Reversible crosslinks in cotton modified with N-hydroxymethylacetylthioacetamide

The reaction of cotton fabric with N-hydroxymethylacetylthioacetamide (HOCH₂-NHCOCH₂SCOCH₃) yields acetylthioacetamidomethylcellulose, which can be saponified under mild conditions to the corresponding thiol derivative, mercaptoacetamidomethylcellulose. Some reactions of the thiol group are discussed, including oxidation to disulfide, repeated reduction-oxidation cycles, and blocking with alkyl halides. Chemical methods were used in establishing the occurrence and extent of the predicted reactions and their dependence on specific variables in the system. Changes in the crease recovery and tensile strength of the cotton derivative obtained in the reactions were found to be qualitatively consistent with the expected structures. The results of this work show that crosslinks can be obtained reversibly in cotton by this sequence of reactions. Intervening side reactions produce a gradual decrease in the yield of the desired products, however, as the number of cycles increases. Mercaptoacetamidomethylcellulose provides a limited but useful model for the investigation of reversible crosslinks in cellulose.     

Tensile recoveries of cotton modified with and without crosslinks

When effect of the substrate is nullified, resiliency can be defined as a function of strain, time, and humidity. Determination of improvement in the immediate, or rapid, tensile recovery readily delineates differences due to chemical modifications. Delayed recovery is usually less improved than immediate. Crosslinking cotton with dimethylolethyleneurea (DMEU) increases tensile strain recovery as the number of crosslinks increase, reduces dependency of recovery upon external strain, and produces maximum recovery at about 65% R.H. Noncrosslinking treatments produce limited increases in tensile strain recovery. Measurements on yarns crosslinked with DMEU and then hydrolyzed indicate that incalculably few residual links may contribute to tensile recovery. N-Methylol-N'-methylethyleneurea treated cotton displays physical blocking and water swelling which aid recovery. Oleoyl chloride esterified cellulose has tensile recovery probably due to molecular entanglements. Its delayed or viscoelastic recovery is the most improved with immediate recovery being the least improved. The higher the moisture regain, the greater tensile modulus reduction under wet conditions. Crosslinking with DMEU under dry conditions lessens this reduction in modulus. Improvements in the tensile recovery of strain and energy, for all samples and with varied conditions of humidity and strain, correspond linearly with unit slope.     

The combination of a hydroxy‐functional organophosphorus oligomer and melamine‐formaldehyde as a flame retarding finishing system for cotton

In previous research, it was found that melamine‐formaldehyde resin can be used as a binder for a hydroxy‐functional organophosphorus flame retarding agent (FR) on cotton. The role that trimethylol melamine (TMM) plays in this flame retarding system was studied. When TMM is applied to cotton, it forms crosslinks between cellulose molecules. When TMM is applied to cotton in the presence of FR, it reacts with FR to form a crosslinked polymeric network in addition to reacting with cotton. The formation of the crosslinked network improves the laundering durability of FR and also increases the fabric stiffness. The number of crosslinks among cotton cellulose formed by TMM decreases as the FR concentration in the system is increased. TMM also functions as a nitrogen provider to enhance the flame retarding performance of FR due to phosphorus–nitrogen synergism. Therefore, the amount of TMM used in a FR/TMM formula plays the most critical role in determining the effectiveness of this flame retarding system. The finish bath pH also plays a significant role in influencing the performance of the flame retarding system on cotton. The optimum pH was found to be around 4. Copyright © 2004 John Wiley & Sons, Ltd.     

Crosslinking cotton with poly(itaconic acid) and in situ polymerization of itaconic acid: Fabric mechanical strength retention

Polycarboxylic acids have been used as nonformaldehyde durable press finishing agents for cotton fabrics. Previously, we found that itaconic acid (IA) polymerized in situ on cotton fabric and also in an aqueous solution in the presence of a K₂S₂O₈/NaH₂PO₂ initiation system. Both poly(itaconic acid) (PIA) and the polymer formed by in situ polymerization of IA are able to crosslink cotton cellulose, thus imparting wrinkle resistance to cotton. In this research, we compared the performance of the cotton fabric crosslinked by PIA and that crosslinked by in situ polymerization of IA. The fabric treated with PIA and that treated with IA had similar wrinkle recovery angles. The cotton fabric treated with IA, however, lost more tensile strength than that treated with PIA due to cellulose degradation. We determined the magnitude of the fabric tensile strength loss attributed to crosslinking by separating the tensile strength loss due to cellulose degradation from the total tensile strength loss, and found that the tensile strength loss caused by crosslinking for the fabric treated with PIA was significantly higher than that for the fabric treated with IA. This can probably be attributed to more concentrated crosslinkages formed on the near surface of the PIA‐treated cotton fabric. PIA had poorer penetration into the amorphous cellulose region in fiber interior due to its much larger molecular size, thus increasing its concentration on the fabric's near surface. The data also suggest that more concentrated crosslinkages on the fabric surface reduced fabric abrasion resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2023–2030, 2003     

A comparative study of swelling properties of hydrogels based on poly(acrylamide‐co‐methyl methacrylate) containing physical and chemical crosslinks

Poly (acrylamide‐co‐methyl methacrylate) hydrogels of different ratios were prepared by using chemical and physical crosslinks to study the effect of nature of crosslinks on swelling behavior of hydrogels. The chemically crosslinked gels were prepared by using NN′‐methylene bis acrylamide, while physically crosslinked hydrogels were prepared by precipitation polymerization method, using dioxane as solvent. Detailed swelling kinetics such as swelling ratio, transport exponent n, diffusion coefficient D and the effect of pH on equilibrium swelling studies. The study revealed that the nature of crosslinks alter the swelling characteristics of the hydrogel. In chemically crosslinked hydrogels the water transport is Fickian in nature, while in the case of the physically crosslinked hydrogels the water transport mechanism is anomalous indicating major change in relaxation mechanism due to nature of crosslinks. The results also indicate that with increasing acrylamide content the swelling ratio of the hydrogels were also increased, but the transport exponent n remains nearly constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 779–786, 2003     

Polymeric multifunctional carboxylic acids as crosslinking agents for cotton cellulose: Poly(itaconic acid) and in situ polymerization of itaconic acid

Multifunctional carboxylic acids have been used as nonformaldehyde durable press finishing agents for cotton. In previous research we found that maleic acid (MA) and itaconic acid (IA) polymerize in situ on cotton fabric at elevated temperatures when both potassium persulfate (K₂S₂O₈) and sodium hypophosphite (NaH₂PO₂) are present, thus imparting wrinkle resistance to the treated cotton fabric. We also found that MA and IA polymerize in aqueous solutions in the presence of K₂S₂O₈ and NaH₂PO₂. In this research, we compared the effectiveness of poly(itaconic acid) (PIA) applied to cotton fabric as a polymer and IA applied as a monomer and allowed to polymerize in situ for crosslinking cotton cellulose. We found that IA is more effective in esterifying cotton cellulose and imparting a high level of wrinkle resistance to the fabric as it polymerizes in situ than PIA applied as a polymer. We also found that tensile strength loss of the cotton fabric crosslinked by IA polymerizing in situ as a function of fabric wrinkle recovery angle is practically the same as that crosslinked by PIA applied as a polymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 319–326, 2001     

Degrees of heterogeneity of distribution of formaldehyde crosslinks in cotton cellulose

The distribution of formaldehyde crosslinks in cotton cellulose has been followed by electron micrographic analyses of fiber cross-sections and by kinetic analyses of rates of reactions of formaldehyde with cotton. Rapid and slow phases of the crosslinking reactions are indicated to extents which vary with the specific processes of reaction. A wide range in heterogeneity of distribution of crosslinks is found among the compositions investigated, the most heterogeneous distribution appearing in a high concentration of crosslinks in peripheral regions of the fiber. It is evident that additional substantial differences among the formaldehyde-crosslinked cottons are due to different extents of reaction of agent per accessible hydroxyl group.     

A measure of effective crosslinks in formaldehyde-modified cotton celluloses

Sol-gel fractions have been measured for cotton celluloses crosslinked with formaldehyde under widely different conditions of reaction and have been employed for estimation of the efficiency of crosslinking in the various processes. Most efficient utilization of formaldehyde for insolubilization of molecular chains is indicated for an aqueous process (form W′) and least efficient utilization is indicated for a nonaqueous process (form D′), the difference in efficiency being approximately a factor of 40. Interpretation of sol-gel data has been made relative to a model assuming random reaction of crosslinking agent throughout the cotton cellulose and by relationships developed by Charlesby and Pinner and by Shultz. This leads to estimates of relative numbers (moles) of effective chain elements per gram, v_e (i.e., twice the number of effective crosslinks), which decrease in the following sequence for cottons at the 0.20% level of formaldehyde (i.e., 6.7 × 10^?5 mole/g.): aqueous process, higher formaldehyde concentration (W′, v_e = 4.8 × 10^?5), vapor process (V, v_e = 1.75 × 10^?5), bake-cure process (C, v_e = 1.37 × 10^?5), aqueous process, lower formaldehyde concentration (W, v_e = 0.95 × 10^?5), nonaqueous process (D, v_e = 0.03 × 10^?5).     

Equilibrium swelling and solvation studies on crosslinked polyacrylamides

Polyacrylamide (PA) crosslinked with four different crosslinking agents, triethyleneglycol dimethacrylate (TEGDMA), N,N′‐methylene bisacrylamide (NNMBA), hexanediol dimethacrylate (HDDMA) and divinylbenzene (DVB), with mole percents ranging from 5 to 20, was prepared by solution polymerization and subjected to swelling and solvation studies. Solubility parameters and cohesive energy density were determined from swelling studies. Molecular weight between crosslinks for these systems were determined by Flory–Rehner analysis. There is a discontinuous volume change for 10% NNMBA and HDDMA crosslinked PA, 15% TEGDMA crosslinked PA and 10 and 15% DVB crosslinked PA in solvent mixtures of acetic acid and water due to phase change occurring at this stage. The hydrogels exhibit inhomogeneous crosslink distribution due to multiple crosslinking, cyclization and network irregularity owing from arising from entanglements. As the percentage of crosslinking increases, crosslinks become more homogeneous due to a decrease in entanglements. Copyright © 2004 Society of Chemical Industry     

Dynamic light scattering from polymer gels: spring-rotor model

Dynamic light scattering behaviour in the form of periodic oscillating correlation functions has been found from measurements on both physically and chemically crosslinked hydrogels. The former were aqueous methyl cellulose at the thermal gelation temperature and the latter were poly(N,N-dimethylacrylamide-co-methyl methacrylate-co-ethylene dimethacrylate) at swelling equilibrium in water. In order to explain the oscillating behaviour, a spring-rotor model is proposed in which the molecular motions inside a gel are modelled as vibrations of springs having various frequencies. These frequencies are equivalent to the rotational frequencies when the free rotor theory was used to process the oscillating correlation functions by a modified CONTIN computer program. The validity of this model is supported by experimental data in three ways. (1) The model fits the experimental data almost perfectly. (2) The main peak positions of the obtained frequency distribution are not affected by the scattering angle. (3) For the chemically crosslinked hydrogels differing only in content of ethylene dimethacrylate, the mean vibrational frequency of the gel spring is higher the shorter the spring, i.e. the lower the average molecular mass between crosslinks. © 1998 SCI     

Mild condition dissolution of high molecular weight cotton cellulose in 1‐butyl‐3‐methylimidazolium acetate/N,N‐dimethylacetamide solvent system

To investigate the effective dissolution of high molecular weight (MW) cellulose macromolecules at ambient conditions, cellulose (DP > 4,000) derived from cotton fiber waste was dissolved in 1‐butyl‐3‐methylimidazolium acetate (BMIMAc)/N,N‐dimethylacetamide (DMAc) solvent in this study. High MW cotton cellulose achieves a solubility between 3% and 5% cellulose concentrations using BMIMAc/DMAc solvent at ambient conditions. Rheological studies showed that all cellulose/solvent solutions displayed a shear thinning behavior. Results from the physical characterization revealed that well‐dissolved cotton cellulose exhibited highly porous structure and the crystalline structure of cotton cellulose was highly disrupted during dissolution and regeneration processes. This study is the first to report on the ability of BMIMAc/DMAc solvent system to dissolve high MW cellulose under ambient conditions, which represents an energy‐saving and environmentally friendly approach. As cellulose used in this study was derived from low quality waste cotton fibers, the potential utilization of such cotton cellulose may create a competitive market for low quality cotton and target advanced applications of cellulose‐based products for green materials and energy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45928.     

Degree of crosslinking and physical properties of dimethyloldihydroxyethyleneurea/acrylic acid crosslinked cotton fabrics after treatment with various metallic salts

Three metallic salts were used to posttreat dimethyloldihydroxyethyleneurea (DMDHEU)/acrylic acid (AA) crosslinked cotton fabrics, and the results showed that at a given value of the tensile strength retention (TSR), the dry crease recovery angle (DCRA) and wet crease recovery angle (WCRA) of the crosslinked and posttreated fabrics were higher than those of the DMDHEU–AA‐treated fabrics, and those of the crosslinked and posttreated fabrics were in the order of Ag⁺ > Cu⁺² > Al⁺³. The DCRA and TSR values for the crosslinked and posttreated fabrics were higher than those for the DMDHEU–AA‐crosslinked fabrics, and those for the crosslinked and posttreated fabrics were in the order of Ag⁺ > Cu⁺² > Al⁺³; however, WCRA values for the crosslinked and posttreated fabrics were lower than those for the DMDHEU–AA‐crosslinked fabrics, and those for the crosslinked and posttreated fabrics were ranked as Ag⁺ > Cu⁺² > Al⁺³ at a given number of crosslinks per anhydroglucose unit. IR spectra clearly revealed the different interactions and bonding states between the hydroxyl group of the cellulose and the various metallic ions and the strength of the interaction. All crosslinked and posttreated fabric samples showed good odor absorption and antibacterial and washing‐fastness properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 584–594, 2005     

Acetals as crosslinking reagents for cotton

Acetals that react with cotton to form cellulose crosslinks are derived from dialdehydes that can form five-or-six-membered tetrahydrofuran or tetrahydropyran rings. These aldehydes themselves are reactive to cotton, but the acetals do not form the aldehyde to react. The acetals were less reactive than the aldehydes and formed crosslinks with a different structure. Intrinsic reactivity of acetals increased with increased branching in the alkoxy group. but the increase was often hidden by the effect from changing solvents. In some instances a greater reactivity with methyl acetals was pronounced. Strength loss in cotton fabric from crosslinking was greater with acetals than with conventional crosslinking agents because even the most reactive acetals were less reactive and required more rigorous reaction conditions than conventional agents.     

Photoinitiated polymerization of N-methylolacrylamide with crosslinked cotton cellulose

The effects of crosslinking both unswollen and swollen cotton cellulose on the photoinitiated reactions of N-methylolacrylamide (NMA) with cotton are reported. Formaldehyde and dimethylolethyleneurea were used as crosslinking agents. Crosslinked cellulose had a decreased efficiency of photoconversion of NMA to poly(N-methylolacrylamide) (pNMA) with cotton. If the cellulose was crosslinked in the swollen state, increased dosages of ultraviolet radiation gave complete conversion of NMA to pNMA with cotton. Cotton that was crosslinked in the unswollen state probably restricted movement of the aqueous solution of NMA within the fiber and fabric structures and decreased chain propagation within the structures. This restriction resulted in decreased photoconversion of NMA to pNMA with cotton. Transmission and scanning electron microscopy of cotton cellulose that was crosslinked in the swollen state and of cotton cellulose that was crosslinked in the unswollen state showed that swollen cotton was less compacted than unswollen cotton.     

Molecular modeling of cellulose in amorphous state part II: effects of rigid and flexible crosslinks on cellulose

It is essential to understand the molecular level response of crosslinked cellulose chain segments upon deformation, in order to develop new agents which convey high durable-press (DP) rating to cellulose fibers with minimal strength loss. In this work models of amorphous cellulose crosslinked with both rigid and flexible crosslinks were constructed computationally for this purpose. Rigid crosslinks bound cellulose molecular segments together and blocked the chain slippage, providing cellulose models with a higher initial modulus and better elastic response. However, the loss of the chain slippage led to stress being distributed unevenly among cellulose chains. Chains in some regions were subjected higher stress and these regions were opened up much more than the rest of the cellulose, which presumably caused models to fail. When conformationally flexible crosslinks were used, breaking strain of cellulose was not significantly reduced but deformation recovery was not improved either, in comparison with the models of untreated cellulose. Conformational transitions were observed in the flexible crosslinks during extension. These results help to explain how and why rigid crosslinks work to provide wrinkle resistant properties and why they also lower tensile strength, and that just using a conformationally flexible crosslinking will not provide any recovery.     

Synthesis and characterization of polysaccharide hydrogel based on hydrophobic interactions

Hydrogels based on hydrophobic, or micellar interactions, are physically crosslinked hydrogels which are an attempt to overcome the poor mechanical properties of traditional, chemically crosslinked gels, such as low shear strength. We have prepared a polysaccharide-based hydrogel with physical crosslinks via hydrophobic interactions. In this work, we have synthesized hydrogel by grafting a hydrophobic moiety dioctylamine onto hydrophilic precursor carboxymethyl cellulose (CMC) through an amide bond formation, where ~33% of the carboxyl group in CMC was reacted with dioctylamine. The thermosensitive hydrogel can arrest 100 mL of deionized water per gram of gelator within few seconds. It showed the moderate rheological property. The hydrogel is nontoxic and does not show any adverse to human hemoglobin. It is a CMC based a unique gelator with high biocompatibility represent to be useful materials for biomedical application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47665.     

Molecular characteristics of polymerized surfactants: influence of introduced crosslinking agent and monomer concentration

Polymerizable surfactants are currently attracting considerable interest due to their promising applications in various fields of science and engineering. The present work is devoted to studies of crosslinked poly(N‐acryloyl‐11‐aminoundecanoic acid) and sodium poly(N‐acryloyl‐11‐aminoundecanoate) that were synthesized in reaction mixtures of various compositions (i.e. with different amounts of a crosslinking agent and monomer concentrations). The products were studied by viscometry, dynamic light scattering, sedimentation velocity ultracentrifugation, flow birefringence as well as equilibrium and non‐equilibrium electric birefringence. It was established that both intramolecular and intermolecular crosslinks are formed in the polymerization process. Molecular optical methods and electro‐optical methods were used to determine the sizes of macromolecules with intramolecular crosslinks and the structures containing intermolecular crosslinks that were prepared at various concentrations of the monomer and the crosslinking agent. It was demonstrated that a simultaneous decrease in the amount of the crosslinking agent and decrease in the initial monomer concentration during the synthesis resulted in a reduction in the number of intramolecular crosslinks and molecular masses of the synthesized crosslinked macromolecules. © 2019 Society of Chemical Industry     

Cetylpyridinium chloride cationic finishing improves the dyeing and antibacterial properties of madder dyed cotton

In this work, after cationic pretreatment of cotton fabric with cetylpyridinium chloride (CPC), the compound of citric acid (CA) and succinic acid (SUA) were used as crosslinking agents to dye cotton fabrics with natural madder dye to improve the dyeing and antibacterial properties and realise the multifunctional finishing of cotton fabric. The effects of mordant dyeing, CA + SUA crosslinked dyeing, and CPC/CA + SUA crosslinked dyeing on the microstructure and properties of cotton fabrics were compared. The dyeing by the three processes occurred primarily in the amorphous zone of the fibres, and all kept the original crystalline form of the cotton. CA + SUA crosslinked dyeing and CPC/CA + SUA crosslinked dyeing increased the thermal stability of the cotton fabric. CPC/CA + SUA crosslinked dyed cotton obtained excellent dyeing results with the colour depth value (K/S) of 12.3 and rubbing fastness and washing fastness of levels 4–5, and the levelness and dye permeability were acceptable. Furthermore, the antibacterial rate against Escherichia coli and Staphylococcus aureus reached 99.99%, and the ultraviolet protection factor (UPF) reached 50+. Moreover, the wrinkle recovery angle (WRA) increased by 55% compared with raw cotton. This showed that CPC/CA + SUA crosslinked dyed cotton had excellent antibacterial, anti-ultraviolet, and anti-wrinkle performances.     

Reaction of hexamethylphosphorous triamide with cotton cellulose

The reactivity of hexamethylphosphorus triamide, (P[N? (CH₃)₂]₃) (HPT), with cotton cellulose was examined under various conditions. HPT was found to react readily with the cellulose to produce a cellulose phosphite and/or phosphate ester having approximately one acidic hydrogen atom per phosphorus atom. The reaction of HPT with cotton cellulose was efficiently catalyzed by dimethylamine hydrochloride (1%). The phosphorus content imparted by the catalyzed reaction on cotton fabrics was approximately twice that imparted by the uncatalyzed reaction. Flame resistance of the treated fabrics ranged from fair to excellent. The treated fabrics also exhibited ion exchange properties and some crosslinking.     

Molecular weights and molecular weight distributions of irradiated cellulose fibers by gel permeation chromatography

Radiation degradation of cellulose fibers was investigated by gel permeation chromatography (GPC). Scoured cotton of Mexican variety (cellulose I), Polynosic rayon (cellulose II), and their microcrystalline celluloses obtained by hydrolysis of the original fibers were irradiated by Co-60 γ-rays under vacuum or humid conditions. The irradiated samples were then nitrated under nondegradative conditions. The molecular weights and molecular weight distributions were measured by GPC using tetrahydrofran as solvent. The relationship between molecular weight and elution count was obtained with cellulose trinitrate standards fractionated by preparative GPC. The degree of polymerization of the fibers decreased with increasing irradiation dose, but their microcystalline celluloses were only slightly degraded by irradiation, especially in microcrystalline cellulose from cellulose I. Degradation of the fibers irradiated under humid conditions was less than that irradiated under vacuum. It was found that the G-values for main-chain scission for the irradiated cellulose I, cellulose II, microcrystalline cellulose I, and microcrystalline cellulose II were 2.8, 2.9, less than 1, and 2.9, respectively, but the G-value for main-chain scission for the irradiated cellulose II was increased to 11.2 at irradiation doses above 3 Mrad. Consequently, it is inferred that cellulose molecules in the amorphous regions are degraded more readily, and the well-aligned molecules in crystalline regions are not as easily degraded by irradiation.