Model reactions and formation of epoxy networks with the phenylbenzoate mesogen

The phenylbenzoate mesogen was introduced into epoxy networks by the crosslinker 4-hydroxyphenyl-4-hydroxybenzoate and by the diglycidylether of 4-hydroxyphenyl-4-hydroxybenzoate, respectively. Rigid networks were synthesized on the basis of 4-hydroxyphenyl-4-hydroxybenzoate and the diglycidylether of bisphenol A, and flexible networks were prepared by reaction of the diglycidylether of butanediol-1.4 with the same dihydroxy compound. Model investigations were used to obtain information about the reactivity differences of the phenolic hydroxyl groups of the bisphenol used for network formation. Furthermore, the thermal properties of the main products isolated from the model reactions are strongly influenced by the substituents at the phenylbenzoate structure. Some of these model substances demonstrate structures that can be also found in the networks. In addition, photoinduced cationic crosslinking of the diglycidylether of 4-hydroxyphenyl-4-hydroxybenzoate results in networks with different thermal properties that are dependent on the temperature of network formation. Moreover, the temperature used during crosslinking influences the formation of ordered structures in the networks. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2653–2688, 1997     

Hydrophilic,cationic large‐core star polymers and polymer networks: Synthesis and physicochemical characterization

Group transfer polymerization was used to prepare hydrophilic, cationic large‐core star polymers (LCSPs) and networks of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and ethylene glycol dimethacrylate (EGDMA) in a two‐step procedure involving the synthesis of linear DMAEMA arms, followed by their crosslinking using a mixture of DMAEMA monomer and EGDMA crosslinker. The degree of polymerization of the linear chains prepared in the first step was kept constant, while the composition of the crosslinking mixture was varied systematically at a constant amount of crosslinker. The monomer/crosslinker molar ratio determined whether LCSPs or polymer networks would be produced. In particular, a high monomer/crosslinker molar ratio led to the formation of networks, whereas LCSPs were formed when a low monomer/crosslinker molar ratio was used. The absolute weight‐average molecular weight of the LCSPs was determined using static light scattering, whereas their hydrodynamic radii and radii of gyration were determined using dynamic light scattering and small‐angle neutron scattering, respectively. The sol fraction extracted from the networks decreased as the monomer/crosslinker molar ratio increased. The degrees of swelling of all of the networks were measured as a function of pH and were found to increase below pH 7. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3958–3969, 2008     

Antioxidant and spectroscopic studies of crosslinked polymers synthesized by grafting polymerization of ferulic acid

A novel, simple synthetic strategy for the preparation of crosslinked polymers with significant antioxidant properties is proposed. Ferulic acid (FA), a well‐known antioxidant compound, due to its reactivity toward free radical process, was inserted into a polymeric network with methacrylic acid (MAA) and ethylene glycole dimethacrylate acting as comonomer and crosslinker, respectively. All the reactants were simultaneously mixed in the polymerization feed and one‐pot radical reaction was carried out. Irregular microparticles were prepared by bulk polymerization and microspheres by precipitation polymerization. The materials were characterized by nuclear magnetic resonance–magic angle spinning (NMR‐MAS) studies, to verify effective FA insertion into polymeric networks, and by morphological, dimensional analyses, and water absorption measurement to study their superficial and swelling properties, respectively. Antioxidant properties of materials were evaluated by linoleic acid emulsion system–thiocyanate assay, determination of scavenging activity on DPPH radicals, determination of available phenolic groups in polymeric matrices, and determination of total antioxidant capacity. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetics of styrene uptake by a polyurethane network during the formation of interpenetrating polymer networks

Due to insolubility of the components, formation of interpenetrating polymer networks (IPNs) requires particular ways of synthesis. Among others, IPNs can be prepared by the sequential technique where a network is swollen in a monomer and its crosslinker, which are then polymerized in situ. The simplest case is to swell at equilibrium; however this leads to IPNs of a given composition. For obtaining other compositions, swelling has to be stopped before equilibrium, or the swollen network (gel) has to be deswollen to a certain extent. Therefore, diffusivity of the monomer within the gel has to be known. The kinetics of monomer uptake was studied for a polyether urethane/styrene-divinylbenzene system which gives transparent materials despite the difference in refractive indexes. This allows direct visual observations of the monomer progress within the network. The results are not fully in agreement with the theories of Tanaka and of Candau which both predict the progression of a solvent in a polymeric gel. Two regimes of swelling depending on the concentration distribution of the monomer within the gel were found.     

Swelling Behaviour of Isotropic Poly(n-butyl acrylate) Networks in Isotropic and Anisotropic Solvents

Summary: The swelling properties of photochemically crosslinked poly(n-butyl acrylate) (PABu) networks in isotropic and anisotropic solvents were investigated experimentally. The purpose of this study was to examine the swelling kinetics of PABu networks in isotropic solvents and to compare the results obtained which those observed in the case of the low molecular weight liquid crystal 4-cyano-4′-n-pentyl-biphenyl known as 5CB. The phase diagrams were established in terms of composition and temperature for isotropic solvents, as toluene, acetone, cyclohexane, and methanol, and 5CB, using the plateau values corresponding to equilibrium states of swelling. The polymer networks were prepared via free radical polymerization/crosslinking processes by ultraviolet (UV) radiation of initial mixtures made up from a monomer, a crosslinker, and a photoinitiator. PABu networks with several crosslinking densities were formed using different quantities of difunctional monomer hexanedioldiacrylate (HDDA). Immersion of these networks in excess solvent allows measuring the solvent uptake by determination of the weight in isotropic solvents and diameter in an anisotropic solvent (5CB). Swelling data were rationalized by calculating weight and diameter ratios considering swollen to dry network states of the samples.     

A molecular dynamics simulation study on polymer networks of end-linked flexible or rigid chains

The differences in formation and structural properties of polymer networks consisting of end-linked flexible or rigid chains were studied by molecular dynamics simulation. Networks were formed from monodisperse, linear, short, flexible or rigid chains with functional end groups and a stoichiometric ratio of trifunctional cross-linkers. The rigid chains had a rodlike shape defined by an angle potential, while the flexible chains had no angle potential. In order to understand the influence of chain rigidity, all parameters of precursor chains (length, reactivity, bond potential, nonbonding potential) were the same, with the exception of the angle potential. The system density rho, corresponding to the concentration of monomer in solvent, was varied from 0.01 to 0.11. Different network structures resulting from the different processes of network formation were observed. Simulations showed that the flexible chains created an inhomogeneous network on a large scale via microgel cluster formation, in agreement with experimental observations, whereas the rigid chains rapidly created a homogeneous network in the entire system volume without first generating microgel clusters, with the additional difference that they gave rise to mutually interpenetrating networks at the local scale.     

ChemNetworks: A complex network analysis tool for chemical systems

Many intermolecular chemical interactions persist across length and timescales and can be considered to form a “network” or “graph.” Obvious examples include the hydrogen bond networks formed by polar solvents such as water or alcohols. In fact, there are many similarities between intermolecular chemical networks like those formed by hydrogen bonding and the complex and distributed networks found in computer science. Contemporary network analyses are able to dissect the complex local and global changes that occur within the network over multiple time and length scales. This work discusses the ChemNetworks software, whose purpose is to process Cartesian coordinates of chemical systems into a network/graph formalism and apply topological network analyses that include network neighborhood, the determination of geodesic paths, the degree census, direct structural searches, and the distribution of defect states of network. These properties can help to understand the network patterns and organization that may influence physical properties and chemical reactivity. The focus of ChemNetworks is to quantitatively describe intermolecular chemical networks of entire systems at both the local and global levels and as a function of time. The code is highly general, capable of converting a wide variety of systems into a chemical network formalism, including complex solutions, liquid interfaces, or even self‐assemblies. © 2013 Wiley Periodicals, Inc.     

Conformation‐Dependent Sequence Design of HP Copolymers: An Algorithm Based on Sequential Modifications of Monomer Units

We present a new modification of the so‐called conformation‐dependent sequence design scheme for HP copolymers which was proposed several years ago (H and P refer to the hydrophobic and polar monomer units, respectively). New method models the real chemical experiments more realistically. We performed Monte Carlo computer simulations using the bond‐fluctuation model for protein‐like copolymers obtained by means of the new “iterative” method and compared the results with those obtained for originally proposed “instantaneous coloring” procedure. Copolymers designed by the “iterative” method are shown to have better‐optimized functional properties. The investigation of the influence of sequence preparation conditions has revealed that the statistical properties of designed HP sequences depend rather strongly on the density of the parent homopolymer globule but not on the composition of H and P units.     

双网络增强自支撑多层膜的制备

通过石英晶体微天平(QCM)研究不同最外层对单体、交联剂、引发剂扩散入多层膜的结果显示,聚乙烯亚胺( PEI)为最外层的多层膜更有利于负电荷分子扩散.将(聚乙烯亚胺/聚丙烯酸)12-聚乙烯亚胺[( PEI/PAA)12-PEI]多层膜浸入带有单体、引发剂、交联剂的溶液后,经过光聚合交联与热交联后可形成自支撑膜.XPS数...     

Superfast Responsive Ionic Hydrogels: Effect of the Monomer Concentration

A series of strong polyelectrolyte gels were prepared in aqueous solution, using the sodium salt of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) as the monomer and N,N'‐methylene(bis)acrylamide (BAAm) as a crosslinker. The gels were both prepared below (?22°C) and above (25°C) the bulk freezing temperature of the water, producing cryogels and hydrogels, respectively. The crosslinker (BAAm) content was set at 17 mol%, while the initial monomer concentration C_o was varied over a wide range. It was found that, at ?22°C, a macroscopic network starts to form at an initial monomer concentration of as low as 0.1 w/v%. In contrast to the conventional hydrogels formed at 25°C, the cryogels have a discontinuous morphology consisting of polyhedral pores of sizes 10⁰–10² μm. The cryogels exhibit superfast swelling properties, as well as reversible swelling–deswelling cycles in water and acetone. An increase in the initial monomer concentration from 2.5 to 10% further increases the response rate of the cryogels due to the simultaneous increase of the porosity of the networks.     

Molecular modeling of matrix chain deformation in nanofiber filled composites

The effects of the oriented fiber filler particles on the microscopic properties of the matrix network chains were investigated by using nanofiber filler particles as reinforcing material. Monte Carlo Rotational Isomeric State simulations were carried out for filled poly(ethylene) (PE) networks to study the dependence of the conformational distribution functions of polymer chains and their elastomeric properties on filler loadings. We were especially interested how the excluded volume effect of the nanofiber particles and their orientation (specifically orientational anisotropy) in the matrix influence elastomeric properties of the network. Distribution functions of the end-to-end distances of polymer chains for both unfilled and filled networks were calculated. Effects of nanofiber reinforcements with varying fiber radii and fiber volume fractions were investigated. We have found that the presence of nanofibers significantly increase the non-Gaussian behavior of polymer chains in the composite. The anisotropic effects of the nanofibers on mechanical properties of polymeric composites were studied as a function of their relative orientation to the direction of deformation. The modulus (reduced nominal stress per unit strain) was calculated from the distribution of end-to-end distances of polymer chains using the Mark–Curro method. Relatively small amount of nanofibers was found to increase the normalized moduli of the composite. Our results are quite in satisfactory qualitative agreement with experimental data reported in the literature. This shows that computer simulations provide a powerful tool in predicting physical properties of composite materials.     

Interconnection networks for parallel molecular dynamics simulation based on hamiltonian cubic symmetric topology

A class of interconnection networks for efficient parallel MD simulations based on hamiltonian cubic symmetric graphs is presented. The cubic symmetric graphs have many desirable properties as interconnection networks since they have a low degree and are vertex- and edge-transitive. We present a method for scheduling collective communication routines that are used in parallel MD and are based on the property that the graphs in question have a Hamilton cycle, that is, a cycle going through all vertices of the graph. Analyzing these communication routines shows that hamiltonian cubic symmetric graphs of small diameter are good candidates for a topology that gives rise to an interconnection network with excellent properties, allowing faster communication and thus speeding up parallel MD simulation.     

Semi‐interpenetrating polymer networks composed of poly(N‐isopropyl acrylamide) and polyacrylamide hydrogels

Three series of semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropyl acrylamide) (PNIPA) and 1 wt % nonionic or ionic (cationic and anionic) linear polyacrylamide (PAAm), were synthesized to improve the mechanical properties of PNIPA gels. The effect of the incorporation of linear polymers into responsive networks on the temperature‐induced transition, swelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with various molar ratios (25:1 to 100:1) of the monomer (N‐isopropyl acrylamide) to the crosslinker (methylenebisacrylamide). The hydrogels were characterized by the determination of the equilibrium degree of swelling at 25 °C, the compression modulus, and the effective crosslinking density, as well as the ultimate hydrogel properties, such as the tensile strength and elongation at break. The introduction of cationic and anionic linear hydrophilic PAAm into PNIPA networks increased the rate of swelling, whereas the presence of nonionic PAAm diminished it. Transition temperatures were significantly affected by both the crosslinking density and the presence of linear PAAm in the hydrogel networks. Although anionic PAAm had the greatest influence on increasing the transition temperature, the presence of nonionic PAAm caused the highest dimensional change. Semi‐interpenetrating polymer networks reinforced with cationic and nonionic PAAm exhibited higher tensile strengths and elongations at break than PNIPA hydrogels, whereas the presence of anionic PAAm caused a reduction in the mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3987–3999, 2004     

岩相及煤阶对煤的燃烧特性的影响

为了确定手选富显微组分煤及焦的燃烧特性，从显微组分和煤阶的角度用热天平的燃烧曲线研究反应性，并给出焦的活化能。煤和焦的比表面积由液氮等温吸附求得，并用扫描电镜观察了焦的表面形态。用灰色关联法分析各显微组分和煤阶对反应性和表面形态的影响。结果表明，镜质组对煤和焦反应性和表面形态均有重大影响，煤的反应性受显微组分的影响比煤焦更显著，若不考虑矿物质的影响，则各因素对煤及焦反应性影响次序为Ｖ＞Ｒ＞Ｉ＞Ｅ。     

Mechanical relaxations in episulfide network polymers

A variety of condensation network polymers have been prepared by the reaction between amine, episulfide, and epoxide monomers. The mechanical relaxations occurring in these systems have been examined using a torsion pendulum and the role of hydrogen bonding in the mechanism of the β relaxation is shown to be insignificant. The chemical reaction between amine and episulfide groups has been investigated by IR spectroscopy and is shown to parallel the reaction between amine and epoxide groups. However, steric and electronic factors are suggested to decrease the extent of reaction when aromatic amines are involved. In the case of networks prepared from blends of episulfide and epoxide monomers, measurements of the gel time, together with the mechanical behavior around the glass transition, indicate that either interpenetrating or two-phase networks are formed. This is postulated to be a consequence of the high reactivity of the episulfide ring compared to the epoxide ring. The blending of small amounts of episulfide monomer with the epoxide monomer prior to curing may provide an effective method for lowering gel times without reducing the crosslink density and its dependent physical properties.     

Polybutadiene model networks —synthesis,mechanical characterization and comparison with rubber elasticity models

Model networks of defined crosslink density are prepared via nonradical statistical crosslinking of polybutadiene in bulk and concentrated solution using a masked bistriazolinedione as crosslinker. The kinetics of crosslinking is monitored by FT-IR-spectroscopy. The reaction follows pseudo-1st-order reaction kinetics. The activation parameter of the crosslinking reaction is estimated from crosslinking at various temperatures. Networks of deuterated polybutadiene are prepared by this reaction in a wide range of crosslink densities. The stress strain behavior is analyzed according to the Junction Constraint-Theory of rubber elasticity (JCT) and to the approach introduced by Graessley accounting for trapped topological constraints. The analysis clearly demonstrates that trapped entanglements contribute to the mechanically effective cycle rank, i.e., to the modulus in this system in the small and large strain limit.     

Horizontal chevron domain formation and smectic layer reorientation in SmC* liquid crystals stabilized by polymer networks

The influence of a polymer network, stabilizing an initial texture of horizontal chevron geometry, on the in-plane smectic C* layer reorientation process is studied for different applied electric field conditions. As expected, the reorientation of smectic layers is strongly slowed down and eventually suppressed by the network, even at rather low monomer concentrations. Polymer network formation in a uniformly reoriented smectic layer state reveals that the network acts in two ways: first it gives a biased elastic torque counteracting a field of such symmetry as to cause a change from the templated layer direction; second it introduces an increased effective viscosity counteracting the reorientation in both directions. The behaviour of samples stabilized by two different kinds of polymer networks, created in between the smectic layers (intra-layer) and across them (inter-layer), is then investigated and discussed.     

Horizontal chevron domain formation and smectic layer reorientation in SmC* liquid crystals stabilized by polymer networks

The influence of a polymer network, stabilizing an initial texture of horizontal chevron geometry, on the in-plane smectic C* layer reorientation process is studied for different applied electric field conditions. As expected, the reorientation of smectic layers is strongly slowed down and eventually suppressed by the network, even at rather low monomer concentrations. Polymer network formation in a uniformly reoriented smectic layer state reveals that the network acts in two ways: first it gives a biased elastic torque counteracting a field of such symmetry as to cause a change from the templated layer direction; second it introduces an increased effective viscosity counteracting the reorientation in both directions. The behaviour of samples stabilized by two different kinds of polymer networks, created in between the smectic layers (intra-layer) and across them (inter-layer), is then investigated and discussed.     

Copolymerization at high conversion when the concentration of one monomer does not change

Exact equations and several computer programs were developed for use in studies on copolymerizations carried to high conversion when the concentration of one of the monomers (A) remains constant. Simple ACSL® and DESIRE® programs are described for simulating such copolymerizations, and their output was used to test programs and procedures that were developed to evaluate monomer reactivity ratios for such copolymerization systems. Based on an integrated form of the copolymer equation, Excel® and Fortran programs were developed for evaluating monomer reactivity ratios from information about initial monomer compositions, copolymer compositions, and the fractions of the second monomer (B) that reacted. A graphical procedure for evaluating monomer reactivity ratios from such data was also developed. A previous program developed for calculating information about monomer sequence distributions in copolymers was modified so that it would apply to copolymerization at high conversion when the concentration of one monomer remains constant. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1118–1128, 2000