Thermally stable interpenetrating polymer networks for second-order nonlinear optical materials

We report several kinds of interpenetrating polymer networks (IPNs) with nonlinear optical (NLO) properties. DMA spectra show that the two components of the IPNs have good compatibility with each other. The NLO materials have good optical transparency. The thermal stability of alignment was improved and the poled order remained very high. (C) 1999 John Wiley & Sons, Inc.

Dynamic mechanical properties of interpenetrating polymer networks based on polyacrylates and epoxy

Interpenetrating polymer networks (IPNs) based on polyacrylate (poly(polyethylene glycol diacrylate), PEGDA) and epoxy(diglycidyl ether of bisphenol A, DGEBA) were prepared simultaneously Dynamic mechanical properties of the SINs (simultaneous interpenetrating networks) with various compositions were studied. Enhanced mechanical properties were found in this case. From the point of view of pre-swollen networks, all of the PEGDA/DGEBA IPNs were composed of the individual pre-swollen networks. A micro-phase segregation system was produced in the SIN. Glass transition temperatures shifted inward, which was attributed to molecular packing effects or mutual-entanglements of molecular segments among the individual pre-swollen networks. In accordance with the additivity of properties, namely the parallel model, the entanglement density between the two polymer networks reached its maximum at 50/50 PEGDA/DGEBA IPN.

Polyepichlorohydrin polyurethane/poly(methyl methacrylate) interpenetrating polymer networks

Polyurethane (PU) based on polyepichlorohydrin/poly(methyl methacrylate) (PECH/PMMA) interpenetrating polymer networks (IPNs) was synthesized by a simultaneous method. The effects of composition, hydroxyl group number of PECH, NCO/OH ratio and crosslinking agent content in IPNs were investigated in detail. Some other glycols, such as poly(ethylene glycol), poly(propylene glycol) and hydroxyl-terminated polybutadiene, were also used to obtain PU/PMMA IPNs. The interpenetrating and fracture behaviors of the IPNs are explained briefly.

Synthesis and characterization of interpenetrating polymer networks based on polyacrylate and epoxy

The synthesis and properties of simultaneously interpenetrating networks (SINs) based on poly(polyethylene glycol diacrylate) (PEGDA) and epoxy (diglycidyl ether of bisphenol A, DGEBA) were studied. The effect of compositional variation on the morphology and properties of products was investigated. The swelling coefficient, densities, glass transition behavior, and thermal stability of these interpenetrating networks (IPNs) are discussed. Microphase separation morphological structures were found in all PEGDA/DGEBA IPNs. Decreased swelling ratios compared to the calculated swelling coefficients based on the weight additivity of the components were obtained after the formation of IPNs. Increased density and thermal stability were also obtained in these IPNs, implying the existence of interpenetration (topological entanglements) among the component networks.

MUTUAL ENTANGLEMENTS IN POLY(VINYL ACETATE) POLY(METHYL ACRYLATE) INTERPENETRATING POLYMER NETWORKS

An equation has been derived for the equilibrium swelling of sequential interpenetrating polymer networks (IPNs), which exhibit a single glass transition temperature and the two components are considered to be compatible. The properties of the equilibrium swelling and elastic modulus of sequential poly(vinyl acetate)/poly(methyl acrylate) IPNs have been discussed according to the derived equation and the Siegfried-Thomas-Sperling formula of the elastic modulus for homo IPNs. In both fully swollen and bulk states, there was favourable evidence for added physical crosslinks in poly(vinyl acetate)/poly(methyl acrylate) IPNs. The Binder-Frisch theory is also discussed.

Fabrication and characterization of microstructured and pH sensitive interpenetrating networks hydrogel films and application in drug delivery field

Novel microstructured and pH sensitive poly(acryliac acid-co-2-hydroxyethyl methacrylate)/poly(vinyl alcohol) (P(AA-co-HEMA)/PVA) interpenetrating network (IPN) hydrogel films were prepared by radical precipitation copolymerization and sequential IPN technology. The first P(AA-co-HEMA) network was synthesized in the present of IPN aqueous solution by radical initiating, then followed by condensation reaction (Glutaraldehyde as crosslinking agent) within the resultant latex, it formed multiple IPN microstructured hydrogel film. The film samples were characterized by IR, SEM and DSC. Swelling and deswelling behaviors and mechanical property showed the novel multiple IPN nanostuctured film had rapid response and good mechanical property. The IPN films were studied as controlled drug delivery material in different pH buffer solution using cationic compound, crystal violet as a model drug.

SAXS measurements of the interface in polyacrylate and epoxy interpenetrating networks with fractal geometry

The interface thickness in two-component interpenetrating polymer networks (IPN) system based on polyacrylate and epoxy were determined using small-angle X-ray scattering (SAXS) in terms of the theory proposed by Ruland. The thickness was found to be nonexistent for the samples at various compositions and synthesized at variable conditions-temperature and initiator concentration. By viewing the system as a two-phase system with a sharp boundary, the roughness of the interface was described by fractal dimension, D, which slightly varies with composition and synthesis condition. Length scales in which surface fractals are proved to be correct exist for each sample and range from 0.02 to 0.4 Angstrom(-1). The interface in the present IPN system was treated as fractal, which reasonably explained the differences between Pored's law and experimental data, and gained an insight into the interaction between different segments on the interface. (C) 1997 Elsevier Science Ltd.

Use of SAXS to characterize the morphology of poly(polyethylene glycol diacrylate)/epoxy resin interpenetrating networks

Interpenetrating polymer networks (IPNs) have been synthesized from prepolymers that form miscible blends. All IPNs made from polyacrylate ((polyethylene glycol diacrylate), PEGDA) and epoxy (diglycidyl ether of bisphenol A, DGEBA) can be made in phase separated states by incorporating crosslinks. However, blends of these prepolymers, having a negative Flory-Huggins interaction parameter, are highly miscible. This indicates that formation of IPNs favours phase separation relative to blends. The microphase separation characteristics in the PEGDA/DGEBA IPNs were determined using smalt-angle X-ray scattering (SAXS). The Debye-Bueche and Guinier methods were used to calculate the correlation lengths of the segregated phases existing in the PEGDA/DGEBA IPNs. The results from SAXS showed that the size of the phase segregation zones changed with composition from about 50 to 100 Angstrom.

亲水性聚合物互穿网络膜的制备、性质和应用研究

本论文采用连续互穿网络技术，自由基的水溶液聚合，制备了一系列pH敏感的互穿网络的水凝胶膜，详细的研究了它们的性质，并探讨了其在药物输送体系潜在的应用。 用溶液聚合和化学交联方法合成了一系列PVA/PAA，PAA-co-PAMPS/PVA全互穿网络水凝胶膜，用红外光谱、DSC、SEM表征了网络的结构特征，并系统的研究了在不同介质中的溶胀性质、机械性质和吸湿性。 用水相沉淀聚合和同时采用化学交联又有物理缠结的互穿网络思想，制备了具有纳米结构、pH敏感的水凝胶膜，进一步得到了透明的PHEMA的水凝胶膜。SEM，FTIR光谱，和紫外可见光谱表征了多重互穿网络的特征。DSC分析表明这种方法使互不相容的PVA, PHEMA 和PMA具有热力学相容性。溶胀和去溶胀动力学表明由于其纳米结构使这种多重的IPN具有快速的响应；且透明的膜具有高的水含量。 本论文的创新之处是同时采用化学交联又有物理缠结的互穿网络技术制备了纳米结构的含PHEMA的水凝胶膜，解决了PHEMA与PVA、PAA、PMA不相容的问题，并进一步获得了溶胀透明的水凝胶膜，透光率最高可达93%。这种方法单体含量低，方便简单，避免了使用有机溶剂，有利于生物医学应用。

Polymeric fullerene oxide films produced by decomposition of hexanitro[60]fullerene

A new poly(fullerene oxide) thin film material has been fabricated by thermal activation and electron bombardment on hexanitro[60]fullerene (HNF) film deposited on a An substrate, all under vacuum conditions. The reaction products in the polymerization process are analyzed by XPS, UPS, IR, TGA-MS and LDI-MS techniques. It is found that the main effect of thermal and radiation treatments is to induce cleavage of -NO bonds from HNF molecules resulted in the release of nitric oxide gas and the formation of fullerene-bound oxyradicals, C-60-C-6. Spectroscopic evidence strongly suggests that rearrangement of fullerenic nitro moieties into nitrito groups is involved in the HNF decomposition process prior to the generation of reactive oxyradical intermediates. Consequently, the intermolecular coupling reaction of these oxyradicals leads to carbon polymer networks containing oxygen-bridged fullerenes. The thermally generated polymeric thin film is stable up to 900 K. Electron bombardment is also effective in both the decomposition of -NO2 groups and the removal of -OH groups present in HNF films. UV irradiation at 365 nm alone is shown to be not as efficient for the polymer formation. (C) 2003 Elsevier Ltd. All rights reserved.

Preparation and Characterization of Nanostructured and High Transparent Hydrogel Films with pH Sensitivity and Application

Novel nanostructured, high transparent, and pH sensitive poly(2-hydroxyethyl methacrylate-co-methacryliac acid)/poly(vinyl alcohol) (P(HEMA-co-MA)/PVA) interpenetrating polymer network (IPN) hydrogel films were prepared by precipitation copolymerization of aqueous phase and sequential IPN technology. The first P(HEMA-co-MA) network was synthesized in aqueous solution of PVA, then followed by aldol condensation reaction, it formed multiple IPN nanostructured hydrogel film. The film samples were characterized by IR, SEM, DSC, and UV-vis spectrum. The transmittance arrived at 93%. Swelling and deswelling behaviors showed the multiple IPN nanostructured film had rapid response. The mechanical properties of all the IPN films improved than that of PVA film. Using crystal violet as a model drug, the release behaviors of the films were studied.

Conformation studies on sol-gel transition in triblock copolymer solutions

The gelation of physically associating triblock copolymers in a good solvent was investigated by means of the Monte Carlo simulation and a gelation process based on the conformation transition of the copolymer that was described in detail. In our simulative system, it has been found that the gelation is closely related with chain conformations, and there exist four types of chains defined as free, dangling, loop, and bridge conformations. The copolymer chains with different conformations contribute to the formation of gel in different ways. We proposed a conformational transition model, by which we evaluated the role of these four types of chains in sol-gel transition. It was concluded that the free chains keeping the conformation transition equilibrium and the dangling conformation being the hinge of conformation transition, while the chain with loop conformation enlarges the size of the congeries and the chain with bridge conformations binds the congeries consisted of the copolymer chains. In addition, the effects of temperature and concentration on the physical gelation, the association of the copolymer congeries, and the copolymer chain conformations' distribution were discussed.

Well-organized structures of ZnS semiconductor nanocrystals using amphiphilic triblock copolymer aggregates as templates

Ring- and rod-shaped P4VP-b-PS-b-P4VP ( PS, polystyrene; P4VP, poly( 4-vinylpyridine)) triblock copolymer aggregates are used as templates to synthesize ZnS nanocrystals. Herein, PVP serves as both a stabilizing agent and a structure- directing agent. The resulting ZnS nanocrystals could be aligned along the corona of the copolymer aggregates in near-perfect structures through control of both the molar ratio of Zn2+ to P4VP and the reaction time. The diameter of the as-synthesized ZnS layer on the surface of polymer template is approximate 2 - 3 nm. High-resolution transmission electron microscopy images reveal that the ZnS particles are single crystal in a zinc blende structure. This method provides a simple, reproducible route at room temperature to prepare assembled hybrid polymer - semiconductor nanocrystal nanocomposites.

Dynamic mechanical studies of the sulfonated butyl rubber ionomers and their blends

Dynamic mechanical properties of sulfonated butyl rubber ionomers neutralized with different amine or metallic ion (zinc or barium) and their blends with polypropylene (PP), high-density polyethylene (HDPE), or styrene-butadiene-styrene (SBS) triblock copolymer were studied using viscoelastometry. The results showed that glass transition temperatures of ion pair-containing matrix and ionic domains (T-g1 and T-g2, respectively) of amine-neutralized ionomers were lower than those of ionomers neutralized with metallic ions, and the temperature range of the rubbery plateau on the storage modulus plot for amine-neutralized ionomers was narrower. The modulus of the rubbery plateau for amine-neutralized ionomers was lower than that of ionomers neutralized with zinc or barium ion. With increasing size of the amine, the temperature range for the rubbery plateau decreased, and the height of the loss peak at higher temperature increased. Dynamic mechanical properties of blends of the zinc ionomer with PP or HDPE showed that, with decreasing ionomer content, the T-m of PP or HDPE increased and T-g1 decreased, whereas T-g2 or the upper loss peak temperature changed only slightly. The T-g1 for the blend with SBS also decreased with decreasing ionomer content. The decrease of T-g1 is attributed to the enhanced compatibilization of the matrix of the ionomer-containing ion pairs with amorphous regions of PP or HDPE or the continuous phase of SBS due to the formation of thermoplastic interpenetrating polymer networks by ionic domains and crystalline or glassy domains.

Miscibility and crystallization behavior of thermosetting polyimide thermoplastic polyimide blends

Compatibility, morphology, crystalline structure and mechanical properties of the blends of a thermosetting polyimide with thermoplastic polyimides consisting of dianhydrides of different lengths have been studied by the use of dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and small-angle X-ray scattering (SAXS) techniques. The results of our research show that the blends change from compatible to semi-compatible when the difference between the length of the dianhydrides of the two components increases. Addition of a thermoplastic polyimide inhibits the crystallization of the thermosetting component. However, this effect decreases with increasing length of the dianhydrides and the distribution of the molecules of the thermoplastic polyimide component changes from interlamellar to interfibrillar. Impact strength and morphology of the fractured surfaces indicate that among the semiinterpenetrating polymer networks (semi-IPN) obtained the toughening effect of the partially compatible one is the best. The results are discussed in terms of charge transfer interaction between imide group and p-phenylene group.