肝素化聚乙烯醇性能研究

用聚乙烯醇(PVA)缩醛化方法,共价键结合肝素。用Schiff试剂染色法、红外光谱分析、X射线光电子能谱法(ESCA)、元素分析等测试方法证明醛基和肝素的存在。力学性能测定表明,肝素化聚乙烯醇的拉伸强度达到12 25MPa,断裂伸长率为400%。生物学指标说明,在全血凝固时间实验(CT)中,肝素化聚乙烯醇的抗凝时间达3h,在活性部分凝血时间实验(APTT)中,缩醛化聚乙烯醇共价键结合肝素非常牢固,没有肝素脱落到血液中,证明肝素化聚乙烯醇具有显著的抗凝血性。     

Poly(vinyl alcohol) nanocomposites with sepiolite and heat‐treated sepiolites

Poly(vinyl alcohol) (PVA) nanocomposites with pristine sepiolite and heat‐treated (HT) sepiolites were prepared by the method of solution dispersion. The measurements of XRD, FTIR, TEM, and AFM were used for the characterization of the nanocomposites. Furthermore, thermal and optical properties were investigated by TG/DTG/DTA and UV‐visible transmission spectra, respectively. Both the effects of sepiolite/polymer ratio and the structural changes in sepiolite on heating were examined in terms of changes in the properties of the nanocomposites. The addition of sepiolite/HT sepiolites into the PVA matrix resulted in a decrease in the thermal decomposition temperatures of the nanocomposites because of the fact that sepiolite and HT sepiolites facilitated the elimination of the water and acetate groups from the PVA in the second step based on the TG/DTG studies. The HT sepiolites‐PVA nanocomposites had lower thermal stability and more influenced optical clarity than those of the sepiolite PVA, at the same filler levels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚乙烯醇薄膜的共混改性

从聚合物结构方面分析了聚乙烯醇（PVA）薄膜的水溶性,提出用共混改性方法提高PVA薄膜的溶解性能。研究了聚丙烯酸不同中和度,不同共混组分组成对薄膜水溶性和力学性能的影响,并利用差示扫描量热法（DSC）、傅立叶红外光谱（FTIR）、广角X射线衍射（WXRD）等手段对共混改性机理进行了分析。     

卤化聚乙烯醇的研究

通过将聚乙烯醇（PVA）直接卤化取代,筛选出Cl,Br等卤化剂,催化剂,并优选出合适的体系,使其既保持PVA的高阻氧性,又能保证加工性时的热稳定性。     

Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Poly(vinyl alcohol) modified with carboxylic acid anhydrides: crosslinking through carboxylic groups

The reaction of carboxylic acid anhydride with poly(vinyl alcohol) (PVA) leads to vinyl alcohol—vinyl ester copolymers which contain carboxylic acid groups. Esterification enables degrees of modification to be reached which depend on the chemical structure of the anhydride introduced and the ratio of the reagents in the feed. The copolymers obtained were characterized by spectroscopic techniques, elemental analysis, and thermal methods. These half-esters reacted in a second step with aromatic diglycidyl ethers to obtain tridimensional networks. This crosslinking reaction through the carboxylic groups was studied by differential scanning calorimetry. The water absorption of the linear and crosslinked polymers was determined gravimetrically as a function of time at room temperature. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1643–1651, 1997     

乙酰乙酰化聚乙烯醇的合成

通过酯交换反应将乙酰乙酰基引入聚乙烯醇(PVA),并采用红外光谱对产物进行了表征。重点讨论了反应温度、反应时间、乙酰乙酸酯用量等因素对酯交换反应的影响。试验发现:随乙酰乙酸酯用量的增加,乙酰乙酰化程度逐渐增大;随反应温度的升高,乙酰乙酰化程度先逐渐提高,后趋于稳定;随反应时间的延长,乙酰乙酰化程度提高,2.5h后趋于平衡。     

Poly(acrylic acid)–poly(vinyl alcohol) copolymers with superabsorbent properties

Biodegradable polyacrylates were produced by a series of novel copolymerization and/or crosslinking techniques using poly(vinyl alcohol) (PVA) moieties modified by the incorporation of olefinic structures. PVA was modified by a tosylation and/or detosylation reaction. The functionalized PVA was copolymerized and/or crosslinked with acrylic acid or its partially neutralized form to give crosslinked polyacrylates that could swell in water. Their swelling behavior was determined under load. Degradation studies were performed in α-chymotrypsin, trypsin, and papain solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 817–829, 1998     

聚乙烯醇改性固体淀粉胶粘剂的研制

介绍新型固体淀粉胶的制备方法。以淀粉为主要原料,经加热催化分步氧化,再加入聚乙烯醇合成树脂改善其性能,然后用硬脂酸钠作为赋型剂。制得的淀粉胶剪切强度比泡花碱高0.01MPa。     

The influence of vanadium pentoxide on the structure and dielectric properties of poly(vinyl alcohol)

Polymers containing metal oxides of nanoscale dimensions have attracted attention because of their unique properties and new findings concerning technological applications. Polymers containing vanadium pentoxide (V₂O₅) have attracted our interest in respect of their potential applications in memory and switching devices. Poly(vinyl alcohol) (PVA) containing different concentrations of V₂O₅ ranging from 0 to 0.5 wt% were prepared. The synthesized PVA/V₂O₅ composites were cast as self‐standing flexible films. The composites were characterized using X‐ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. An attempt was made to study the relaxation characteristics of PVA/V₂O₅ samples. The permittivity and dielectric loss were determined as a function of V₂O₅ concentration. The results show that the optimum concentration is 0.3 wt%. The electrical conductivity and dielectric modulus in the temperature range 303–433 K at various frequencies (10–100 kHz) for the optimum concentration were investigated. XRD and FTIR results show that the addition of V₂O₅ reduces the crystallinity of PVA due to the interaction of vanadium ions with the OH groups of PVA. The application of the dielectric modulus formulism gives a simple method for evaluating the activation energy of the dielectric relaxation. The frequency dependence of the electrical conductivity follows the Jonscher universal dynamic law. The conductivity in the direct regime is described by the small polaron model. The electrical conductivity and dielectric properties show that Hunt's model is well adapted to PVA/V₂O₅ films. Copyright © 2010 Society of Chemical Industry     

聚乙烯醇醇解度测定的定量核磁共振技术研究

建立了新的测定聚乙烯醇醇解度的定量核磁共振技术(QNMR)。结果表明:在实验温度303 K、脉冲等待时间2 s时,定量核磁共振方法得到的结果与滴定法十分吻合,而且精密度、重复性、稳定性均能达到要求。该方法具有快速准确、操作简便,不需对样品进行分离,可直接分析等特点。     

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.

     

Influence of Syndiotacticity on Poly(vinyl alcohol)–Iodine Complex Formation

The extent of colour development in an aqueous poly(vinyl alcohol) (PVA)–iodine complex solution increased with increasing syndiotacticity up to a certain syndiotactic content, then decreased with increasing syndiotacticity. The complex formation depended on the content of the syndiotactic pentad sequence length in the PVA molecules. The most suitable content of the syndiotactic pentad for forming complexes was around 12% in the case of reaction at 30°C. A 0·5% solution of syndiotactic PVA (S-PVA) with an syndiotactic diad (s-(diad)) content of 63·8% changed into a sol, whereas that with an s-(diad) content of 58% did not change after standing for 2h at 30°C, and the colour due to the iodine complex in the latter was deeper than in the former. The gel prepared from the 0·5% solution of S-PVA with an s-(diad) content of 63·8% was hardly coloured. In the solutions containing two kinds of s-PVA having different syndiotacticities, additivity for the extent of colour development did not hold, and the extent was lower than the sum of that of the components. The decrease in the extent of colour development at higher syndiotacticity was due to the formation of microgels. The absorption maximum shifted to a longer wavelength with increasing syndiotacticity. The length of polyiodine increased with increasing syndiotacticity. © of SCI.     

Properties of branched and network poly(vinyl alcohols) prepared with poly(vinyl alcohol) having aldehyde groups at the chain ends

Branched and network poly(vinyl alcohols) (PVAs) were prepared with inter-acetalization of the PVA with aldehyde groups at the chain ends which was prepared by the cleavage of 1,2 glycol bonds in commercial PVA. The numbers of branches estimated from molecular weights were compared with those estimated by theory. Huggins' constant and crystallinity decreased with increasing branch number. Dissolution of branched PVAs into dimethylsulphoxide was not so easy compared with commercial PVA. The colour of branched PVA–iodine complex decreased rapidly with standing while that of commercial PVA decreased gradually. Network PVAs with Young's modulus of 1–8 MPa were prepared.     

Improvement of Permeability of Poly(vinyl alcohol) Hydrogel by Using Poly(ethylene glycol) as Porogen

The porous structure of PVA hydrogel achieved with varying content and varying molecular weight of PEG was investigated. It was found that with increasing content or molecular weight of PEG, the diffusion coefficient D _e and UV transmission of ink solution increased, indicating that the permeability and mass transfer capability of the gel beads were enhanced. The swelling rate constant k and equilibrium swelling rate of the gel were significantly improved by addition of PEG, and many pores formed inside the gel to provide channels for microbial metabolites. With increasing molecular weight of PEG, the size of pores became increasingly large.     

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     

水溶性聚乙烯醇的熔融纺丝

用共混的方法,在聚乙烯醇中加入复配增塑剂,通过共混仪探究其可纺性,通过差示扫描量热仪、热失重分析仪、强力仪等对纤维的熔点、分解温度以及强度进行测试,通过测定纤维在热水中的溶解时间探究其水溶性的好坏。结果表明:在满足材料强度要求的前提下,当复配增塑剂的质量分数达到43.6%时,改性聚乙烯醇具有很好的可纺性,且具有很好的水溶性。     

Glycerol-modified poly(vinyl alcohol)/poly(ethylene glycol) self-healing hydrogel for artificial cartilage

Poly(vinyl alcohol) (PVA) hydrogels have shown potential applications in bionic articular cartilage due to their tissue-like viscoelasticity, good biocompatibility and low friction. However, their lack of adequate mechanical properties is a key obstacle for PVA hydrogels to replace natural cartilage. In this study, poly(ethylene glycol) (PEG) and glycerol were introduced into PVA, and a PVA/PEG–glycerol composite hydrogel was synthesized using a mixing physical crosslinking method. The mechanical properties, hydrophilicity and tribological behavior of the PVA/PEG–glycerol hydrogel were investigated by changing the concentration of glycerol in PEG. The results showed that the tensile strength of the hydrogel reached 26.6 MPa at 270% elongation at break with 20 wt% of glycerol plasticizer, which satisfied the demand of natural cartilage. In addition, the excellent hydrophilicity of glycerol provides good lubricating properties for the composite gel under dry friction. Meanwhile, self-healing and cellular immunity assays demonstrated that the composite gel could have good self-healing ability and excellent biocompatibility even in the absence of external stimuli. This study provides a new candidate material for the design of articular cartilage, which has the potential to facilitate advances in artificial joint cartilage repair. © 2022 Society of Industrial Chemistry.     

聚乙烯醇改性及降解研究进展

从材料学的改性技术和环境学的相容性两个角度综述了国内外聚乙烯醇生物降解的研究概况。通过聚乙烯醇溶液及薄膜的降解过程的介绍,指出化学改性和微生物降解的结合将是今后处理含聚乙烯醇类废水和固体废弃物的主要方法。