High Water Resistance and Enhanced Mechanical Properties of Bio-Based Waterborne Polyurethane Enabled by in-situ Construction of Interpenetrating Polymer Network

In this study,acrylic acid was used as a neutralizer to prepare bio-based WPU with an interpenetrating polymer network structure by thermally induced free radical emulsion polymerization.The effects of the content of acrylic acid on the properties of the resulting waterborne polyurethane-poly(acrylic acid)(WPU-PAA)dispersion and the films were systematically investigated.The results showed that the cross-linking density of the interpenetrating network polymers was increased and the interlocking structure of the soft and hard phase dislocations in the molecular segments of the double networks was tailored with increasing the content of acrylic acid,leading to enhancement of the mechanical properties and water resistance of WPU-PAA films.Notably,with the increase in content of acrylic acid,the tensile strength,Young’s modulus,and toughness of the WPU-PAA-110 film increased by 3 times,and 8 times,and 2.4 times compared with WPU-PAA-80,respectively.The WPU-PAA-100 film showed the best water resistance,and the water absorption rate at 96 h was only 3.27%.This work provided a new design scheme for constructing bio-based WPU materials with excellent properties.

Interpenetrated Structures for Enhancing Ion Diffusion Kinetics in Electrochemical Energy Storage Devices

The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices(EESDs)by increasing surface area,thickness,and active materials mass loading while maintaining good ion diffusion through optimized electrode tortuosity.However,conventional thick electrodes increase ion diffusion length and cause larger ion concentration gradients,limiting reaction kinetics.We demonstrate a strategy for building interpenetrated structures that shortens ion diffusion length and reduces ion concentration inhomogeneity.This free-standing device structure also avoids short-circuiting without needing a separator.The feature size and number of interpenetrated units can be adjusted during printing to balance surface area and ion diffusion.Starting with a 3D-printed interpenetrated polymer substrate,we metallize it to make it conductive.This substrate has two individually addressable electrodes,allowing selective electrodeposition of energy storage materials.Using a Zn//MnO_(2) battery as a model system,the interpenetrated device outperforms conventional separate electrode configurations,improving volumetric energy density by 221%and exhibiting a higher capacity retention rate of 49%compared to 35%at temperatures from 20 to 0℃.Our study introduces a new EESD architecture applicable to Li-ion,Na-ion batteries,supercapacitors,etc.

PREPARATION AND PROPERTIES OF GEL POLYMER ELECTROLYTE BASED ON PVDF/ACRYLATE INTERPENETRATING POLYMER NETWORK FOR DYE-SENSITIZED SOLAR CELL

The gel polymer electrolytes（GPEs）based on poly（vinylidence fluoride）（PVDF）/acrylate interpenetrating polymer network（IPN）are prepared.The micro-phase separation type GPEs are characterized by Fourier transform infrared（FTIR）spectroscopy,scanning electron microscope（SEM）,respectively.Moreover,the conductivity and the voltage-current curves of the electrolytes are measured by electrochemical workstation.The higher porosity and electrolyte uptake are observed in the membranes prepared at lower crosslinker concentration.The suitable cross-linking acrylate monomer improves the porosity and the electrochemical behavior of GPE.A dye-sensitized solar cell（DSSC）employing PGE based on PVDF/poly（ethylene glycol dimethacrylate）（PEGDMA）IPN yields an open-circuit voltage of 0.674 V,short-circuit current of 8.476 mA·cm-2and the conversion efficiency of 2.710% under 100 mW·cm-2illumination.

Wide-band underwater acoustic absorption based on locally resonant unit and interpenetrating network structure

The interpenetrating network structure provides an interesting avenue to novel materials. Locally resonant phononic crystal （LRPC） exhibits excellent sound attenuation performance based on the periodical arrangement of sound wave scatters. Combining the LRPC concept and interpenetrating network glassy structure, this paper has developed a new material which can achieve a wide band underwater strong acoustic absorption. Underwater absorption coefficients of different samples were measured by the pulse tube. Measurement results show that the new material possesses excellent underwater acoustic effects in a wide frequency range.Moreover, in order to investigate impacts of locally resonant units,some defects are introduced into the sample. The experimental result and the theoretical calculation both show that locally resonant units being connected to a network structure play an important role in achieving a wide band strong acoustic absorption.

Synthesis and Crystal Structure of a Novel 2-Fold Interpenetrating Three-dimensional Coordination Polymer,{[Co_3(byip)_2(bix)_3(H_2O)_2]·H_2O}_n

The title coordination polymer including two crystallographically independent Co2＋ ions is hydrothermally synthesized, in which the Co（1） 2＋ ion is four-coordinated by two carboxylate oxygen atoms from two different 5-（benzoic acid-4-yldiazenyl）isophthalate （byip3-） anions and two nitrogen atoms from two distinct 1,4-bis（imidazol-1-ylmethyl） benzene （bix） ligands displaying a tetrahedral geometry. The Co（2） 2＋ ion is six-coordinated by two water molecules at the apical positions, and two carboxylate oxygen atoms and two nitrogen atoms at the equatorial positions, affording a slightly distorted octahedron. Two Co（1）2＋ and two Co（2）2＋ ions are linked together by four byip3- anions forming a 44-membered motif and these motifs are further arranged into a three-dimensional framework through bix ligands along the a axis with a larger channel （ca. 22.70×11.01）. Each individual network interpenetrates with the other identical network in a parallel fashion to generate a 2-fold interpenetrating array with the {62.84}{63}2{64.82}2 topology.

Preparation,Morphology and Damping Property of PU/UP Interpenetrating Polymer Networks

Interpenetrating polymer networks （IPNs） composed of acrylate-modified polyurethane （PU）/unsaturated polyester （UP） resin via simultaneous polymerization with various component ratios of PU/UP were prepared. The polymerization processes of IPNs were traced through infrared spectrum （IR） techniques, by which the phase separation in systems could be controlled effectively. Results for the morphology and miscibility among multiple phases of IPNs, obtained by transmission electron microscope （TEM） indicated that the domains between two phases were constricted in nanometer scales. The dynamic mechanical thermal analyzer （DMTA） detection results revealed that the loss factor （tanS） and loss modulus （E″） increased with the polyurethane amounts in system, and the peak value in curves of tanδ and E″ appeared toward low temperature ranges. Maximum tanδ values of all samples were above 0.3 in the nearly 50℃ ranges. Also, the mechanical properties of PU/UP IPNs were studied in detail.

Synthesis and Structure of a Novel 3-Fold Interpenetrating Three-dimensional Coordination Polymer:[Ni(Hbyip^(2-))(bix)_(0.5)(H_2O)]_n

A three-dimensional coordination polymer,[Ni（Hbyip2-）（bix）0.5（H2O）]n,has been hydrothermally synthesized.Each Ni2＋ ion is five-coordinated by three carboxylate O atoms from three different 5-（benzoic acid-4-yldiazenyl）isophthalate（Hbyip2-） anions,one N atom from one 1,4-bis（imidazol-1-ylmethyl）benzene（bix） ligand and one O atom from an aqua ligand displaying a distorted square-pyramid.Each Ni atom is defined by three Hbyip2-anions and each Hbyip2-anion adopts a tris（mono-dentate） ligand coordinating to three Ni2＋ ions affording a 36-membered inorganic ring.These rings are further arranged into an undulated two-dimensional layer parallel to the（101） plane.Adjacent two-dimensional networks are linked by bix ligands into a three-dimensional {63,83}{63} framework with a large channel（ca.26.3 × 13.6） along the [100] direction.Each individual {63,83}{63} network interpenetrates with two others in a parallel fashion to generate a 3-fold interpenetrating network.

Studies on the Morphology of Natural Rubber/Polyacrylate Interpenetrating Polymer Networks

The interpenetrating polymer network(IPN) systems have attracted a lot of attention because of their unique two-phase structure and properties. There have been many publications concerning the IPNs in which poly (isoprene) (PIP) or polyacrylates (PAC) is formed as one of the networks.In the present study, Four serles of natural rubber(NR)/PAC IPNs were prepared and their morphologies were investigated with dynamic mechanics analysis(DMA) and transmission electron microscopy (TEM).

Polymerization Process and Morphology of Polyurethane/Vinyl Ester Resin Interpenetrating Polymer Networks

A series of polyurethane （PU）/vinyl ester resin （VER） simultaneous IPNs （interpenetrating polymer networks） with different component ratios and comonomers types introduced to VER were synthesized and the polymerization processes were traced by Fourier transform infrared spectroscopy （FTIR） to study the kinetics of IPNs and hydrogen bonding action within multi-component. Furthermore, the relationship of polymerization process with morphology was investigated in detail for the first time by the morphological information given by chemical action between two networks besides physical entanglement, atomic force microscope （AFM） observation and dynamic mechanical analysis （DMA）. The results indicated that the degree of hydrogen bonding （Xb,UT,%）, calculated from functional group conversional rate and fine structures gained from FT-IR spectra of two networks, were affected by PU/VER weight ratios and comonomer types of VER. The relationship of formation kinetics and morphology showed that the change of Xb,UT （%） values exhibited excellent consistency with that of phase sizes observed by AFM and detected by DMA.

Synthesis and Hydrogen-bonded Interpenetrating Grid Structure of 5,5'-Bis[4-(2-hydroxyethyl)phenyl]diazo-dipyrromethane

A new 5,5＇-bisdiazo-dipyrromethane compound 3 has been synthesized and cha- racterized. The crystal of 3 is of orthorhombic, space group Iba2 with a = 19.1914（17）, b = 9.8396（8）, c = 13.7643（12） A, V= 2599.2（4） A3, Z = 4, C29H34N602, Mr = 498.62, Dc = 1.274 g/cm3, F（000） = 1064, μ（MoKa） = 0.083 mm-1, the final R = 0.0302 and wR = 0.0786 for 6361 observed reflections with I 〉 2σ（/）, and R = 0.0320 and wR = 0.08006 for all data. It reveals that the molecules of compound 3 assemble into grid structures through a R22（7） type hydrogen bonding motif between azopyrrole and hydroxyl group. The grids interpenetrate each other with the assistance of C-H...π interaction.

Interpenetrating polymers supported on microporous polypropylene membranes for the transport of chromium ions

Modifying polypropylene membranes with interpenetrating polymer networks(IPNs) through the incorporation of poly(glycidyl methacrylate-N-methyl-D-glucamine)(P(GMA-NMG)) was performed by in situ synthesis via radical polymerization. The surface of the polypropylene membrane was activated by hydrophilic grafted polyelectrolyte, and then, pressure injection was used for the impregnation of the reactive solution in the membrane.Two types of pore-filled membranes were synthesized, chelating interpenetrating homopolymer networks of P(GMA-NMG), and chelating-ion exchange interpenetrating polymer networks(e.g., P(GMA-NMG)/P(AA),P(GMA-NMG)/P(AMPSA), and P(GMA-NMG)/P(Cl VBTA)). After their synthesis, the modified polypropylene membranes were characterized using techniques such as the electrokinetic potential, SEM, FT-IR, and Donnan dialysis to corroborate the chromium ion transport. The P(GMA-NMG) and complex network membranes exhibited a hydrophilic character with a water-uptake capacity between 20% and 35% and a percentage of modification between 4.0% and 7.0% in comparison with the behavior of the unmodified polypropylene membrane.Hexavalent chromium ions were efficiently transported from the food chamber at p H 9.0 when the 65.2%MTA1 P(Cl VBTA) homopolymer IPN membrane and 48.5% MTAG P(GMA-NMG)/P(Cl VBTA) IPN membrane were used. Similarly, hexavalent chromium ions were removed from the food chamber at pH 3.0 when MTAG(63.30%) and MTA1(35.68%) were used in 1 mol·L^(-1)Na Cl solution as the extraction reagent.

Microstructure of nickel foam/Mg double interpenetrating composites

The magnesium matrix double interpenetrating composites reinforced by nickel foam were fabricated by pressureless infiltration technology.Then the morphology of the nickel reinforcement and the microstructures of composites were characterized by SEM.The results show that not only is the nickel foam reinforcement reticular in three dimensions,but also the struts of foam keep the network structure,which ensures that the Ni foam/Mg composites are double interpenetrating.The interface bonding of composites between magnesium matrix and nickel foam reinforcement is good,without reaction around the interface,which is the indispensable condition that advanced composites should possess.Magnesium matrix distributes in the windows of nickel foam,the triangle center holes and microhole of nickel struts,and the composites have double interpenetrating structure,which makes the composites have unique properties.

Thermoreversible Thickening and Self-assembly Behaviors of pH/Temperature Dually Responsive Microgels with Interpenetrating Polymer Network Structure

The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN microgels) were synthesized by seed emulsion polymerization. The results obtained by dynamic laser light scattering( DLLS) show that the microgels have good pH /temperature dual sensitivities. The temperature sensitive component and the pH sensitive component inside the microgels have little interference with each other. The rheological properties of the concentrated PNIPAM /PAA IPN microgel dispersions as a function of temperature at pH 4. 0 or 7. 0 were investigated by viscometer,and the results displayed that only at pH 7. 0 the dispersions presented thermoreversible thickening behavior. Then the PNIPAM /PAA fibers were prepared by self-assembly of the PNIPAM /PAA IPN microgels in the ice-crystal templates formed by unidirectional liquid nitrogen freezing method. Field emission scanning electron microscopy( FESEM) images indicate that the PNIPAM /PAA fibers are rounded,randomly orientated and interweaved.

Structural characteristics and properties of polyurethane modified TDE-85/MeTHPA epoxy resin with interpenetrating polymer networks

Diglycidyl-4,5-epoxycyclohexane-1,2-dicarboxylate(TDE-85)/methyl tetrahydrophthalic anhydride (MeTHPA) epoxy resin was modified with polyurethane(PU) and the interpenetrating polymer networks(IPNs) of PU-modified TDE-85/MeTHPA resin were prepared. The structural characteristics and properties of PU-modified TDE-85/MeTHPA resin were investigated by Fourier transform infrared(FTIR) spectrum,emission scanning electron microscopy(SEM) and thermogravimetry(TG). The results indicate that epoxy polymer network (Ⅰ) and polyurethane polymer network (Ⅱ) of the modified resin can be obtained and the networks (Ⅰ) and (Ⅱ) interpenetrate and tangle highly each other at the phase interface. The micro morphology presents heterogeneous structure. The integrative properties of PU-modified TDE-85/MeTHPA epoxy resin are improved obviously. The PU-modified TDE-85/ MeTHPA resin's tensile strength reaches 69.39 MPa,the impact strength reaches 23.56 kJ/m,the temperature for the system to lose 1% mass (t1%) is 300 ℃,and that for the system to lose 50% mass (t50%) is 378 ℃. Compared with those of TDE-85/MeTHPA resin,the tensile strength,impact strength,t1% and t50% of the PU-modified resin increases by 48%,115%,30 ℃,11 ℃,respectively. The PU-modified TDE-85/MeTHPA resin has the structure characteristics and properties of interpenetrating polymer networks.

Synthesis and Characterization of Polyurethane and Epoxy Resin Interpenetrating Polymer Network

A series of Polyurethane (PU)/bisphenol A based Epoxy Resin(EP) Interpenetrating Polymer Networks(IPN) were synthesized and characterized by SEM, DSC, TGA and DMTA. It was found that IPN shows the best compatibility and damping properties when the ratio of PU/EP is 80 to 20. The results show that chain-extender and higher molecular weight of PPG are able to improve the properties of compatibility, damping and thermal properties.

Damping properties of silicone rubber/polyacrylate sequential interpenetrating networks

Silicone rubber/polyacrylate sequential interpenetrating polymer networks(IPNs) were prepared by silicone rubber sheet dipped into the solution composed of different acrylate monomers and benzoyl peroxides(BPOs) for different time at room temperature and then acrylate polymerized at 80℃for 2 h. The molecular structure and damping properties of sequential IPNs were studied by means of FT-IR and dynamic mechanical analysis(DMA), respectively. The FT-IR spectrum shows that polyacrylate distributes unevenly along the thickness direction of IPNs, i.e. the concentration of polyacrylate decreases from the midst to the surface of the IPNs. The DMA shows that cold crystallization of silicone in the temperature range from -47℃to -30℃is reduced and loss factor of IPNs is improved after interpenetrating with polyacrylate. This suggestes that IPNs can be used as damping materials.

SYNTHESIS, STRUCTURE AND PROPERTIES OF INTERPENETRATING SULFONIC ACID RESINS WITH HIGH CAPACITY

Two series of interpenetrating sulfonic acid resins (ISAR), 10×n and n×10, were prepared by means of the wet method, and the physicochemical, thermodynamic and kinetic properties of the ISAR were measured. The results show: 10×n resins exhibit better properties than n×10 ones, mainly in higher apparent degree of crosslinking and larger conformational entropy effect, among which, 10×1 resin exhibits the best thermodynamic and kinetic properties. In the DTA graphs of n×10 resins, there are two T_g and two T_(ox), but in those of 10×n, only one T_g and one T_(ox). This result well supports the conclusion that 10×n resins have much better interpenetrating structural aspects.

Microstrueture and Properties of Fluoroelastomer/Butadiene-Acrylonitrile Rubber Interpenetrating Polymer Networks

Interpenetrating polymer networks （IPNs） based on fluoroelastomer/butadiene-acrylonitrile rubber （FKM/NBR） by molten blending at a high temperature and chemical cross-linking of two components were prepared. The influence of the two networks component on the mechanical properties and thermostabilities was studied. The experimental results show that the mechanical properties of the IPNs are superior to those of the individual FKM and NBR networks due to forming the case of interpenetrating and intercross-linking between the two networks, the mechanical properties and thermal resistance exhibit higher values when 80/20 （w/w） FKM and NBR is blended and respectively cured simultaneously. The co-continuous morphology of the IPNs in the blends of 80/20 （w/w） FKM/NBR is found by transmission electron microscopy （TEM）, the differential scanning calorimetry （DSC） determination shows that the blends of 80/20 （w/w） FKM/NBR have better compatibility, and the glass transition temperature of the elastomer is -21.5 ℃.

SYNTHESIS AND CHARACTERIZATION OF POLYDIMETHYLSILOXANE/POLYSTYRENE SEMIINTERPENETRATING POLYMER NETWORKS

The synthesis of pseudo- and semi-interpenetrating polymer networks (IPNs) based on polydimethylsiloxane (PDMS) and polystyrene (PS) is described. IPNs were obtained by simultaneous and in situ sequential synthesis procedure. The preliminary studies on IPNs properties such as transition temperature, microphase separation and mechanical behaviors have been carried out by using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The experimental evidence clearly showed that semi-IPNs obtained by sequential synthesis procedure have higher interpenetrating extent than pseudo-IPNs synthesized by simultaneous procedure. Over the full composition, the PDMS/PS IPNs are immiscible. The pseudo-IPNs microphase separation can be greatly subdued through the formation of grafting bonds between two networks as well as the kinetic rate-matching of the individual network crosslinking.

Taste masking of ofloxacin and formation of interpenetrating polymer network beads for sustained release

The objective of this study was to carry out taste masking of ofloxacin(Ofl) by ion exchange resins(IERs)followed by sustained release of Ofl by forming interpenetrating polymer network(IPN) beads. Drug-resin complexes(DRCs) with three different ratios of Ofl to IERs(1:1, 1:2, 1:4) were prepared by batch method and investigated for in vivo and in vitro taste masking. DRC of methacrylic acid-divinyl benzene(MD) resin and Ofl prepared at a ratio of 1:4 was used to form IPN beads. IPN beads of MD 1:4 were prepared by following the ionic cross-linking method using sodium carboxymethyl xanthan gum(SCMXG) and SCMXG-sodium carboxymethyl cellulose(SCMXG-SCMC). IPN beads were characterized with FT-IR and further studied on sustained release of Ofl at different pH. In vivo taste masking carried out by human volunteers showed that MD 1:4 significantly reduced the bitterness of Ofl. Characterization studies such as FT-IR, DSC, P-XRD and taste masking showed that complex formation took place between drug and resin. In vitro study at gastric pH showed complete release of drug from MD 1:4 within 30 min whereas IPN beads took 5 h at gastric pH and 10 h at salivary pH for the complete release of drug. As the crosslinking increased the release kinetics changed into non-Fickian diffusion to zero-order release mechanism. MD 1:4 showed better performance for the taste masking of Ofl and IPNs beads prepared from it were found useful for the sustained release of Ofl at both the pH, indicating a versatile drug delivery system.