PVP/PVA半互穿网络材料的制备及其性能研究

以N-乙烯基吡咯烷酮(NVP)为单体、N,N-亚甲基双丙烯酰胺(BIS)为交联剂、过硫酸铵(APS)为引发剂,在聚乙烯醇(PVA)水溶液中原位聚合制备了半互穿网络结构(semi-IPN)的复合聚合物,并用红外光谱、表面接触角、吸水率以及拉力测试对材料的结构和性能进行了表征。结果表明：所制备的材料具有温敏特性,当交联剂用量达到一定值时,semi-IPN膜的伸长率和弹性模量都存在一个最大值;增加PVA的用量,semi-IPN膜的表面接触角减小,伸长率和弹性模量则增加明显。     

尼龙-66与衣康酸的接枝共聚反应

以过硫酸钾／硫酸为引发剂,使尼龙-66纤维与衣康酸进行接枝共聚。研究了尼龙-66纤维接枝率与硫酸浓度、过硫酸钾浓度、衣康酸浓度、反应温度、时间和预处理时间之间的关系。实验结果表明,硫酸浓度为0．5mol／L,反应温度50℃,反应时间40h时,接枝率较高,预处理时间对接枝率也有较大影响。     

The miscibility of poly(vinyl alcohol)/poly(N-vinylpyrrolidone) blends investigated in dilute solutions and solids

Poly(vinyl alcohol) (PVA) (polymer A) and poly(N-vinylpyrrolidone) (PVP) (polymer B) are known to form a thermodynamically miscible pair. In the present study the conclusion on miscibility of PVA/PVP solid blends, confirmed qualitatively (DMTA, FTIR) and quantitatively (DSC, χ_AB = − 0.69 at 503 K) is compared with the miscibility investigations of PVA/PVP solution blends by the technique of dilute solution viscometry. The miscibility of the ternary (polymer A/ polymer B/ solvent) system is estimated on the basis of experimental and ideal values of the viscosity parameters k, b and [η]. It is found that the conclusions on miscibility or nonmiscibility drawn from viscosity measurements in dilute solution blends depend: (i) on the applied extrapolation method used for the determination of the viscosity interaction parameters, (ii) on the assumed definition of the ideal values and (iii) on the thermodynamic quality of the solvent, which in the case of PVA depends on its degree of hydrolysis. Hence, viscometric investigations of dilute PVA/PVP solution blends have revealed that viscometry, widely used in the literature for estimation of polymer-polymer miscibility can not be recommended as a sole method to presume the miscibility of a polymer pair.     

Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, ¹H NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times.     

冠醚配位作用的热力学性质——水液溶中1,4,7,10,13,16-六氧杂环十八烷与若干钾盐配位作用的负离子效应

本文用量热滴定法测定了1,4,7,10,13,16-六氧杂环十八烷(以下称18-冠-6)与KCl,KBr,KI, KClO_4,KNO_3,KBrO_3及K_2S_2O_3共八种钾盐在水溶液中, 25 ℃时的配位作用, 直接计算了配合物稳定常数及配位反应热。实验结果表明, 18-冠-6与KNO_3,K_2S_2O_3形成的配位化合物, 其稳定常数最高。讨论了阴离子对配位稳定性的影响。     

细菌纤维素(BC)增强PVA/PVP复合水凝胶的制备及性能表征

通过冷冻-熔融法制备了细菌纤维素/聚乙烯醇/聚乙烯吡咯烷酮(BC/PVA/PVP)双网络复合水凝胶,并采用X射线衍射,红外光谱,扫描电镜,力学性能测试等手段对凝胶的结构和性能进行表征.研究发现PVA、PVP通过氢键作用均匀地吸附于纤维微丝周围,将BC纤维有效地分开,因而干燥后的复合凝胶在热水中浸泡后仍可恢复原状;X射线...     

Preparation and Characterization of Poly Vinyl Alcohol/Poly Vinyl Pyrrolidone/Clay Based Nanocomposite by Gamma Irradiation

A series of PVA/PVP/clay nanocomposite were prepared by gamma irradiation with different clay contents of (0.15, 0.3, 1, 1.5, 3 and 5 wt%). The gelation content and swelling behavior were investigated. The morphology and structure of PVA/PVP/clay nanocomposite and dispersion of the clay nanoparticles in the polymeric matrix were examined by infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The introduction of clay into polymeric matrix was investigated by X-ray diffraction pattern (XRD) and Transmission electron microscope (TEM). It is observed that, the increase of the clay content causes a decrease in the swelling percent. The thermal stability studies confirmed that the introduction of clay lead to an increase in the thermal stability. The TEM results showed that the clay nanoparticles are interchelated or exfoliated in the polymeric matrix. Some desirable characteristics such as relatively good swelling and excellent barrier capability against microbe penetration suggested that PVA/PVP/clay nanocomposite can be a good candidate as a wound dressing.     

Preparation,Characterization and Controlled Release Investigation of Biocompatible pH-Sensitive PVA/PAA Hydrogels

In the present research hydrogel films based on polyvinyl alcohol (PVA) and polyacrylic acid (PAA) blend, with various crosslink densities, have been prepared through different thermal treatment. The results of FTIR and DSC confirmed quality and quantity of conclusion on miscibility of PVA/PAA blends, respectively. Besides, biocompatibility of the samples has been proved in cytotoxicity tests using L929 cells, according to ISO10993–5. Water uptake of the hydrogel blends is measured. pH sensitivity properties of blends are studied with and without boiling in NaOH solutions where the effect of swelling in water before boiling has also been investigated. Preswellings in water and NaOH concentration have been found to be mainly effective on pH sensitivity of PVA/PAA blends. Biocompatibility and pH sensitivity behavior make these hydrogels appropriate candidates to orally deliver drugs such as insulin and peptides that can be released in basic pH of intestine. The stability of these films in acidic solutions and its expansion and also the consequent release of drugs in basic solutions have been studied by using Teofilin as a model drug by UV-spectrophotometeric measurements.     

Miscibility and orientation behavior of poly(vinyl alcohol) / poly(vinyl pyrrolidone) blends

The miscibility of poly(viny1 alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) blends is investigated by differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD). The molecular orientation induced by uniaxial stretching of the blends is also examined by WAXD and birefringence measurements. It is shown by the DSC thermal analysis that the polymer pair is miscible, since a single glass transition temperature (T_g) is situated between the T_gs of the two homopolymers at every composition. The T_g versus composition curve does not follow a monotonic function but exhibits a cusp point at a PVP volume fraction of a little under 0.7, as in a case predicted by Kovacs' theory. The presence of a specific intermolecular interaction between the two polymers is suggested by an observed systematic depression in the melting point of the PVA component. A negative value of the polymer-polymer interaction parameter, χ₁₂ = 0.35 (at 513 K), is estimated from a thermodynamic approach via a control experiment using samples crystallized isothermally at various temperatures. The extent of optical birefringence (Δn) of the drawn blends decreases drastically with increasing PVP content up to 80 wt %, when compared at a given draw ratio, and ultimately Δn is found to change from positive to negative at a critical PVP concentration of a little over 80 wt %. Discussion of the molecular orientation behavior takes into consideration a birefringence compensation effect in the miscible amorphous phase due to positive and negative contributions of oriented PVA and PVP, respectively.     

ATRP-template dispersion polymerization of methacrylic Acid/PVP

ATRP-template dispersion polymerization of methacrylic acid （MAA） on the template of polyvinyl pyrrolidone （PVP K-30） was carried out in the aqueous solution by using methyl 2-bromopropionate （MBP）/CuC1/2,2＇-bipyridine （bpy） as the initiation system. The scanning electron microscopy （SEM）, dynamic light scattering （DLS） and gel permeation chromatography （GPC） were employed for evaluating the results of polymerization. As a result, the minimonomer droplets formed due to the H-bond interaction of PVP-MAA. The stability of droplets was dependent on pH and the concentrations of both PVP and MAA. When pH 〈 2, the coagulum of PVP-MAA formed, whereas when pH 〉 4.5, the droplets were not observable by DLS. In order to prepare the stable latex, the concentration of PVP should be lower than 9 wt%, whilst the concentration of MAA should be lower than 5.5 wt%. The optimum condition was pH 2.4, PVP 4.76 wt% and MAA 5 wt%, by which the stable latex of ca. 50 nm nanoparticles of PMAA/PVP was prepared by ATRP polymerization and simultaneously the molar mass of PVP was duplicated by PMAA according to GPC diagrams. In contrast, by using AIBN, KPS and KPS-Na2SO3 redox initiation system, the coagulum accompanying with the larger molar mass of PMAA was obtained, irrespective of pH and concentrations of PVP and MAA.     

PVA／PVP共混体系的非等温结晶动力学

用Mandelkern和Ziabicki理论方法求得PVA及PVA/PVP共混物结晶动力学参数Z_C和动力学结晶能力G_C值,并进行了讨论。得到的Avrami指数n不随冷却速度变化,但随非晶组分PVP的加入有所减小,加入量达百分之四十以后n由3降到2;G_C值则随非晶组分的加入而增大,当PVP加入量大于百分之三十时,G_C值不再发生明显变化。同时实验表明该高聚物及其共混体系不适合于Ozawa非等温结晶动力学方程。     

Preparation and characterization of aqueous stable electro-spun nanofibers using polyvinyl alcohol/polyvinyl pyrrolidone/zeolite

Cross-linked polyvinyl alcohol/polyvinyl pyrrolidone/zeolite fibers were prepared in the presence of potassium peroxodisulphate (K₂S₂O₈) under the curing process by the electrospinning technique. The narrowest nanofibers of PVA/PVP (50:50) were prepared under optimum experimental conditions of 2.5 × 10^?4 mol of K₂S₂O₈, an applied voltage of 22 KV, the distance of 15 cm and the feed rate of 0.2 mL/h. The progress of the cross-linking was examined by immersion of the prepared nanofibers in water and following the swelling degrees. By raising the K₂S₂O₈ amount and curing time, the cross-linking density was increased. X-ray diffraction (XRD) demonstrated that the crystallinity of the nanofibers was decreased by the increase of K₂S₂O₈ and the lowest crystallinity was observed for PVA/PVP (70:30). The contact angle of nanofibers was decreased from 72° to 34 by increasing PVP ratio from 30 to 70. The morphology of the nanofibers before and after immersion in the simulated body fluid (SBF) was studied using electron scanning microscopy (SEM) and PVA/PVP (70:30) showed the highest changes in the morphology while the lowest one was observed for PVA/PVP (50:50). Moreover, the cross-linked PVA/ PVP with the ratio of 50:50 had the narrowest diameter of 200 ± 100 nm, and by addition of about 0.5% zeolite, it was even reduced more to 150 ± 50 nm. The cross-linked nanofibers (50:50) with 0.5 wt% and 1.5 wt% zeolite nanoparticles showed the tensile modules of 416.26 and 703.52 MPa, respectively, while in the absence of zeolite, it was209.25 MPa. Fibroblast L929 cells were cultured on the cross-linked PVA/PVP/zeolite (50:50:0.5) nanofiber, and the cell proliferation and growth was evaluated by MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay. Fibroblasts grew on the surface of scaffold showed good morphology and proliferation after seven days and the absorption amount was increased from 0.075 to 0.78     

Spectroscopic and Discharge Studies on Graphene Oxide Doped PVA/PVP Blend Nanocomposite Polymer Films

Graphene oxide (GO) nanoparticles were synthesized by modified Hummers method. The synthesized GO nanoparticles were incorporated in polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend polymers for the preparation of nanocomposite polymer films by solution cast technique. Different characterizations such as XRD, UV–Vis and FTIR were carried-out on to the prepared nanocomposite polymer films. The thermal analysis of the films was studied by DSC. The morphology of PVA/PVP:GO polymer films confirms GO was exfoliated within the PVA/PVP matrix and also reveals the heterogeneous phase of nanocomposite polymer electrolyte systems. From the conductivity studies the highest conductivity of PVA/PVP: GO (0.45: 0.3) was found to be 8.05 × 10^–4 S/cm at room temperature. Solid state battery has been fabricated with the configuration of Mg⁺/(PVA/PVP:GO)/(I₂ + C + electrolyte) and its cell parameters were calculated for a constant load of 100 kΩ.     

PEO／PVP共混体系结晶行为

本文用WAXD、PLM、DSC方法研究了聚氧化乙烯(PEO)/聚乙烯基吡咯烷酮(PVP)共混体系的结晶行为,探索了两组分聚合物间相互作用及体系结晶度与非晶组分含量的关系。DSC研究表明PEO/PVP共混体系具有两个玻璃化转变温度,分别是纯组分的T_g,无相容性。应用Avrami和LH方程对其动力学参数进行了研究。偏光显微镜观察了共混物结构形态。     

PVP-b-PLA修饰Fe_3O_4磁性纳米粒子的制备与表征

通过硅烷偶联剂与Fe3O4磁性纳米粒子偶合在其表面引入C C端基,进一步与N-乙烯基吡咯烷酮(NVP)加成聚合制备含端羟基PVP包裹的磁体,再引发丙交酯(LA)开环聚合制得PVP-b-PLA修饰的Fe3O4纳米粒子.通过XRD、GPC、FTIR、SEM、TG、DSC和激光粒度仪等,对产物进行分析和表征,结果表明,纳米Fe3O4与PVP以及PVP与PLA之间均为化学键联,PVP和PLA是以嵌段共聚物的形式存在且两者之间存在明显的微相分离,纳米Fe3O4表面聚合物包覆率为35%,厚度约13 nm.此外,该PVP-b-PLA包覆的磁性纳米粒子比饱和磁化强度为53 emu/g,与未包覆相比下降约25%.     

离子色谱法测定尿液中的C2O42-、Ca2+、Mg2+

利用离子色谱法测定尿液中的草酸根、钙、镁离子：测定草酸根时，先在尿液中加入氯化钙使之转化成草酸钙沉淀，分离后用盐酸溶解草酸钙沉淀，然后进行测定测定钙、镁离子时，在酸性尿液中加入氧化剂过硫酸钾，在微沸状态下氧化尿液中的有机物，从而避免对色谱柱的污染：草酸根、钙、镁离子的回收率分别为108．3％～109．7％、94．9％～100．7％、97．2％～97.4％，相对标准偏差分别为2．4％、2.5％、3．1％。     

Enhanced thermal stability of poly(vinyl alcohol) in presence of melanin

A novel method was developed to enhance the thermal stability of PVA by using natural and synthetic melanins from oxidation of dopamine. Thermogravimetric (TG) curves indicated that the synthetic melanin changed the thermal degradation behaviors of PVA and largely improved the decomposed temperature by 80–110 °C in nitrogen when incorporation of synthetic melanin with low content (0.5–2 mass%). The thermal degradation kinetics suggested the activation energies of PVA/synthetic melanin blends were much higher than these of pure PVA. Isothermal TG curves conformed that the PVA/synthetic melanin blends exhibited more thermal stability than pure PVA. Moreover, the chemical structure changes of macromolecular after degradation were characterized by using fourier transform infrared and the results suggested that elimination reaction on the first degradation step did not took place for the PVA/synthetic melanin blends at 270 °C.     

Thermal,structural and morphological assessment of PVP/HA composites

Composites of poly(vinyl pyrrolidone)/hydroxyapatite (PVP/HA), at variable proportions (100/0; 80/20; 50/50; 20/80 wt%) were prepared and characterized by Fourier transformer-infrared spectroscopy (FT-IR), wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetry/differential thermogravimetry (TG/DTG). PVP carbonyl stretching was slightly shifted to lower frequency in composites indicating the formation of hydrogen bonding with HA hydroxyl groups. At the first cycle of heating, the calorimetric curves revealed a broad peak the intensity of which was reduced insofar as the amount of PVP decreased in the composites. This peak was attributed to the PVP enthalpy relaxation. According to the TG/DTG curves, PVP degraded into two steps sharply perceivable in the composites. The first decay was ascribed to the release of the pyrrolidone pendant groups and the following one concerned the burning of the hydrocarbon chains. The HA molecules seem to exert a catalytic action on the PVP degradation.     

Effects of Electron Beam Irradiation on the Structural Properties of PVA/PAM/CMC Ternary Polymer Blends

Ternary miscible blends based on various ratios of poly(vinyl alcohol) (PVA), poly(acrylamide) (PAM) and carboxymethyl cellulose (CMC) were prepared by solution casting in the form of thin films. The structure‐property behavior of the ternary PVA/PAM/CMC blends, before and after they had been exposed to various doses of electron beam irradiation, was investigated by FT‐IR spectroscopy, SEM, XRD and stress‐strain curves. The visual observation showed that the cast films of the individual polymers PVA, PAM, and CMC and their blends over a wide range of composition are clear and transparent indicating the miscibility of PVA/PAM/CMC ternary blends. The FT‐IR analysis of pure polymers or their ternary blends before or after electron beam irradiation proved the formation of hydrogen bonding. In addition, it was found that the intensity of the different absorption bands depends on the ratio of PAM and CMC in the ternary blend. The XRD patterns showed that the peak position for the ternary blends decreases with increasing the ratio of CMC in the blend. However, the peak position for the ternary blend based on equal ratios of pure polymers was not affected by blending and was found in the same position as in the XRD pattern of pure PVA. The SEM micrographs give support to the visual observation indicating the complete miscibility of PVA/PAM/CMC ternary blends. The improvement in morphology leads to improvement in the tensile mechanical properties of the ternary polymer blends.     

Effect of melt flow rate of polycarbonate and cobalt catalyst on properties of PET/PC (80/20 wt%) reactive blending

The influence of PC melt flow rate (MFR) on phase behavior, thermal and rheological properties of catalysed and non-catalysed poly(ethylene terephthalate)/polycarbonate (PET/PC) (80/20 wt%) reactive blending were investigated. Two types of PC named PC1 and PC2 with MFR 3.1 and 10.8 g/10 min, respectively, were used. Each PC and the catalyst showed significant influence on calorimetric properties, thermal stability and WAXS patterns of the blends. Regarding to TG/DTG, the blends degraded in two steps which were attributed to PET rich phase and PC one and permit to infer that a partially miscible blends were produced.