Preparation and photochromic properties of pyrazolones/polyvinyl alcohol composite films

Novel photochromic composite films have been successfully fabricated by dispersing pyrazolone derivative:1,3-Diphenyl-4-(3-chlorobenzal)-5-hydroxypyrazole 4-phenylsemicarbazone (1a) into hydrosol of polyvinyl alcohol (PVA). The microstructure, photochromic behaviors and thermal bleaching properties were investigated by Raman spectroscopy, X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and ultraviolet-visible absorption spectroscopy (UV-vis). The results showed that 1a was not only blended but also well dispersed in the PVA polymer films with a suitable content of chromophore. Upon UV light irradiation, the composite films gradually changed from colorless to yellow and recovered fully to the initial state upon thermal bleaching. The time constants of photochromic reactions were almost the same as those of 1a observed in their crystalline state, indicating that the photochromic phenomenon is barely disturbed by the polymer matrix.     

多酸含量对无机/高分子复合薄膜结构及光致变色性能的影响

制备了一系列不同浓度的钨磷酸/聚乙烯醇(PWA/PVA)复合薄膜, 通过红外光谱、原子力显微镜、紫外-可见吸收光谱对复合薄膜的结构和光致变色性能进行了研究. 红外光谱分析结果表明, Keggin结构钨磷酸和聚乙烯醇分子的基本结构在复合薄膜中仍然存在, 钨磷酸分子与高分子底物间存在氢键作用, 形成电荷转移桥. 原子力显微镜(AFM)结果表明复合前后PVA薄膜表面形貌发生了显著变化, 复合膜表面形貌随钨磷酸含量的不同而不同. 在紫外光照射下, 复合薄膜由无色变为蓝色. 复合膜的升色速度和褪色速度均随着钨磷酸含量的增加而加快. 这些结果表明钨磷酸含量对复合膜的微结构存在影响, 从而导致了复合膜具有不同的光致变色性能.     

Conformational,optical, electro-optical,and dynamic characteristics of cross-linked poly(N-acryloyl-11-aminoundecanoic acid)

Polymerizable surfactants now attract a great interest due to high potential of their practical application as components of pseudostationary phase in micellar chromatography, drug carriers, and “building blocks” for molecular design of nanoparticles and nanostructured polymer materials, for encapsulation of various biological preparations. In the present work, we have studied poly(N-acryloyl-11-aminoundecanoic acid) (cross-linked comb-like polymer). Cross-linked polymers were obtained via copolymerization of the surfactant bearing double bond in hydrophobic tail with hydrophobic bifunctional cross-linker in micellar solution. Of special interest was the comparison between cross-linked and non-cross-linked polymers and influence of alkaline medium on characteristics of these samples. Non-cross-linked polymers were obtained by hydrolysis of the cross-linked product (treating with NaOH). The mixture of cyclohexanol and dioxane (1:1 volume ratio) was used as a solvent. Detailed studies of the obtained polymers by viscometry, dynamic light scattering, flow birefringence, and equilibrium and non-equilibrium electric birefringence were performed. It was established that during cross-linking process, two types of bonds are formed (the ones inside individual molecules and between several polymer chains). It was shown that cross-linked macromolecular nanoparticles can be transformed into comb-like polymers.     

Properties of composite solid polymer electrolyte using hyperbranched polymer with ether-linkage

The cross-linked composite solid polymer electrolytes composed of poly(ethylene oxide), lithium salt (LiN(SO₂CF₃)₂), and a hyperbranched polymer whose repeating units were connected by ether-linkage (hyperbranched polymer (HBP)-2) were prepared, and their ionic conductivity, thermal properties, electrochemical stability, mechanical property, and chemical stability were investigated in comparison with the non-cross-linked or cross-linked composite solid polymer electrolytes using hyperbranched polymers whose repeating units were connected by ester-linkage (HBP-1a, 1b). The cross-linked composite solid polymer electrolyte using HBP-2 exhibited higher ionic conductivity than the non-cross-linked and cross-linked composite solid polymer electrolytes using HBP-1a and HBP-1b, respectively. The structure of the hyperbranched polymer did not have a significant effect on the thermal properties and electrochemical stability of the composite solid polymer electrolytes. The tensile strength of the cross-linked composite solid polymer electrolyte using HBP-2 was lower than that of the cross-linked composite solid polymer electrolyte using HBP-1b, but higher than that of the non-cross-linked composite solid polymer electrolyte using HBP-1a. The HBP-2 with ether-linkage showed higher chemical stability against alkaline hydrolysis compared with HBP-1a with ester-linkage.     

Electron irradiation induced microstructural modifications in BaCl2 doped PVA: A positron annihilation study

Thin films of pure and 10 wt% BaCl₂ doped poly(vinyl alcohol) (PVA) were prepared by solution casting method. These films were subjected to electron irradiation for different doses ranging from 0 to 400 kGy in air at room temperature. The effect of electron irradiation on the optical and free volume related microstructures of these polymer films was studied using positron annihilation lifetime spectroscopy, FTIR and UV-vis techniques. The FTIR spectral studies indicate that the electron irradiation induces chemical modifications within the doped PVA, which results in chain scission as well as cross-linking of the polymer. The positron lifetime study on these irradiated polymers shows that the chain scissions and cross-linking within the polymer matrix affect the free volume content and hence the microstructure. The UV-vis optical absorption studies show that the induced microstructural change by electron irradiation also modifies the optical properties. Using UV-vis spectra, the optical energy band gap was estimated and it decreases with increase in electron dose. A correlation between positron results and optical results is obtained and electron irradiation induced microstructure modifications within the doped polymer are understood. The results highlight the usefulness of positron annihilation technique in the study of the microstructure of irradiated polymers.     

Effect of interfacial adhesion on the mechanical properties of poly(vinyl chloride) modified with cross-linked poly(methyl methacrylate) particles prepared by seeded emulsion polymerization

The effect of interfacial adhesion on the mechanical properties of an incompatible polymer blend was investigated. For this purpose, the preparation of non-cross-linked and cross-linked poly(methyl methacrylate) particles having mean sizes of about 0.8 μm was completed by seeded emulsion polymerization, and the number and the distribution of cross-linked points in the particles were varied. The emulsion particles obtained were powdered by a freeze–dry method and dispersed into a poly(vinyl chloride) matrix by melt blending. The non-cross-linked particles were completely dissolved in the matrix because poly(methyl methacrylate) has good compatibility with poly(vinyl chloride). On the other hand, in the case of the cross-linked particles, the mutual diffusion of the polymer molecules was restricted within the particle/matrix interfacial regions owing to the cross-linked points. Additionally, interfacial structures with different concentration slope dependent upon the number and the distribution of inner cross-linked points were developed with the same domain size. Mechanical and fracture properties were measured. As a result, both yield stress and fracture toughness decreased with a decrease in the interfacial adhesion, and the decrease was found to occur as a result of interfacial debonding. When the interfacial adhesion was sufficient it was never observed that the level was lower than that of the components. Received: 6 April 2000 Accepted: 29 September 2000     

Modification of Polymer Membranes for Use in Organic Solvents

The chemical stability of polymer membranes, i.e., their ability to preserve the size, shape, and pore structure in contact with aggressive organic solvents, largely determines their separation characteristics in filtration of organic media. Methods for enhancing the stability of porous membranes based on commercial polymers (polysulfone, polyphenylsulfone, polyacrylonitrile) by chemical and/or physical modification are considered. Chemical modification consists in covalent cross-linking of matrix polymer chains; in some cases, cross-linking of macromolecules requires their preliminary functionalization. Physical modification involves blending of a matrix polymer with another polymer. A promising way to stabilize various membranes is combining a matrix polymer with a chemically cross-linked additional polymer, i.e., forming a semi-interpenetrating network.

     

Polyaniline/poly(vinyl alcohol) (PAN/PVA) composite films: the synergy of film structural stiffening, redox amplification, and mobile species compositional dynamics

In this work, we report an unexpected but significant improvement of the redox behavior of conducting polyaniline (PAN) films by trapping intrinsically nonconducting poly(vinyl alcohol) (PVA) in the matrix of the polymer acting as stiffening and/or cross-linking agents. Film structural stiffening of PAN/PVA inclusion was studied in relation to film compositional dynamics. PAN and PAN/PVA composite films were potentiodynamically deposited using high-frequency electrochemical quartz crystal microbalance under electrochemical potentiodynamic control. From the simultaneously obtained measurements of nanogravimetric and cyclic voltammetric data, it has been found that the presence of PVA in the deposition solution increased the rate of PAN film growth as a function of PVA concentration. Characterization of the resultant composite films in monomer-free acidic electrolyte solutions showed significantly enhanced redox behavior of PAN/PVA composite films (with different PVA contents) compared to pure PAN by a factor of ～2–4. For the study of structure–composition relationships of composite polymer films, fluxes of instantaneous mobile species dynamics (ion/solvent) as a function of film redox conversion and potential cycling were correlated with film structural stiffening and the observed unusual redox enhancement of PAN/PVA composite films. Using various experimental timescales, we were able to resolve bound (associated with ion transfer) and free solvent compositional dynamics (associated with thermodynamic activity balance).     

Effect of rubbing-induced polymer chain alignment on adhesion and friction of glassy polystyrene surfaces

The friction and adhesion properties of polystyrene surfaces are studied below the glass transition temperature by means of atomic force microscopy in argon. Even at a temperature far below the glass transition, the repeated sliding of a polystyrene bead tip on the non-cross-linked polystyrene surface causes significant reduction of friction and adhesion forces. There is no measurable wear of the polystyrene surface due to repeated sliding. These decreases are associated with the alignment of the outermost polymer segments induced by repeated rubbing. There are only little changes in friction and adhesion on the cross-linked polystyrene surface in which the covalent cross-linking prevents chain realignment.     

Sago/PVA blend membranes for the recovery of ethyl acetate from water

Sago starch is a relatively new polymeric material for development of a hydrophilic membrane for dehydration of alcohol/water. In this study sago based membranes were developed through casting technique for the dehydration of ethyl acetate at azeotropic conditions via pervaporation. Sago was blended with polyvinyl alcohol (PVA) to produce blended sago–PVA membranes with improved physical and chemical properties. The membranes were cross-linked using three different approaches; firstly, using glutaraldehyde, secondly using thermal treatment (80 °C) and thirdly by using both glutaraldehyde and thermal treatment. The effects of various cross-linking methods on the intrinsic properties of hydrophilic polymer membrane were investigated. The membranes were characterized using Fourier transform infrared (FTIR), differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The effect of operating conditions such as feed temperature and concentration on the separation factor and flux was discussed. Sago starch polymer shows very high performance and very good stability after polymer blending and cross-linking, which is promising for use in industrial applications.     

Water and polymer dynamics in chemically cross-linked hydrogels of poly(vinyl alcohol): a molecular dynamics simulation study

A topologically extended model of a chemically cross-linked hydrogel of poly(vinyl alcohol) (PVA) at high hydration degree has been developed for a molecular dynamics simulation with atomic detail at 323 K. The analysis of the 5 ns trajectory discloses structural and dynamic aspects of polymer solvation and elucidates the water hydrogen bonding and diffusion in the network. The features of local polymer dynamics indicate that PVA mobility is not affected by structural constraints of chemical junctions at the investigated cross-linking density, with a prevailing dumping effect due to water interaction. Simulation results are validated by a favorable comparison with findings of an incoherent quasi-elastic neutron scattering study of the same hydrogel system.     

Crosslinking of poly(vinyl alcohol) using functionalized gold nanoparticles

We report on the preparation of a new class of polymer hydrogels obtained through the chemical crosslinking reaction of poly(vinyl alcohol) (PVA) and functionalized gold nanoparticles. Carboxylic group functionalized gold nanoparticles were synthesized, dispersed in a PVA matrix and allow to react with the hydroxyl groups of PVA at high temperature. FT-IR and swelling experiments carried out on the cross-linked samples confirmed that the crosslinking reaction took place. This is the first time, to our knowledge, that functionalized nanoparticles are used as chemical crosslinking agents.     

Polymer-additive extraction via pressurized fluids and organic solvents of variously cross-linked poly(methylmethacrylates)

Variously cross-linked poly(methylmethacrylates) (PMMAs) are synthesized with three additives incorporated at theoretically 1000 microg of the additive per gram of prepared polymer. The additives are Irganox 1010, Irganox 1076, and Irgafos 168. The in-house" synthesized polyacrylates are then subjected to supercritical fluid extraction (SFE) to determine if additive recovery is a function of percent cross-linking. Although considerable work in this regard has been performed with non-cross-linked polyolefins, the literature is lacking regarding polyacrylates. Some additive degradation apparently occurs during the synthesis, as judged by the increased complexity of the extract high-performance liquid chromatographic trace and the low percent recoveries observed especially for the Irganoxes. For low polymer cross-linking (1%), it appears that both PMMA synthetic reproducibility and readily observed polymer swelling during SFE are serious issues that adversely affect additive percent recovery and precision of results. Higher percent cross-linking yields more consistent analytical data than low percent cross-linking, even though the amount of additive extracted in all PMMA samples (regardless of cross-linking percentage) is essentially the same whether the extraction is via SFE or liquid-solid extraction with methylene chloride. Results for comparably cross-linked poly(ethylmethacrylate) and poly(butylmethacrylate) are similar to PMMA.     

Electro-electrodialysis of hydriodic acid using the cation exchange membrane cross-linked by accelerated electron radiation

Electro-electrodialysis (EED) of hydriodic acid with HI molality of ca. 9.5 mol/kg was examined in the presence of iodine using a commercial cation exchange membrane (CMB) as a separator. For the increase of the selectivity of proton permeation, the membrane was cross-linked by accelerated electron radiation. The membrane properties (area resistance, ion exchange capacity (IEC), water content) of the cross-linked membranes were measured. The area resistance in 2 mol/dm³ KCl solution of the cross-linked membranes decreased as compared with that of the non-cross-linked membrane (original of CMB membrane). The IEC and water content of cross-linked membranes at each dose rate had almost the same value as that of non-cross-linked membrane. Electro-electrodialysis of hydriodic acid with HI molality of ca. 9.5 mol/kg was examined at 75 °C with 9.6 A/dm². The cross-linked cation exchange membrane by accelerated electron radiation had higher selectivity of the proton permeation by cross-linking structure of polymer than that of the non-cross-linked membrane.     

Photoinduced shape fixity and thermal-induced shape recovery properties based on polyvinyl alcohol bearing coumarin

In this paper, polyvinyl alcohol (PVA) bearing coumarin with different degrees of substitution (DS) are synthesized by esterifying hydroxyl of PVA with 7-carboxylmethoxycoumarin. The grafted polymer has photosensitive property and presents photocrosslinking due to the photodimerization between pendant coumarin groups, which affords PVA–coumarin sample photoinduced shape fixity properties. PVA–coumarin can be cross-linked after being illuminated under UV light of 360 nm; this provides the possibility that the sample has shape memory properties only if the cross-linking extent is suitable. The shape memory properties were induced by thermal as most shape memory polymer do. In fact, the shape fixity and recovery has strong relationship with DS, irradiation time, and thickness of sample. The effect of DS on the grafted polymer structure and properties has been studied by differential scanning calorimetry, thermogravimetric analysis, and UV spectra.     

Investigation of the porosity of silica and alumina with chemically bonded polystyrene

The effect of modification of porous silica and alumina with a copolymer of styrene and vinylsilane on the porosity of oxides have been investigated by means of low temperature nitrogen sorption. Only small changes of the specific surface area and of the specific pore volume were observed on modification of oxides with non-cross-linked copolymer. The specific surface area significantly increased after the cross-linking of the deposited polymeric layer while the specific pore volume remains almost unaffected. A broad hysteresis loop appears in the nitrogen sorption isotherm for the alumina modified with the cross-linked polymer. The porosity of oxides modified by chemisorption method differed strongly from that observed for composites modified by physisorption of polymer.     

Ultrathin polymer film formation by collision-induced cross-linking of adsorbed organic molecules with hyperthermal protons

A new synthetic approach for the formation of ultrathin polymer films with customizable properties was developed. In this approach, the kinematic nature of proton collisions with simple organic molecules condensed on a substrate is exploited to break C-H bonds preferentially. The subsequent recombination of carbon radicals gives a cross-linked polymer thin film, and the selectivity of C-H cleavage preserves the chemical functionalities of the precursor molecules. The nature and validity of the method are exemplified with theoretical results from ab initio molecular dynamics calculations and experimental evidence from a variety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymer films with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, and polyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involves an unusual mix of physical and chemical processes including charge exchange, projectile penetration, kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.     

One-pot synthesis of highly folded microparticles by suspension polymerization

A facile method of preparing highly folded cross-linked polymeric microparticles has been developed via one-pot suspension polymerization under high-speed homogenization. The wrinkles result from the evaporation of solvent in the cross-linked microparticles. The effects of microparticle cross-linking density and solvent on the polymer have been studied in detail. It was found that a medium cross-linking density (DVB/St = 0.5 by weight) is optimal for producing the most folded surface and the higher the solvent content, the deeper the surface wrinkles. This method is very simple and in principle can be applied to produce wrinkled microparticles with other chemical compositions.     

聚乙烯醇多孔膜的制备及其对二氧化钛的负载研究

以聚乙烯醇(PVA)为聚合物基体,戊二醛为交联剂,乙酸为催化剂,聚乙二醇6000(PEG-6000)为致孔剂,制备了聚乙烯醇多孔膜(porous PVA films,PPF多孔膜);再将实验室自制的二氧化钛溶胶(TiO_2)负载于PPF多孔膜上,制备得到聚乙烯醇原位负载二氧化钛功能薄膜(PPF-TiO_2)。采用红外光谱、扫描电镜、分光光度计等分别考察了PPF多孔膜的交联条件、负载前后PPF-TiO_2功能薄膜的形貌,PPF-TiO_2功能薄膜对甲基橙的去除率。研究结果表明,为制备适宜交联度及孔径的PPF多孔膜,戊二醛浓度为5%(wt),PEG-6000用量为PVA用量的0.6倍为宜;PPF多孔膜对TiO_2负载的温度为40℃,负载时间为2h能够获得负载量为43%的PPF-TiO_2功能薄膜。此外,PPF-TiO_2功能薄膜比商品化TiO_2对甲基橙的降解率(100mg/L)更快,且具有可循环使用的优势。     

Poly(vinyl alcohol) multilayer mixed matrix membranes for the dehydration of ethanol–water mixture

We have developed multilayer mixed matrix membranes (MMMMs) consisting of a selective mixed matrix membrane (MMM) top layer, a porous poly(acrylonitrile-co-methyl acrylate) [poly(AN-co-MA)] intermediate layer and a polyphenylene sulfide (PPS) nonwoven fabrics substrate. The selective MMM layer was formed by incorporating KA zeolite in poly(vinyl alcohol) (PVA) matrix followed by the cross-linking reaction of PVA with fumaric acid. The fumaric acid induced cross-linking reactions were confirmed by Fourier-transformation infrared (FTIR), and their effects on PVA thermal stability and glass transition temperature were characterized by thermolgravimetric analysis (TGA) and differential scanning calorimetry (DSC). The separation performance of the newly developed MMMMs was investigated in terms of permeance and selectivity (as well as flux and separation factor) with respect to zeolite content, feed temperature and composition for the ethanol–water separation by pervaporation. It is found that the separation performance of the MMMM is superior to that of multilayer homogenous membranes (MHM) containing no zeolite. For example, the MMMM with 20 wt.% KA zeolite loading exhibits a much higher selectivity than that of MHM (1279 versus 511) at 60 °C if the feed is a mixture of 80/20 (wt.%) ethanol/water. In addition, the activation energy of the water permeation is significantly reduced from 16.22 to 10.12 kJ/mol after adding of KA zeolite into the PVA matrix, indicating that water molecules require a much less energy to transport through the MMMM because the presence of hydrophilic channels in the framework of zeolite. The excellent pervaporation performance of the MMMM is also resulted from the good contact between zeolite-incorporated and polymer matrix cross-linked by fumaric acid.