Combination of bifunctional aldehydes and poly(vinyl alcohol) as the crosslinking systems to improve paper wet strength

Two bifunctional aldehydes (i.e., glyoxal and glutaraldehyde) are used as the crosslinking agents to improve paper wet strength in the presence of fully hydrolyzed poly(vinyl alcohol) (PVA) as a co‐reactant. These bifunctional aldehydes alone improve paper wet strength but diminish its folding endurance. The use of PVA as a co‐reactant not only improves paper wet strength but also increases its dry strength and folding endurance. Glutaraldehyde is able to impart much higher levels of wet strength to the treated paper than glyoxal when a catalyst is present. The wet strength of the treated paper increases as the amount of PVA added is increased, and it also increases as the molecular weight (M_w) of the PVA increases. The data suggest that the reaction between glutaraldehyde and PVA promotes the formation of interfiber crosslinking, thus improving the wet strength without diminishing the flexibility of the treated paper. The use of a catalyst is critical to achieve high levels of durable wet strength of the treated paper. We studied the effects of different Lewis acids as the catalysts for crosslinking of pulp cellulose by glutaraldehyde and found that Zn(NO₃)₂ is the most effective one. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1673–1680, 2004     

Paper wet performance and ester crosslinking of wood pulp cellulose by poly(carboxylic acid)s

Poly(carboxylic acid)s have been used as crosslinking agents for wood pulp cellulose to increase the wet strength of paper. In this research, we evaluated the effects of two multifunctional carboxylic acids, i.e., 1,2,3,4-butanetetracarboxylic acid (BTCA) and poly(maleic acid) (PMA), on the wet strength retention, dimensional stability, wet stiffness, and folding endurance of the treated paper. We observed that the wet strength retention, dimensional stability, and wet stiffness of the treated sheets increase, whereas the folding endurance decreases as the poly(carboxylic acid) concentration applied to those sheets increases. We measured the ester carbonyl band absorbance in the spectra of the treated paper. The linear correlation between the ester carbonyl band absorbance and wet strength, dimensional stability, and wet stiffness indicates that the improvement in the wet performance of the treated paper is directly attributed to the ester crosslinking of the wood pulp cellulose by poly(carboxylic acid)s. The data presented in this article also indicate that FTIR spectroscopy can be used for predicting the performance of the paper crosslinked by poly(carboxylic acid)s. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 649–658, 1998     

Comparison of the kraft paper crosslinked by polymeric carboxylic acids of large and small molecular sizes: Dry and wet performance

Polycarboxylic acids have been used as crosslinking agents for wood pulp cellulose for improving paper wet strength. Our previous research showed that low‐molecular‐weight polymeric carboxylic acids are effective in improving paper wet strength retention and reducing its flexibility. In this research, we compared two polymeric carboxylic acids, that is, poly(maleic acid) (PMA) with M_n of 800 and poly(methyl vinyl ether‐co‐maleic acid) (PMMA) with M_n of 1,130,000 for improving paper wet strength. The kraft paper sheets were treated at a 2% acid level and cured at different temperatures. The dry strength, wet strength, and folding endurance of the treated sheets were measured. We found that PMA and PMMA have comparable effectiveness in improving paper wet strength and wet stiffness. However, the treatment with PMA increases paper brittleness and severely diminishes paper folding endurance, whereas the treatment with PMMA increases both the dry strength and folding endurance by enhancing the paper's toughness. This striking difference in the performance of the treated paper is attributed to the different nature of the crosslinkages formed on the sheets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 907–912, 1999     

Rapid synthesis of high strength cellulose–poly(vinyl alcohol) (PVA) biocompatible composite films via microwave crosslinking

The present study describes microwave (MW)-assisted rapid synthesis of biocompatible poly(vinyl alcohol) (PVA) composite films that demonstrate synergy between reinforcement and crosslinking. Bacterial cellulose (5% w/w) nanowhiskers (reinforcement) and tartaric acid 35% (w/w) (crosslinker) are incorporated in PVA to prepare crosslinked cellulose–PVA composite films. The properties of thus prepared crosslinked cellulose–PVA composite films are compared with samples crosslinked with conventional hot air oven heating (CH). Crosslinking by both of the methods reduces water absorption of PVA by around an order of magnitude and improves its thermal stability. An increase in strength from 42 (PVA) to 172 MPa and 159 MPa for MW and CH crosslinked samples, respectively is also observed. Although composites prepared using MW and CH show similar properties, MW takes only 14 min compared to 2 h in case of CH. Notably, the prepared composites demonstrate hemocompatibility and cytocompatibility, and may also be explored for biomedical applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47393.     

Mechanical strength of durable press finished cotton fabric part V: Poly(vinyl alcohol) as an additive to improve fabric abrasion resistance

Multifunctional carboxylic acids, such as 1,2,3,4‐butanetetracarboxylic acid (BTCA), are effective crosslinking agents for cotton cellulose and have become the most promising nonformaldehyde durable press (DP) finishing agents to replace the traditional formaldehyde‐based dimethyloldihydroxylethyleneurea (DMDHEU) and its derivatives. DP finishing imparts wrinkle resistance to cotton fabrics and also severely reduces the strength and abrasion resistance of finished fabrics. In this research, we investigated the use of poly(vinyl alcohol) (PVA) as an additive to improve the abrasion resistance of the cotton fabric crosslinked by BTCA. We found that addition of PVA improves the abrasion resistance of the crosslinked cotton fabric when the concentration of PVA exceeds 0.6% in the finish solution. We also found that the use of PVA as an additive has no negative effect on the wrinkle recovery angle (WRA), DP rating, and tensile strength of the treated cotton fabric. This is probably because the molecules of PVA stay on the surfaces of the cotton fibers due to their large molecular sizes. PVA competes with cellulose to esterify BTCA, thus reducing the number of crosslinkages formed on the cotton fiber surface. The reaction of PVA and BTCA may also form a protective layer on the fiber surface, thus reinforcing the mechanically weak points on the fiber surface. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3940–3946, 2004     

Synergistic strengthening of composite films by crosslinking graphene oxide reinforcement and poly(vinyl alcohol) with dicarboxylic acids

High‐strength plastic materials with excellent biodegradability, non‐toxicity and economically wide availability are in high demand. Herein, we demonstrate graphene oxide (GO) composite of poly(vinyl alcohol) (PVA) as a potential bioplastic material by chemical crosslinking. For a potential bioplastic material, PVA has to be addressed for its high water absorbing capacity along with improvement in tensile strength and thermal stability. These issues were addressed by enhancing the interfacial binding between PVA and GO, covalent bonds between the two being introduced by crosslinking with dicarboxylic acids, namely succinic acid (SuA) and adipic acid (AdA). Crosslinking of neat PVA with dicarboxylic acids also resulted in enhanced swelling resistance and thermal stability. The greatest improvement in tensile strength and swelling resistance was observed for a GO crosslinked with diacids due to the synergistic effect of reinforcement and crosslinking. Improvements of 225 and 234% in the tensile strength of PVA (31.19 MPa) were observed for 5% GO–PVA samples crosslinked with 6.25 mmol AdA and 7.5 mmol SuA, respectively. For the same samples, water uptake was 44 and 29%, respectively, compared to the non‐crosslinked PVA (359%). © 2017 Society of Chemical Industry     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of “glutaraldehyde” functionality on network formation in poly(vinyl alcohol) membranes

The use of higher‐functionality oligomers of glutaraldehyde on network formation was investigated and compared with glutaraldehyde monomer in step‐growth reactions. The effect of using such oligomers in network formation depends on the stoichiometry, which alters either the branching or both the branching and crosslinking of the network. This was demonstrated in the properties of poly(vinyl alcohol) (PVA) networks crosslinked with glutaraldehyde using cryogenic scanning electron microscopy, water swelling studies, and protein transfer across membranes. General guidelines were given for the proper use of glutaraldehyde solutions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 780–792, 2005     

Influence of crosslinking methods toward poly(vinyl alcohol) properties: Microwave irradiation and conventional heating

In this study, crosslinking of poly(vinyl alcohol) (PVA) with tartaric acid, as crosslinker, is performed using microwave irradiation. A comparison between the properties of PVA crosslinked using microwave irradiation and conventional heating methods is also discussed. While the water absorption, tensile and thermal properties of PVA crosslinked by either of the methods are comparable, microwave irradiation took only one‐eighth (14 min) of the time compared to conventional heating. In comparison with PVA (42 MPa), the strength of PVA crosslinked with 35% TA increased to 145 and 153 MPa for conventional heating and microwave irradiation, respectively. Water absorption of crosslinked PVA film is successively reduced to less than 30% in comparison with PVA (～200%). Moreover, the crosslinked films are stable at higher temperatures in comparison with PVA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46125.     

Preparation and characterization of polyacrylic acid‐poly(vinyl alcohol)‐based interpenetrating hydrogels

Some structural features of hydrogels from poly(acrylic acid) (PAAc) of various crosslinking degrees have been investigated through mechanical and swelling measurements. Interpenetrating polymer hydrogels (IPHs) of poly(vinyl alcohol) (PVA) and PAAc have been prepared by a sequential method: crosslinked PAAc chains were formed in aqueous solution by crosslinking copolymerization of acrylic acid and N,N‐methylenebisacrylamide in the presence of PVA. The application of freeze–thaw (F–T) cycles leads to the formation of a PVA hydrogel within the synthesized PAAc hydrogel. The swelling and viscoelastic properties of the IPHs were evaluated as a function of the content of crosslinker and the application of one F–T cycle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5789–5794, 2006     

Effect of gelatin on the swelling behavior of organic hybrid gels based on N‐isopropylacrylamide and gelatin

Organic hybrid gels based on poly(N‐isopropylacrylamide) and a natural polymer, gelatin, were prepared through two‐step crosslinking with genipin or glutaraldehyde. The effects of the gelatin content on the swelling behaviors and physical properties of these hybrid gels were investigated. The results indicated that the swelling ratio decreased with an increase in the content of gelatin in these hybrid gels. The swelling ratio for the gel crosslinked by genipin was significantly smaller than that for the gel crosslinked by glutaraldehyde. The results also showed that the gel crosslinked with genipin had a higher crosslinking density and a higher gel strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1092–1099, 2005     

Chitosan,itaconic acid and poly(vinyl alcohol) hybrid polymer networks of high degree of swelling and good mechanical strength

Chitosan is a biodegradable, non‐toxic, biocompatible polymer convenient for use in drug delivery. In this study, hybrid polymeric networks (HPNs) based on chitosan, itaconic acid and poly(vinyl alcohol) (PVA) were prepared and characterized. Chitosan was dissolved in itaconic acid in order to obtain ionic crosslinking with the dicarboxylic acid. In the second step, this chitosan/itaconic acid network was mixed with PVA and chemically crosslinked with glutaraldehyde. The chitosan/itaconic acid ratio was kept constant, while the concentrations of PVA and glutaraldehyde were varied. All samples were characterized using swelling studies, dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction and scanning electron microscopy. The equilibrium degrees of swelling obtained for the HPNs were higher than most of the values reported for chitosan hydrogels obtained by dissolving chitosan in acetic acid or HCl aqueous solutions. This method of synthesis also resulted in hydrogels with better mechanical properties and thermal stability. By changing the PVA content and the degree of crosslinking, it is possible to finely tune the properties of the HPNs, which could make them suitable as potential matrices in controlled drug delivery. Copyright © 2010 Society of Chemical Industry     

Mechanism of crosslinking of papers with polyfunctional carboxylic acids

Brief thermal curing of papers treated with an aqueous solution of polyfunctional carboxylic acids and NaH₂PO₄ imparts substantial wet strength to the papers. The effectiveness of such carboxylic acids increases with their functionality in the order 1,2,3,4-butanetetracarboxylic acid (BTCA) > tricarballylic acid (TCA) ? succinic acid. The two main stages of the curing reaction of papers, i.e., pendant attachment of the polyfunctional carboxylic acids via esterification with cellulosic hydroxyl groups, and its further reaction with another cellulose hydroxyl group producing crosslinks of the cellulose fibers were analyzed separately using a combination of acid-base and conductometric titrations. The extent of reaction of the polyfunctional carboxylic acids with paper was followed by pH titration, which shows the total decrease in acid functions as the curing progresses and is directly related to the total consumption of carboxylic acids groups by ester attachment and ester crosslinking steps. The conductometric titration, on the other hand, measures the increase in carboxylic acids bound to cellulose units of the paper as a direct result of previous esterification steps. Our studies reveal that the reaction of BTCA with papers is essentially quantitative after 15 min of curing. The amount of once-reacted BTCA increases in the initial phases of the curing reaction and then decreases as more and more carboxylic acid units are converted into crosslinking sites, while the amount of crosslinked BTCA increases throughout the curing reaction. The reaction profile of papers with TCA differs from that of BTCA in that the curing reaction is initially dominated by the formation of ester appendages; crosslinking becomes the main reaction only after extended curing times. We attribute this difference to the ability of BTCA to form an highly reactive difunctional crosslinking reagent at the outset of the curing reaction, while TCA is initially monofunctional in its reaction with cellulosic hydroxyl groups (formation of a monoanhydride). The relationship between the wet tensile strength of the treated papers and their degree of crosslinking is also discussed. © 1995 John Wiley & Sons, Inc.     

Crosslinking of poly(vinyl alcohol) using dianhydrides as hardeners

The crosslinking reaction of poly(vinyl alcohol) (PVA) with 3,3′,4,4′-tetracarboxybenzophenone dianhydride, pyromellitic carboxylic acid anhydride, and Epiclon B-4400 as hardeners was studied either in solution or by differential scanning calorimetry. A catalyst agent had to be used in all cases. Depending on the concentration of hardener and catalyst, differences are observed. T_g values increase with the ratio of hardener and catalyst, while activation energies decrease with the amount of catalyst but little changes can be seen when different dianhydride amounts are used. The thermal properties of the final products were unaltered by the hardener used. The decomposition temperature is initiated at a similar temperature in linear and crosslinked PVA, but while uncured PVA undergoes a complete degradation in one step, crosslinked PVA degrades in several steps. © 1996 John Wiley & Sons, Inc.     

Starch crosslinked with poly(vinyl alcohol) by boric acid

Starch was crosslinked with poly(vinyl alcohol) (PVA) by boric acid. A suitable plasticizer and defoamer were added to obtain the brei. A film from the starch and PVA (SP film) was prepared by casting. The effects of various factors, such as the crosslinking temperature, the PVA content, and the amounts of glycerol and boric acid, on the tensile strength and breaking elongation were studied. The results showed that the SP film prepared by boric acid crosslinking had excellent mechanical properties. The film‐forming properties, transmittance, and water resistance of the SP film were also investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1394–1397, 2005     

Applications of bifunctional aldehydes to improve paper wet strength

Glyoxal and glutaraldehyde behave very differently for improving wet strength of paper. It is found that glyoxal is very efficient for improving temporary wet strength of paper without the presence of a catalyst and exposure to elevated temperatures. When a metal salt, such as Zn(NO₃)₂, is used as a catalyst and the curing temperature is increased, the durable wet strength of glyoxal‐treated paper increases at the expense of its flexibility, as shown by reduced stretch and folding endurance. Glutaraldehyde is not able to provide any improvement in wet strength to paper, even under high curing temperatures, provided no catalyst is used. With the aid of a metal salt catalyst, glutaraldehyde imparts excellent durable wet strength to paper without significantly sacrificing folding endurance, and the wet strength of glutaraldehyde‐treated paper increases steadily as curing temperature increases. The different behavior of glyoxal and glutaraldehyde may be attributed to their different reactivity toward cellulose. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2539–2547, 2002     

Preparation and characterization of chitosan/poly(vinyl alcohol) blend fibers

Chitosan and poly(vinyl alcohol) blend fibers were prepared by spinning their solution through a viscose‐type spinneret at 25°C into a coagulating bath containing aqueous NaOH and ethanol. The influence of coagulation solution composition on the spinning performance was discussed, and the intermolecular interactions of blend fibers were studied by infrared analysis (IR), X‐ray diffraction (XRD), and scanning electron micrograph (SEM) and by measurements of mechanical properties and water‐retention properties. The results demonstrated that the water‐retention properties and mechanical properties of the blend fibers increase due to the presence of PVA in the chitosan substract, and the mechanical strength of the blends is also related to PVA content and the degree of deacetylation of chitosan. The best mechanical strength values of the blend fibers, 1.82 cN/d (dry state) and 0.81 cN/d (wet state), were obtained when PVA content was 20 wt % and the degree of deacetylation of chitosan was 90.2%. The strength of the blend fibers, especially wet tenacity could be improved further by crosslinking with glutaraldehyde. The water‐retention values (WRV) of the blend fibers were between 170 and 241%, obviously higher than pure chitosan fiber (120%). The structure analysis indicated that there are strong interaction and good miscibility between chitosan and poly(vinyl alcohol) molecular resulted from intermolecular hydrogen bonds. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2558–2565, 2001     

Nanofiltration membranes based on poly(vinyl alcohol) and ionic polymers

Nanofiltration membranes based on poly(vinyl alcohol) (PVA) and ionic polymers, such as sodium alginate (SA) and chitosan, were prepared by casting the respective polymer solutions. The membranes prepared from PVA or PVA–ionic polymer blend were crosslinked in a isopropanol solution using glutaraldehyde as a crosslinking agent. The membranes were characterized with Fourier transform infrared spectroscopy and X‐ray diffractometry and swelling test. The membranes crosslinked through the acetal linkage formation between the  OH groups of PVA and the ionomer and glutaraldehyde appeared to be semicrystalline. To study the permeation properties, the membranes were tested with various feed solutions [sodium sulfate, sodium chloride, poly(ethylene glycol) with 600 g/mol of molecular weight (PEG 600), and isopropyl alcohol]. For example, the permeance and the solute rejection of the 1000 ppm sodium sulfate at 600 psi of upstream pressure through the PVA membrane were 0.55 m³/m² day and over 99%, respectively. The effects of the ionomers on the permeation properties of the PVA membranes were studied using the PVA–SA and PVA–chitosan blend membranes. The addition of small amount of ionic polymers (5 wt %) made the PVA membranes more effective for the organic solute rejection without decrease in their fluxes. The rejection ratios of the PEG 600 and isopropanol were increased substantially. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1755–1762, 1999     

Enhanced oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) blended with poly(acrylic acid) for packaging applications

To enhance the oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) (PVA) and expand its food packaging applicability, five crosslinked poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blend films were prepared via esterification reactions between hydroxyl groups in PVA and carboxylic acid groups in PAA. The physical characteristics of the blends, including the thermal, barrier, mechanical and optical properties, were investigated as a function of PAA ratio. With increasing PAA content, the crosslinking density was significantly increased, resulting in changes in the chemical structure, morphology and crystallinity of the films. The oxygen transmission rate of pure PVA decreased from 5.91 to 1.59 cc m^?1 day^?1 with increasing PAA ratio. The water resistance, too, increased remarkably. All the blend films showed good optical transparency. The physical properties of the blend films were strongly correlated with the chemical structure and morphology changes, which varied with the PAA content. © 2016 Society of Chemical Industry     

Elaboration of ion‐exchange membranes with semi‐interpenetrating polymer networks containing poly(vinyl alcohol) as polymer matrix

Ion‐exchange membranes were prepared with semi‐interpenetrating networks (s‐IPNs) by mixing a film‐forming polymer, poly(vinyl alcohol) (PVA), for the crosslinked matrix and a polyelectrolyte for the specific ion‐exchange property. Poly(sodium styrenesulfonate) (PSSNa), poly(styrenesulfonic acid) (PSSH), and poly(acrylic acid) (PAA) were used as anionic polyelectrolytes. Polyethyleneimine (PEI), poly(1,1‐dimethyl‐3,5‐dimethylenepiperidinium chloride) (PDDPCl), and poly(diallyldimethylammonium chloride) (PDDMACl) were used as cationic polyelectrolytes. Membranes with PVA 60% and polyelectrolyte 40% showed the best compromise among mechanical, homogeneous, and ion‐exchange properties. Gaseous dibromoethane was used as a crosslinking agent to form the PVA network and for efficient entrapment of the polyelectrolyte in the membrane. The crosslinking time (tc) was optimized for each type of membrane and its influence was studied by thermogravimetric analysis of the sample and scanning electron microscopy observations. The best results (large ion‐exchange capacity and small swelling ratio) were obtained for PVA/PAA and PVA/PSSNa/PSSH membranes. Among anion‐exchange membranes, PVA/PEI gave the best permselectivity (low co‐ion leakage) and the highest ion‐exchange capacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1572–1580, 2002; DOI 10.1002/app.10420