聚酰胺6／乙烯-乙烯醇无规共聚物共混体系的相容性及性能研究

研究了不同比例乙烯-乙烯醇无规共聚物(EVOH)和聚酰胺6(PA6)共混物的相容性及性能。扫描电子显微镜下观察结果表明二者具有较好的相容性;红外光谱分析和流变实验证实了EVOH与PA6分子间氢键的存在,氢键的作用会随着EVOH含量的增加而增强;阻透性能的测试表明在PA基体中加入EVOH会极大提高基体的阻透性,在EVOH基体中加入少量的PA6对EVOH的阻透性影响很小。     

Surface Modification of Poly(vinyl alcohol) Fibers

The surfaces of PVA fibers prepared by in situ fibrillation were modified by first crosslinking using glyoxal and then attaching cationic and anionic groups by grafting. Crosslinking prior to modification was beneficial in minimizing the solubility of the fibers in the aqueous medium in which they were modified. Heterogeneous modification techniques were employed so that fiber properties could be preserved. PAA and PDMC were grafted from the PVA microfibrils using the KPS/NaS₂O₃ redox initiating system. Grafting was confirmed by FTIR and NMR spectroscopy. The modified PVA fibers were also analyzed by DSC, TGA, and SEM.

     

聚乙烯醇／水滑石共混纤维的制备及其性能研究

采用凝胶纺丝法制备聚乙烯醇／水滑石（PVA／HT）共混纤维。通过扫描电镜（SEM）观察水滑石在PVA／HT共混纤维中的分散状况和共混纤维的表面形态。从傅里叶变换红外光谱（FT-IR）可以看出HT和PVA之间存在明显的氢键作用;热重分析（TG）测试表明水滑石的加入可以有效提高PVA的热性能;加入适量的HT可以提高PVA纤维的断裂强度;随着HT含量的增加,PVA／HT共混纤维的最大拉伸倍数下降且表面易产生缺陷。     

Preparation and properties of keratin–poly(vinyl alcohol) blend fiber

Keratin–poly(vinyl alcohol) (PVA) blend fibers containing 13–46 wt % of –SSONa⁺ (S‐sulfo) keratin were prepared by the wet‐spinning technique. They were formed by dehydration of an aqueous solution of S‐sulfo keratin and PVA (spinning dope) in a coagulation bath of sodium sulfate–saturated solution and subsequently drawn. Keratin–PVA fibers showed higher tenacity than that of wool, presumably originating from the high mechanical strength of the PVA component. The heat treatment at about 200°C improved the waterproof characteristics such as shrinkage of keratin–PVA fibers more conspicuously than did PVA fibers. That is, after heat treatment at 195°C for 10 min, keratin–PVA blend fiber shrank 20% in water at 60°C, whereas PVA fiber shrank 56%. Differential thermal analysis suggested the crosslinking of disulfide bonds between keratin molecules during the heat treatment, whereas the additional crystallization of PVA component was not observed. Adsorption of heavy metal and toxic gas to keratin–PVA fibers was also investigated. Keratin–PVA fiber was found to adsorb Ag⁺ and formaldehyde gas more efficiently than PVA. Thus, blends of keratin and PVA were advantageous for both polymer fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 756–762, 2004     

Hybrid Hydrogels Based on Poly(vinyl alcohol) (PVA)/Agar/Poly(ethylene glycol) (PEG) Prepared by High Energy Electron Beam Irradiation: Investigation of Physico‐Mechanical and Rheological Properties

A series of hybrid hydrogels based on poly(vinyl alcohol) (PVA)/agar/poly(ethylene glycol) (PEG) prepared by a solution casting method using e‐beam irradiation are investigated to determine the effect of agar and PEG content (1, 2, and 4 wt%) on their physicomechanical and rheological properties. The gel content of the hydrogels decreases with increasing agar and PEG contents. The equilibrium swelling of PVA hydrogel decreases on blending with agar while adding PEG to PVA/agar increases the swelling by about 400%. No obvious change in the dehydration behavior of the hybrid hydrogels is observed on changing agar and PEG contents. The solid‐like rheological behavior of the hydrogels is not significantly affected by agar content, while it approaches a liquid‐like behavior at high PEG loading. The tensile strength of the hybrid hydrogels is improved by increasing agar content, while its elongation‐at‐break is decreased. On the other hand, the opposite results are found regarding the influence of PEG and its content on the mechanical properties of the hybrid hydrogels.

     

Preparation and characterization of poly(vinyl alcohol)‐poly(vinyl pyrrolidone) blend: A biomaterial with latent medical applications

Aqueous solutions of poly(vinyl alcohol) and poly(vinyl pyrrolidone) are blended and films are produced by casting method with the further intention of being used as bio‐materials with latent medical application. Glutaraldehyde, 4,4′‐diazido‐2,2′‐stilbenedisulfonic acid disodium salt tetra‐hydrate are used as crosslinker agents, whereas lactic acid is the plasticizer in the blend. The obtained films are characterized by differential scanning calorimetry (DSC), mechanical properties, swelling and solubility behavior. DSC measurements show that the blends exhibit a single glass transition temperature indicating that they are miscible, even in the presence of the plasticizer and crosslinker agents. By the combination of all mentioned additives, a relevant enhancement of the swelling is observed, accompanied by a stabilization of the solubility during the tested time. Finally, mechanical properties show an appropriate performance in the studied parameters. As a consequence, the obtained films could be suitable for use as medium or long‐term implants. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dye–fiber interactions in PET fibers: Hydrogen bonding studied by IR‐spectroscopy

Dye–fiber interactions are studied in poly (ethylene terephthalate) fibers by FT‐IR spectroscopy. It is shown for the first time that DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) serves as an easy applicable and accurate technique for the study of fibrous structures. This article focuses on the possible hydrogen bond interactions in the dye–fiber system, where the PET fibers are dyed with anthraquinone‐based disperse dyes. The dyes and related anthraquinone structures are studied in both the dilute solution state, the solid state, and as present in the PET fibers. It is proven that 1‐amino anthraquinones show strong “chelate‐type” intramolecular hydrogen bonding in all three states. In the fibers an important supplementary intermolecular hydrogen bonding with the C?O groups in the PET fiber is observed. The extend of hydrogen bonding seems to be prone to dye concentration variations. Further analysis by modulated differential scanning calorimetry links the hydrogen bonding to an intrinsic plasticizing effect of the dyes affecting the dye diffusion process. This thus offers a tool for the fundamental understanding of the dyeing process and possible observed differences in dyeing behavior in dye–fiber systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of the blending time on the properties and non-isothermal crystallization behavior of PA6/EVOH blends

Both polyamide 6 (PA6) and ethylene vinyl alcohol copolymer (EVOH) have high fractional crystallinity. Non-isothermal crystallization kinetics is highly important for the design of processing operations. Furthermore, PA6 and EVOH undergo a chemical reaction to form copolymer when melt blended for a sufficiently long time. Therefore, the effects of the blending time on the mechanical properties, rheological properties, and non-isothermal crystallization kinetics of PA6/EVOH blends were investigated. Non-isothermal crystallization kinetics were analyzed through the Jeziorny and Mo′s equations, and the Mo′s equation more appropriately described the crystallization behavior of the blends. Mechanical properties, melt viscosity, and storage modulus gradually enhanced with an increase in the blending time, and the elongation at break first increased and then decreased with an increase in the blending time because when the blending time increased, the degree of the reaction between PA6 and EVOH increased, causing adhesion at interfaces and intermolecular interaction to enhance and causing a decrease in molecular chain fluidity. The former leads to an increase in the mechanical properties of the blend, and the latter renders the regular arrangement of chains for crystallization highly difficulty; hence, crystallization fractions in the blend gradually decrease.     

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     

Effect of the fiber content and plasticizer type on the rheological and mechanical properties of poly(vinyl chloride)/green coconut fiber composites

A series of poly(vinyl chloride) (PVC)/green coconut fiber (GCF) composites, with dioctyl phthalate (DOP) or thermoplastic polyurethane (TPU) as a plasticizer, were prepared by melt mixing. Their properties were studied in the molten state with an advanced nonlinear harmonic testing technique; in the solid state, the hardness and impact resistance were evaluated, and scanning electron microscopy was used for fractured surfaces. The effect of the fiber loading was investigated, as well as the role of the plasticizer. PVC–GCF composites are heterogeneous materials that, in the molten state, exhibit essentially a nonlinear viscoelastic character, in contrast to pure PVC, which has a linear viscoelastic region up to 50–60% strain. The complex modulus increases with the GCF content but in such a manner that the observed reinforcement is at best of hydrodynamic origin, without any specific chemical (i.e., permanent) interaction occurring between the polymer matrix and the fibers. As expected, PVC offers good wetting of GCFs, as reflected by the easy mixing and the rheological and mechanical properties. Fibers can be incorporated into PVC up to a 30% concentration without any problem, with the PVC/plasticizer ratio kept constant. Higher GCF levels could therefore be considered. Replacing DOP in part with TPU gives some benefit in terms of impact resistance, likely because of the viscoelastic nature of the latter and the associated energy absorption effects. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

PVA水凝胶中水的状态研究

用环氧氯丙烷作交联剂,制备了聚乙烯醇（PVA）亲水水凝胶。并用示差扫描量热法（DSC）对不同含水量的此种亲水水凝胶进行了测试,获得了各种状态水进入水凝胶聚合物网络体系的先后顺序情况,并研究了PVA水凝胶中三种状态水的含量随水凝胶含水量的变化而变化的规律。     

聚乙烯醇/稻草上段粉末复合材料的制备及性能研究

采用热压法制备了聚乙烯醇（PVA）/稻草上段粉末复合材料,研究了PVA用量、热压温度、热压时间对复合材料拉伸性能、弯曲性能和硬度的影响。采用扫描电子显微镜对复合材料的微观结构进行了表征。结果表明,复合材料的拉伸强度随PVA用量的增加呈现明显的上升趋势,适当提高热压温度和增加热压时间有利于提高复合材料的拉伸强度,但提高幅度不大。复合材料的硬度存在不均匀性,而且受原料配比和加工条件的影响较小。当PVA用量为40 %,热压温度为140 ℃,热压时间为14 min,复合材料的拉伸强度最佳为7.54 MPa。     

拉伸条件对高强PVA纤维结构和性能的影响

将聚乙烯醇(PVA)加入到二甲基亚砜(DMSO)和水(质量比94:6)的混合溶剂中,以甲醇为凝固剂,采用干湿法凝胶纺丝,经热拉伸和热定型后,制得高强度PVA纤维。探讨了拉伸工艺对高强PVA纤维结构和性能的影响。结果表明:对于负拉伸为40%,初拉伸2倍,220℃热拉伸9.9倍,热定型2 min的PVA纤维,纤维的结晶结构比较完善,断裂强度为17.8 cN/dtex,初始模量为310.7 cN/dtex;PVA纤维在光学显微镜下观察到的横纹反映出结晶聚集体的光学现象,横纹较多时,纤维的断裂强度和初始模量较高。     

Uniaxial tensile and structural properties of poly(vinyl alcohol) films: The influence of heating and film thickness

Poly(vinyl alcohol) as pure or composite materials is widely used in the food and textile industries, andbiomedical applications due to some important properties such as uniaxial tensile, biocompatibility, and noncarcinogenicity. Investigation of the influence of the film thickness and heating on the uniaxial tensile, spectroscopic, and surface properties of PVA films investigated in this study is quite important for improving the properties of such materials and their applicability in different conditions. In this study, with the influence of heating, a necking behavior was observed at around 2% for thin films and 4–9% strain for thicker PVA films for which a kind of transition point at around 1–2% strain was observed. The mechanical strength of PVA films, strain at break, and Young's modulus were enhanced greatly as the temperature increased from 80 to around 110 °C, and then most of them decreased. The degree of crystallinity increased linearly with the heat temperature from around 36–40%. Although PVA thin films obtained a very smooth surface structure after being heated at 80 °C, with increasing heat temperature, the surface roughness of both thin and thick PVA films increased and the PVA thin films obtained more degraded film surface. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44915.     

Acid-treated Bentonite as filler in the development of novel composite PVA hydrogels

In this study, novel eco-friendly hydrogel adsorbents were synthesized based on poly(vinyl alcohol) (PVA) and different contents of an acid-treated bentonite (1–5 wt %). The hydrogels were prepared by freezing–thawing, which is a simple and nontoxic method. The materials were morphologically and thermally characterized by means of swelling assays, X-ray diffraction, scanning electron microscopy, dynamic scanning calorimetry, and thermogravimetric analysis in order to evaluate the effect of acid-treated bentonite loading. The composite hydrogels showed very distinct porous structure and thermal features in comparison to neat PVA as a consequence of the addition of the clay. Moreover, the performance of the obtained composite hydrogels was tested toward the adsorption of cationic (methylene blue) and anionic dyes (methyl red and methyl orange) from aqueous media. The presence of acid bentonite seems to be beneficial for improving the removal capacity of PVA-based hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47663.     

Molecular Orientation and Mechanical Properties of Poly(Vinyl Alcohol) Fibers

Abstract

A number of poly(vinyl alcohol) fibers with different draw ratios was characterized by measuring the birefringence, crystalline orientational order, crystallinity, tensile strength, and modulus. The birefringence, tensile strength and modulus increased with increasing draw ratio whereas the crystallinity and crystalline order parameters remained constant within narrow limits. The increase in birefringence has to be attributed solely to an increase in chain orientation in the amorphous phase of the semicrystalline fiber. The tensile strength and modulus are therefore directly related to the chain orientation in the amorphous phase. With the aid of a simple two-phase model it was found that the modulus of the amorphous phase in its disordered conformation was 4.8 GPa. The intrinsic birefringence of the amorphous phase was found to be 79 × 10^?3, i.e. much higher than the value obtained for the crystalline phase (52 × 10^?3). When this value was used in calculations, it was found that the order parameter of the amorphous phase increased from around 0.1 for a draw ratio of 1 to approximately 0.6 for a draw ratio of 5, whereas the order parameter of the crystalline phase was close to 1 for all draw ratios.     

后处理对PVA吹塑薄膜性能的影响

以增湿法制备了PVA吹塑薄膜，研究了含水率对薄膜力学性能及光学性能的影响。结果表明，随着PVA吹塑薄膜含水率的增加，其拉伸强度下降，但断裂伸长率增加。适当的含水率可以减小薄膜的雾度。通过热处理工艺可以提高薄膜的结晶度和力学性能，80℃以上长时间热处理可以延长薄膜的水溶时间。     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001