentration was increased. The polycarboxylic acids were fairly effective against both bacteria, even at lower concentrations, when they were applied to stand‐alone cotton fabrics, whereas the antibacterial activity decreased somewhat after the use of polycarboxylic acid and triclosan in the same recipes. Adding polycarboxylic acids to the antibacterial finishing recipes enhanced the durability after 50 launderings, and the durability of the recipes containing BTCA was much higher than that of the recipes containing CA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pore and crosslinking structures of cotton cellulose crosslinked with DMDHEU‐maleic acid

Two dicarboxylic acids (maleic acid and tartaric acid) were used in conjunction with DMDHEU as the crosslinking agents to treat cotton fabric samples. The treated fabrics then were dyed with direct red 81. The results show that the values of the dye absorption, equilibrium absorption, rate constants, and the pore index of structural diffusion resistance constant for the various crosslinking agents are ranked as DMDHEU‐tartaric acid > DMDHEU‐maleic acid > DMDHEU alone at the same dyeing temperature. The activation energies for the three crosslinked fabrics are in the rank of DMDHEU > DMDHEU‐maleic acid > DMDHEU‐tartaric acid. The CL length values for the various crosslinking agent systems are in the series of DMDHEU‐tartaric acid > DMDHEU‐maleic acid > DMDHEU alone for a given number of CL/AGU. The values of the pore index of structural diffusion resistance constant and dyeing rate constant are increased with the increase of CL length. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 143–148, 2005     

Polycarboxylic acids as crosslinking agents for grafting cyclodextrins onto cotton and wool fabrics: Study of the process parameters

In this paper we describe a new method for the grafting of cyclodextrins (CDs)onto cotton or wool fabrics. The novelty principally concerns the chemical approach of the grafting reaction that was carried out in the presence of polycarboxylic acids, such as 1,2,3,4‐butanetetracarboxylic acid, citric acid, or polyacrylic acid. All types of native or CD derivatives could be used successfully as long as they carried enough remaining hydroxyl groups. For example, the amount of native β‐CD fixed onto the fabrics increased up to 12% in weight, whereas this value decreased to only 3% for the randomly methylated derivative of β‐CD (RAMEB). We observed that phosphorous salts, such as sodium mono‐ and dihydrogen phosphate or sodium dihydrogen hypophosphite, catalyzed the reaction. On the other hand, the conventional and convenient pad–dry–cure technique that is currently used at the industrial scale in textile processing was applied. We report that the polycarboxylic acids play the role of linking agent through an esterification (or amidification) reaction with the OH (or NH₂) groups of both CD and cotton (or wool) fibers. In addition, this reaction could lead to the graft of a copolymer formed between CD and the polycarboxylic acid. The reaction yield depends on the concentration and nature of the aforementioned reactants and catalysts and on the curing conditions (time and temperature). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1449–1456, 2002     

Effect of plasma pretreatment on the wrinkle‐resistance properties of cotton fibers treated with a 1,2,3,4‐butanetetracarboxylic acid–sodium hypophosulfite system with titanium dioxide as a cocatalyst

A 1,2,3,4‐butanetetracarboxylic acid (BTCA)–sodium hypophosulfite (SHP) wrinkle‐resistance system played an important role in improving the wrinkle‐resistance properties of cotton fibers. In this study, titanium dioxide (TiO₂) was used as a cocatalyst to further enhance the wrinkle‐resistance properties of BTCA–SHP‐treated cotton fabrics, that is, those treated with (1) 5% BTCA and 10% SHP; (2) 5% BTCA, 10% SHP, and 0.1% TiO₂; and (3) 5% BTCA, 10% SHP, and 0.2% TiO₂. In addition, the effect of plasma as a pretreatment process on the wrinkle‐resistance properties of the three treatment systems was also studied. The experimental results reveal that the wrinkle‐resistance properties of cotton fibers were improved after different wrinkle‐resistance treatments. In addition, the plasma pretreatment further enhanced the wrinkle‐resistance treatments to different extents, depending on the process parameters. Scanning electron microscopy images confirmed that such plasma pretreatment conditions imparted the best crosslinking effect on the cotton fibers. However, the wrinkle‐resistance‐treated cotton specimens had lower tensile strength and tearing strength values compared to the control sample, whereas the plasma pretreatment and cocatalyst may have compensated for the reduction in the mechanical strength caused by the wrinkle‐resistance agents. In this article, the optimum conditions for the plasma pretreatment on the basis of the result of the wrinkle‐recovery angle were analyzed with an L₉(3)³ orthogonal array testing strategy technique. The results showed that plasma treatment conditions with (1) a 10 mm/s speed, (2) a 0.1 L/min oxygen flow rate, and (3) a 4‐mm jet‐to‐substrate distance together caused a significant improvement in the wrinkle‐resistance properties of the cotton fibers treated with the three different BTCA treatments. Moreover, the treatment speed was the dominant factor, followed by jet‐to‐substrate distance and oxygen flow rate, in affecting the extent of improvement. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

IR spectroscopy study of cyclic anhydride as intermediate for ester crosslinking of cotton cellulose by polycarboxylic acids. V. Comparison of 1,2,4-butanetricarboxylic acid and 1,2,3-propanetricarboxylic acid

In recent years extensive efforts have been made to use multifunctional carboxylic acids as formaldehyde-free crosslinking agents for cotton to replace the traditional formaldehyde-based N-methylol reagents. In our previous research we found that a polycarboxylic acid esterifies cellulose through the formation of a five-membered cyclic anhydride intermediate by dehydration of two adjacent carboxyl groups. In this research we used Fourier transform IR (FTIR) spectroscopy to study the formation of cyclic anhydride intermediates and crosslinking of cotton by 1,2,4-butanetricarboxylic acid (BTA) and 1,2,3-propanetricarboxylic acid (PCA). BTA and PCA form five-membered cyclic anhydrides in the same temperature range. Both acids form the anhydrides at lower temperatures when a catalyst is present. When an acid molecule is bonded to cotton through an ester linkage, only PCA is able to form a second anhydride intermediate. We found that PCA is a more effective crosslinking agent, and it imparts higher levels of wrinkle resistance to the cotton fabric than BTA. Therefore, the formation of a five-membered cyclic anhydride by a polycarboxylic acid accelerates the esterification of cotton by the acid. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2142–2150, 2001     

Modular Phosphine‐Aminophosphine Ligands Based on Chiral 1,2,3,4‐Tetrahydro‐1‐naphthylamine Backbone: A New Class of Practical Ligands for Enantioselective Hydrogenations

A series of new chiral phosphine‐aminophosphine ligands [(R)‐HW‐Phos] has been prepared from (R)‐1,2,3,4‐tetrahydro‐1‐naphthylamine through a two‐step procedure, and successfully applied in the rhodium‐catalyzed asymmetric hydrogenation of various functionalized olefins such as α‐enol ester phosphonates, α‐enamido phosphonates, (Z)‐β‐(acylamino)acrylates and so on. Excellent enantioselectivities have been achieved in the hydrogenation of most substrates tested, demonstrating the high potential of these newly developed phosphine‐aminophosphine ligands in asymmetric catalysis. The present research also discloses that these newly developed phosphine‐aminophosphine ligands are more efficient than that derived from (S)‐1‐phenylethylamine, suggesting that the increased rigidity conferred by a cyclohexyl fragment in these phosphine‐aminophosphine ligands has a positive effect in the asymmetric induction.     

Esterification of n‐butyric acid with n‐butyl alcohol and transesterification of (R, S)‐phenylethanol by lipase immobilized on cellulose acetate–TiO2 gel fibre

Lipase (EC 3.1.1.3) was immobilized on cellulose acetate–TiO₂ gel fibre by the sol–gel method. The immobilized lipases were used for esterification of n‐butyric acid with n‐butyl alcohol and enantioselective acylation of (R, S)‐phenylethanol using vinyl acetate as an acyl donor. Compared with native lipase, the activity of the immobilized lipase was stable and relatively unaffected by the water content of the solvent and the substrate concentration. The data indicate that the lipases are immobilized on the fibre surface and that enzyme activity is influenced by bound water. However, the thermal reactivity and enantioselectivity of the immobilized lipase were less than those of native lipase. This may not reflect thermal inactivation of the enzyme but rather significant thermal contraction of the gel fibre by cellulose crystallization, resulting in liberation of bound water and a decrease in the amount of enzyme which is available for the reaction. Copyright © 2001 Society of Chemical Industry     

Controlled heterogeneous modification of cellulose fibers with fatty acids: Effect of reaction conditions on the extent of esterification and fiber properties

The controlled heterogeneous partial modification of cellulose fibers with fatty acids, partially preserving the fiber structure, was investigated. The effect of reaction conditions, such as reaction time, fatty acid chain length, and solvent types (swelling and non swelling), on the extent of esterification and fiber properties was evaluated by elemental analysis, IR‐ATR, X‐ray diffraction, ¹³C CPMAS NMR, contact angle measurement, thermogravimetry, and scanning electron microscopy. The degree of substitution (DS) increased with reaction time and with the swelling effect of the reaction medium and decreased with the fatty acids chain length. Higher the DS, higher is the decrystallization of cellulose as a result of the heterogeneous esterification reaction. The esterification with fatty acids enhanced the hydrophobic character of the fibers, but decreased their thermal stability. These properties are not strongly affected by the DS in the range investigated, viz. up to 1.4. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1093–1102, 2006     

Preparation of a starch‐graft‐acrylamide/kaolinite superabsorbent composite and the influence of the hydrophilic group on its water absorbency

A novel starch‐graft‐acrylamide/kaolinite superabsorbent composite with water absorbency 4000 times (g ) was synthesized by a graft copolymerization reaction among acrylamide, potato starch and kaolinite ultrafine powder, followed by saponification with NaOH. The influence of the hydrophilic group on water absorbency was investigated. It was found that the combined absorbent effect of —CONH₂, —COONa and —COOH groups was superior to that of a single group, and the composite with the molar ratio of 8:6:3 for the —CONH₂, —COONa and —COOH groups exhibits the highest water‐absorbent ability. Copyright © 2003 Society of Chemical Industry     

Regulating the pore structure of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) oxidized cellulose membranes: impact of drying method and organic solvent processing

Cellulose‐based membrane is a satisfactory candidate for the separator of lithium‐ion batteries due to its renewability, abundant pore structure and outstanding thermal–chemical stability. In this study, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) oxidized cellulose fiber (TOCF) membranes with different oxidation degrees were prepared. Membranes with high oxidation degree are faced with a pore closure issue, resulting in low porosity. In order to improve the pore structure, the TOCF membranes were dried differently through air drying, vacuum drying and freeze drying. Furthermore, air‐dried membranes were processed by three organic solvents – n‐butyl alcohol, carbon tetrachloride and n‐heptane. The physical properties, pore structure characteristics, mechanical properties and the electrochemical performance of the membranes were measured and characterized. From the results, freeze drying is found to provide the highest porosity and mean pore diameter. Unfortunately, Young’s modulus of the freeze‐dried membranes is the smallest as well. However, membranes processed by n‐butyl alcohol have weak tensile properties. Compared to non‐processed membranes, membranes processed by organic solvents present better pore structure and significantly better electrochemical performance. With all properties considered, TOCF membranes processed by carbon tetrachloride or n‐heptane are qualified for serving as battery separators as they possess improved pore structure, enhanced Young’s modulus, considerable tensile strength and improved electrochemical properties. © 2020 Society of Chemical Industry     

Melting‐reactive dyes for mass coloration of nylon based on blend compatibilization: Perylene‐3,4,9,10‐tetracarboxylic acid dianhydride

The mass coloration of nylon‐1010 with a melting‐reactive dye, an economically favorable and environmentally friendly method of coloration, is described. Perylene‐3,4,9,10‐tetracarboxylic acid dianhydride (PTAD) was used as a melting‐reactive dye for nylon‐1010, and it showed high thermal stability. A chain‐extending reaction was confirmed by an ultraviolet–visible spectroscopic analysis. The effect of the proportion of added PTAD on the intrinsic viscosity of the polymer was studied, and increased amounts resulted in increased intrinsic viscosity. The light fastness of the colored fibers was found to be 4. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2164–2167, 2002     

Kinetic study on the esterification of geraniol and acetic acid in organic solvents using surfactant‐coated lipase

Surfactant‐coated lipase (SCL) was prepared by coating the surface of Candida cylindracea lipase with the non‐ionic surfactant, Span 85. SCL catalyzed the esterification of geraniol and acetic acid. The ester product, geranyl acetate, is an important component of flavor and fragrance compounds. The SCL prepared in this work had low solubility in organic solvent, unlike those prepared by other investigators. A kinetic study of the mechanism of the lipolytic esterification and the reaction rate for facilitating the scale‐up of the reactors indicated a ping‐pong bi bi model with competitive substrate inhibition by acetic acid and dead‐end inhibition by acetic acid. Experimental data agreed with the proposed model. Kinetic parameters, K_i , K_{m (AA)} , K_m(GOH) and V_max , were determined which visualized the reaction mechanism of the SCL esterification. © 1999 Society of Chemical Industry     

Crosslinked acrylic pressure‐sensitive adhesives. I. Effect of the crosslinking reaction on the peel strength

For pressure‐sensitive adhesives (PSAs) composed of poly(co‐ethyl acrylate‐2‐ethylhexyl acrylate‐2‐hydroxyethyl methacrylate) as a base resin and polyisocyanate as a crosslinker, the relationship between the crosslinking reaction and peel strength was investigated. A 90° peel test of cured PSA films under various storage conditions was carried out. At the same time, the isocyanate (NCO) consumption in these PSA films was monitored by attenuated total reflectance/Fourier transform infrared spectroscopy. The peel strength of the PSA compounded with the crosslinker decreased as the NCO groups were consumed. The elevation of the aging temperature promoted the crosslinking reaction and increased the decrement in the peel strength. The peel strength of noncrosslinked and crosslinked PSA films increased with the contact time. A high storage temperature made the increment in the peel strength increase. The addition of the crosslinker to the PSA films reduced the increment in the peel strength. Furthermore, PSA films with residual NCO groups possessed stronger peel strengths than fully cured films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1493–1499, 2003     

Insoluble porous conjugated polymer films via phase separation and photo‐crosslinking for the trace detection of 2,4‐dinitrotoluene

A novel conjugated polymer film with microscale/submicroscale porous morphology fabricated from crosslinked poly(fluorene‐co‐carbazole) (PFC1) was developed for the detection of 2,4‐dinitrotoluene (DNT). The fluorescent conjugated polymer PFC1 with pendant photo‐crosslinkable coumarin groups was synthesized by Suzuki coupling polymerization. Taking advantage of the phase separation of PFC1/polystyrene (PS) blends in the film and the solvent‐resistant network, porous structured films were prepared by removal of PS. Films with porous morphologies exhibited marked responsive sensitivity to trace DNT vapor due to the unique porous structure favoring the diffusion of and association with DNT molecules. The formation of a crosslinked network by dimerization of the coumarin moieties may be beneficial for isolating the polymeric backbones, thus to some extent preventing chain aggregation. This facile fabrication method enabled the crosslinked porous films to be efficient fluorescence chemosensors towards the detection of trace amounts of DNT vapor.© 2012 Society of Chemical Industry     

New methods for acylation of pure and sawdust‐extracted cellulose by fatty acid derivatives—Thermal and mechanical analyses of cellulose‐based plastic films

This work deals with the synthesis of cellulosic plastic films obtained in homogeneous conditions by microwave‐induced acylation of commercial or chestnut tree sawdust cellulose by fatty acids. The acylation reaction was studied according to N,N‐dimethyl‐4‐aminopyridine (DMAP) amount, DMAP simultaneously playing the role of catalyst and proton trapping base. This study clearly showed that DMAP does not influence degrees of substitution (DS), massic, and molar yields. Plastic films synthesized in the absence of DMAP showed a decrease in mechanical behavior. Organic (tributylamine) or inorganic bases (CaCO₃, Na₂CO₃) were then added to replace DMAP basic activity, and no changes were observed. Concerning thermal and mechanical properties of plastics obtained with various bases, glass transition temperatures (T_g) and degradation temperature (T_d) were found constant whatever the base, and the best mechanical properties were obtained for films synthesized in the presence of CaCO₃. The same remarks were made concerning the valorization of chestnut tree sawdust cellulose. Microbial biodegradation of plastic films with DS = 2.2 led to a loss of their mechanical behaviors. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1266–1278, 2005     

Properties of regenerated cellulose films plasticized with α‐monoglycerides

Regenerated cellulose (RC) films were plasticized with glycerol, glycerin α‐monobutyrate, glycerin α‐monocaproate, glycerin α‐monocaprylate, and glycerin α‐monocaprate. The structure and properties of the films were investigated by using Fourier transform IR, wide‐angle X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, and tensile tests. The experimental results showed that the addition of plasticizer enhanced the elongation at break, thermal stability, and crystallinity and lowered the tensile strength of the films. The formation of hydrogen bonds between the cellulose and plasticizers weakened the inter‐ and intra‐hydrogen bonds among cellulose molecules, leading to reduced tensile strength. These α‐monoglycerides have relatively good plasticizing effects. Compared with glycerol, the resistance against water washing of the synthesized compounds was significantly enhanced. With the increase of the carbochain length of the α‐monoglycerides, the plasticizing effect decreased but the resistance against water washing was enhanced. When the RC films were immersed in a 10% glycerin α‐monocaproate solution, the elongation at break increased to 15% and stayed at 14.8% after water washing. Glycerin α‐monocaproate might be better for plasticizing RC films than others. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3500–3505, 2003