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1.
化学交联与热处理对聚乙烯醇膜性能的影响   总被引:1,自引:0,他引:1  
采用相转化法制备聚乙烯醇膜,分别研究了化学交联以及热处理对膜结构和性能的影响,利用红外光谱获得膜的交联度和结晶度。结果表明随着处理时间的延长,膜的交联度或者结晶度增加;溶涨试验结果表明热处理后膜的孔隙率下降,而化学交联对膜的孔隙率影响不大;力学性能测定表明膜在干态与湿态下,力学性能差别巨大,化学交联的膜在干态下的性能要大大好于湿态下的力学性能,而热处理的膜正好相反,热处理后膜的机械性能湿态要好于干态。  相似文献   

2.
Poly(vinyl alcohol) (PVA) membranes crosslinked with L‐malic acid were prepared, and the effects of the heat‐treatment temperature and crosslinker concentration on their swelling and hygroscopic performances were investigated. Both the swelling and hygroscopic performances of the PVA membranes decreased with increasing heat‐treatment temperature; while the former decreased, the latter increased with increasing crosslinker concentration. The PVA membranes were characterized with differential scanning calorimetry (DSC), acid–base titration, and Fourier transform infrared spectrometry. The DSC results indicated that there was freezing and nonfreezing water in the swollen membranes, whereas there was only nonfreezing water in the moistened membranes. In addition, acid–base titration analysis revealed that both increased heat‐treatment temperature and increased crosslinker concentration increased the bilateral ester group levels (crosslinking degree) and decreased the content of freezing water. By contrast, the content of hydrophilic groups decreased and increased with increasing heat‐treatment temperature and crosslinker concentration, respectively; this resulted in decreased and increased levels of nonfreezing water, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44481.  相似文献   

3.
In our previous research, we found that crosslinking paper using poly(carboxylic acid)s with different molecular weight or using the combination of glutaraldehyde and poly(vinyl alcohol) (PVA) significantly improved the wet strength of the paper. In this research, we studied the mechanism of paper wet strength development using crosslinking systems with different molecular weight by measuring scanning electron microscopic (SEM) images, wet strength, folding endurance, wet thickness, water retention, and Z‐direction tensile strength of the treated paper. The paper crosslinked by a high‐molecular weight (MW) poly(carboxylic acid) shows more swelling by water than that crosslinked by a low‐MW polycarboxylic acid in the SEM micrographs even though both treated paper samples have similar wet strength. Thus, the data suggest that high‐MW poly(carboxylic acid)s promote the formation of interfiber crosslinking. Crosslinking paper by glutaraldehyde, a crosslinking agent of small molecular size, improves wet strength and reduces flexibility and swellability of paper because of the formation of intrafiber crosslinking. Combining glutaraldehyde with PVA as a coreactant increases wet strength and also retains flexibility and swellability of the treated paper because of the formation of interfiber crosslinking. The hypothesis that PVA reacts with glutaraldehyde to form a polymeric pentanedialated‐PVA crosslinking system and promotes the formation of interfiber crosslinking on the paper is supported by the data of wet strength, folding endurance, wet thickness, water retention, and Z‐direction tensile strength of the treated paper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 277–284, 2006  相似文献   

4.
A series of poly(vinyl alcohol) (PVA)‐based single‐layer organic polymeric membranes were prepared via the crosslinking of PVA with different amounts of formaldehyde. Meanwhile, for comparison, both a three‐layer organic polymeric membrane and a hybrid composite membrane were also prepared by the layer‐upon‐layer method. Their thermal stability and tensile properties were investigated to examine the effect of crosslinking on the membrane performances. Thermogravimetric analysis and differential scanning calorimetry thermal analyses showed that the thermal degradation temperature of the single‐layer crosslinked membrane C reached up to 325°C. Tensile testing indicated that the three‐layer organic polymeric membrane E had excellent tensile strength among these single‐layer and three‐layer membranes. The swelling properties revealed that the swelling degree value of these membranes decreased with an increase in methanol concentration; this suggests that they were not easily swollen by the methanol solution, which is meaningful for the separation of organic mixtures. Field emission scanning electron microscopy images exhibited that the crosslinking of functional groups impacted their structures and confirmed that their mechanical properties were related to their structures. These findings suggest that the crosslinking of functional groups is an effective method for adjusting the tensile strength of PVA‐based organic polymeric membranes and related hybrid composite membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

5.
A novel physicochemical crosslinked nanocomposite hydrogel based on polyvinyl alcohol (PVA) and natural Na‐montmorillonite (Na+‐MMT) was synthesized by chemical crosslinking of nanocomposite hydrogel followed by a freezing‐thawing process. The effects of physical crosslinking, as well as physicochemical crosslinking, on the structure, morphology, and properties (thermal, mechanical, swelling, and deswelling) of nanocomposite hydrogels were investigated and compared with each other. The structure and morphology of nanocomposites were studied by Fourier transform infrared, X‐ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy techniques. The thermal and mechanical properties of nanocomposites that were affected by physical and physicochemical crosslinking were evaluated by thermogravimetric analysis, differential scanning calorimeter, dynamic mechanical analysis, hardness test, and Water vapor transmission rate (WVTR) experiments. The results showed that the physicochemical crosslinking of a PVA nanocomposite leads to a reduction in crystallinity and melting temperature, as well as an increase in the Hardness and WVTR compared to a physically crosslinked PVA nanocomposite hydrogel. The swelling and deswelling experiments were performed using a gravimetric method, and it was shown that controlled crosslinking of PVA nanocomposite hydrogel with glutaraldehyde causes the swelling ratio to increase and the cumulative amount of water loss to decrease. The swelling (sorption) and deswelling (desorption) kinetics data for physically and physicochemical crosslinking of nanocomposite hydrogels were fitted with a fickian model. It is concluded that through control crosslinking of PVA nanocomposite can lead to a hydrogel with higher swelling capacity than that is in conventional PVA nanocomposite hydrogel. POLYM. COMPOS., 37:897–906, 2016. © 2014 Society of Plastics Engineers  相似文献   

6.
In this work, three dianhydrides with similar chemical structures, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA), 4,4′‐oxydiphthalic anhydride (ODPA), and pyromellitic dianhydride (PMDA), are employed for the crosslinking modification of poly(vinyl alcohol) (PVA) membranes for ethanol dehydration via pervaporation. The changes in crosslinking degree, surface hydrophilicity, and glass‐transition temperature are investigated and compared. Compared to the pure PVA membrane, all crosslinked membranes show higher fluxes but lower separation factors, because of the higher fractional free volume and the lower hydrophilicity by the crosslinking of the PVA matrix, respectively. In addition, all crosslinked PVA membranes exhibit similar flux, and the separation factor presents a decreasing order of PVA/PMDA‐2 > PVA/ODPA‐2 > PVA/BTDA‐2, which is in the reverse order of their hydrophilicity, probably because of the reduction in the swelling resistance. With the PMDA content increasing from 0.01 to 0.04 mol/(kg PVA) in the PVA/PMDA crosslinked membranes, the crosslinking degree is enhanced and the hydrogen bonding is weakened, resulting in a flux increase from 120.2 to 190.8 g m?2 h?1, but the separation factor declines from 306 to 58. This work is believed to provide useful insight on the chemical modification of PVA membranes for pervaporation and other membrane‐based separation applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46159.  相似文献   

7.
Chemically and physically crosslinked chitosan membranes were prepared by treating chitosan (Ch) with glutaraldehyde (GA) and sulfuric acid (SA). FTIR and XRD results were employed to confirm the formation of covalent and ionic crosslinks between Ch, GA, and SA. The states of water in non‐crosslinked and covalently and ionically crosslinked chitosan membranes containing different amount of water were investigated by low temperature differential scanning calorimetry measurements. The equilibrium swelling in water was examined gravimetrically. Two types of water were found in the polymer samples, i.e., freezing water and non‐freezing water. The effect of crosslinking process on water state and water uptake was analyzed. The water uptake decreased after chitosan crosslinking with GA, but significantly increased after later crosslinking with SA. The amount of non‐freezing water was generally smaller in crosslinked membranes. An impact of molecular and supermolecular structure on water uptake and state of water in non‐crosslinked and crosslinked chitosan membranes was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1707–1715, 2013  相似文献   

8.
A facile synthesis concept focusing on the poly(vinyl alcohol) (PVA) concentration induced interfacial energy effects in seed swelling polymerization was realized for the successful fabrication of a series of monodispersed poly(methyl methacrylate) (PMMA) microparticles with four crosslinking agents, 2,2‐bis[(methacryloyloxy)methyl]butyl methacrylate, 1,2‐ethanediyl bis(2‐methylacrylate), 1,3‐divinylbenzene and 1,2‐ethanediyl diacetate. We revealed a special role of PVA in regulating the diffusion of crosslinking agents as well as the swelling degree of latex seeds and, more noticeably, the consequent improved mechanical properties of the crosslinked PMMA microparticles formed. The highest recovery rate obtained from the PMMA microparticles with 0.6 wt% PVA approached 67%, which is higher than or comparable to reported values. This work not only developed a new facile synthesis approach for producing highly uniform tough crosslinked PMMA microparticles for more potential applications but also provided valuable insights into fundamental aspects of seed swelling polymerization. © 2019 Society of Chemical Industry  相似文献   

9.
Cotton knitted fabrics were treated with poly(ethylene glycol) (PEG) in the presence of polyhydric alcohol etherified dimethylol dihydroxy ethylene urea as the crosslinker and magnesium chloride hexahydrate as the catalyst. In wet–dry cycles, the fabrics treated with 30% PEG1500 in the presence of 15% crosslinker and 3% catalyst showed obvious wet‐driven shape‐memory behaviors in terms of a 12% shrinkage rate in the wet state and a 80% shrinkage‐recovery rate in the dry state. The results of weight gain, morphological structures, Fourier transform infrared spectra, and X‐ray diffraction pattern tests confirmed PEG deposits on the surface of the treated fabrics, demonstrated the crosslinking of cotton cellulose with PEG and crosslinker, and also explained the wet‐driven shape‐memory mechanism. The results from differential scanning calorimetry show that the treated fabrics with wet‐driven shape‐memory behaviors had a phase‐change enthalpy and heat‐storage capacity. The crosslinking of cotton cellulose with PEG had a strong influence on the mechanical performance and air permeability of the cotton knitted fabrics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43473.  相似文献   

10.
An ideal hydrogel with excellent adhesive performance has drawn much attention in research and applications. In this paper, a photo‐crosslinked polyvinyl alcohol bearing styrylpyridinium group/cellulose nanocrystals (PVA‐SbQ/CNC) composite hydrogel is designed through photo‐crosslinking technology for preventing the physical crosslinking of polyvinyl alcohol to maintain enough hydroxy groups in the hydrogel. Thus, the hydrogel exhibits excellent adhesive behavior not only for various solid substrates (plastics, rubbers, glasses, metals, and woods) but also muscle and fat. In addition, the formation mechanism, the swelling behavior, and mechanical strength are also investigated. Also, these results show that photo‐crosslinked PVA‐SbQ/CNC hydrogel possesses high swelling rate, super stretchability, and high toughness. Moreover, adhesive, mechanical, and swelling properties of PVA‐SbQ/CNC hydrogels can be changed with the increase of total incident light intensity. It is anticipated that the photo‐crosslinked PVA‐SbQ/CNC hydrogel would play a significant role in the applications of wound dressing, medical electrodes, tissue adhesives, portable equipment, and super absorbent materials. In this sense, the simple photo‐crosslinking strategy would provide new ideas for designing soft and adhesive materials through controlling the balance of cohesion and adhesion.  相似文献   

11.
Flat‐sheet composite membranes were developed by the traditional phase inversion technique using poly;(vinyl alcohol) (PVA). PVA composite pervaporation (PV) membranes were prepared with crosslinked PVA selective layer and porous polyacrylonitrile (PAN) and polyether sulfone (PES) substrate layer material as supports for separating heat sensitivity substance ε‐caprolactam (CPL) from CPL/water mixtures. Glutaraldehyde was used as crosslinking agent. The effect of the composition of glutaraldehyde on membrane stability and structure were investigated. The operating parameters, such as feed concentration and operating temperature, remarkably affected PV performance of the composite membranes. The composite membranes with PVA casted on PAN (PVA/PAN) showed superior PV performance than that casted on PES (PVA/PES). This study has also shown that the type of porous support plays an important role in the PV performance. As a result, this work has presented the information needed of the behavior of PV membranes for dehydration applications of industrial caprolactam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4005–4011, 2007  相似文献   

12.
Cotton print cloth was treated with a solution of formaldehyde in concentrated orthophosphoric acid (a strong cellulose swelling agent). The treatment produces a crosslinked cotton with extremely high wet wrinkle recovery and moisture absorptivity, and very low dry wrinkle recovery. The variations in physical properties are explained in terms of crosslink distribution throughout the fiber and specifically by differences in interlamellar and intralamellar crosslinking. Data on the chemical and physical properties of the fabric as well as electron micrographs of fiber cross-sections are presented and compared or contrasted with data from similar treatments employing other solvents such as water (a moderate swelling agent), acetic acid (a weak swelling agent), and sulfuric acid (a solvent which restricts crosslinking to the periphery of the fiber). Although the treatment causes extensive fiber swelling, it produces very little change in crystallinity and no change in crystal lattice type. Also discussed are the effects of combining this wet crosslinking and conventional dry-cure crosslinking with methylol amides in a two-stage process, in which the wet crosslinking is used either as a pretreatment or as an aftertreatment.  相似文献   

13.
Using Na+ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H2SO4 as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H2O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H2O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

14.
Poly(vinyl alcohol)(PVA) films chemically crosslinked with glutaraldehyde(GA) in the presence of HCl were prepared by casting from aqueous solutions. The PVA and PVA gels were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA); their swelling characteristics and tensile strength were also determined. The DSC results for the gels displayed depressions of the melting and crystallization temperatures, as well as a decrease of the heat of fusion, when compared to those of PVA free of crosslinker. The DMA analysis revealed that: (1) The glass transition temperature of the wet PVA was lower than that of the dry one, indicating that the water had a plasticizing effect. (2) The gels had a lower glass transition temperature than PVA. (3) The glass transition temperature of the wet gels increased with increasing crosslink density. Possible explanations are provided for these observations. Whereas the thermogravimetric curves of PVA exhibited a single degradation peak, two degradation peaks were detected for the crosslinked PVA. The wet PVA and PVA gels displayed lower tensile strengths and higher elongations than the dried ones. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1816–1823, 2001  相似文献   

15.
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  相似文献   

16.
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  相似文献   

17.
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  相似文献   

18.
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  相似文献   

19.
用静电纺丝法制备了含有交联结构的PVA纳米纤维,并通过红外光谱分析(FT-IR)、扫描电子显微镜(SEM)、热分析(TG、DTA)对制品的结构和形貌进行了表征;通过对制品进行接触角、溶胀度的测定,考察了电纺条件和加热后处理对交联度的影响以及交联度对吸水率的影响;提出了静电场力可作为动力学条件促进化学反应的新概念。  相似文献   

20.
Cellular poly(vinyl alcohol) (PVA) hydrogels that exhibit enhanced swelling kinetics from an initial dry state were prepared by freezing and thawing techniques in the presence of NaCl. Gels that were dried immediately after preparation demonstrated a dual‐sorption effect upon swelling. Gels that were exposed to a 10‐day washing period to remove NaCl and excess PVA chains before drying showed an increased initial rate of swelling and overall water content. Freeze/thawed, cellular PVA gels showed overall enhanced swelling with increased mechanical strength over traditional gels prepared by chemical or irradiative crosslinking techniques. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2075–2079, 2000  相似文献   

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