Fluorinated semi-interpenetrating polymer networks for enhancing the mechanical performance and storage stability of polymer-bonded explosives by controlling curing and phase separation rates

Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.

Anion exchange membranes with a semi-interpenetrating polymer network using 1,6-dibromohexane as bifunctional crosslinker

An anion exchange membrane(AEM)is generally expected to possess high ion exchange capacity(IEC),low water uptake(WU),and high mechanical strength when applied to electrodialysis desalination.Among different types of AEMs,semi-interpenetrating polymer networks(SIPNs)have been suggested for their structural superiorities,i.e.,the tunable local density of ion exchange groups for IEC and the restrained leaching of hygroscopic groups by insolubility for WU.Unfortunately,the conventional SIPN AEMs still struggle to balances IEC,WU,and mechanical strength simultaneously,due to the lack of the compact crosslinking region.In this work,we proposed a novel SIPN structure of polyvinylidene difluoride/polyvinylimidazole/1,6-dibromohexane(PVDF/PVIm/DBH).On the one hand,DBH with two cationic groups of imidazole groups are introduced to enhance the ion conductivity,which is different from the conventional monofunctional modifier with only one cationic group.On the other hand,DBH has the ability to bridge with PVIm,where the mechanical strength of the resulting AEM is increased by the increase of crosslinking degree.Results show that a low WU of 38.1%to 62.6%,high IEC of 2.12—2.22 mmol·g^(-1),and excellent tensile strength of 3.54—12.35 MPa for PVDF/PVIm/DBH membrane are achieved.This work opens a new avenue for achieving the high-quality AEMs.

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.

In situ formed cross-linked polymer networks as dual-functional layers for high-stable lithium metal batteries

Lithium-metal anodes(LMAs)have been recognized as the ultimate anodes for next-generation batteries with high energy density,but stringent assembly-environment conditions derived from the poor moisture stability dramatically hinder the transformation of LMAs from laboratory to industry.Herein,an in situ formed cross-linked polymer layer on LMAs is designed and constructed by a facile thiol-acrylate click chemistry reaction between poly(ethylene glycol)diacrylate(PEGDA)and the crosslinker containing multi thiol groups under UV irradiation.Owing to the hydrophobic nature of the layer,the treated LMAs demonstrate remarkable humid stability for more than 3 h in ambient air(70%relative humidity).The coating humid-resistant protective layer also possesses a dual-functional characterization as solid polymer electrolytes by introducing lithium bis(trifluoromethanesulfonyl)imide in the system in advance.The intimate contact between the polymer layer and LMAs reduces interfacial resistance in the assembled Li/LiFePO_(4)or Li/LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cell effectively,and endows the cell with an outstanding cycle performance.

Study of Hydrophobic Nature of Fullerene-Based Poly (Methyl Hydro Siloxane) and Polyacrylonitrile Interpenetrating Polymer Network

In this study, the effect of combining different molecular domains on single platform has been reported that revealed a proper packing and interpenetration of fullerene spheres with the monomeric species. The fabricated IPN system exhibits hydrophobic behavior in nature. An interpenetrating polymer network (IPN) of fullerene-based poly (methyl hydro siloxane) (PMHS) and polyacrylonitrile (PAN) was prepared. The synthesized polymer network was characterized using infrared (IR) spectroscopy, differential scanning calorimetric analysis (DSC), and scanning electron microscopic (SEM) technique. The IPN was analyzed by IR spectroscopy, which depicts presence of fullerene at 500 cm−1 and 1632 cm−1, presence of PHMS at 1050 cm−1, 1250 cm−1, 2225 cm−1, and 3000 cm−1 and presence of PAN at 3077 cm−1, 1299 cm−1, 1408 cm−1 and 2083 cm−1. Shifting in band positions indicated the interpenetration of the reacting species. DSC endotherm showed crystalline peak (Tc) at 117˚C, which indicated the crystalline nature of the synthesized IPN. The absence of Tg peak and clear observable Tc peak revealed crystalline behavior of polymeric network. The microstructure of the polymer network was observed by SEM technique, which revealed transparent and dual-phase morphology of the IPN surface. The fluorescent emission spectra of polymeric network were recorded on a spectrofluorometer which revealed fluorescent excitation and emission spectra of the IPN. The Emission spectra generated by radiative decay of excitations exhibit a maximal peak at 450 nm, suggesting that the synthesized IPN nanosheets were typically high-intensity blue light emitting materials. The FTIR investigations revealed multiple non-covalent interactions achieved by polymerization with physical anchoring on the polymeric network surfaces. Such interactions can be recognized as the driving force for the fabrication of hydrophobic flexible silicon-based materials with a self-cleansing action.

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.

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).

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.

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.

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 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.

Semi-Interpenetrating Novolac-Epoxy Thermoset Polymer Networks Derived from Plant Biomass

Bio-based phenol-formaldehyde polymer (BioNovolac) was developed by reacting molar excess of bio-oil/phenolwith formaldehyde in acidic medium. Glycidyl 3,5-diglycidoxybenzoate (GDGB), was prepared by directglycidylation of α-resorcylic acid (RA), a naturally occurring phenolic monomer. GDGB was crosslinked in thepresence of BioNovolac by anionic polymerization. Fourier transform infrared spectroscopy (FTIR) confirmedthe formation of semi-interpenetrating polymer networks. The glass transition temperature and moduli of biobasedcrosslinked systems were observed to increase with increasing GDGB content. Active chain density andmass retention measured by dynamic mechanical analysis (DMA) and Soxhlet extraction, respectively, indicated ahigh crosslink density of the cured networks. Scanning electron microscopy (SEM) images depicted thehomogeneity of the bulk phase. The preparation of bio-based epoxy-novolac thermoset network resulted inreduced consumption of petroleum-based chemicals.

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.

AN EPOXY/(METHYL METHACRYLATE)INTERPENETRATING POLYMER NETWORK FOR NONLINEAR OPTICS

An interpenetrating polymer networks (IPN) consisting of an epoxy-based polymer network and a polymethyl methacrylate network were synthesized and characterized. The IPN showed only one T-g, and hence a homogeneous-phase morphology was suggested. The second-order nonlinear optical coefficient (d(33)) of the IPN was measured to be 1.72 X 10(-7) esu. The study of NLO temporal stability at room temperature and elevated temperature (100 degrees C) indicated that the IPN exhibits a high stability in the dipole orientation due to the permanent entanglements of two component networks in the IPN system. Long-term stability of second harmonic coefficients was observed at room temperature for more than 1000 h.

Effect of Polymer Network Morphology on the Performance of Polymer Dispersed Liquid Crystal (PDLC) Composite Films

The effects of the morphologies of liquid crystal (LC) droplets left in polymer network on the performance of polymer dispersed liquid crystal composite films were investigated.By adjusting the relative content range of the crosslinking and diluents,the morphologies of polymer network can be changed.Therefore,the properties of PDLC composite films with imparity polymer morphologies were obtained by experiments and the finite element simulation.Results of the experimental and finite element simulation showed that the electro-optical properties of PDLC composite films were inversely proportional to the domain size of the polymer network and the mechanical properties were proportional to the domain size of the polymer network.

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.

Preparation of Semi-interpenetrating Polymer Network of Silicon Rubber and Poly(methyl methylacrylate) Using Supercritical CO_2

The heterogeneous free-radical polymerization of methyl methylacrylate (MMA) and divinylbenzene (DVB) as cross-linker within supercritical carbon dioxide-swollen silicon rubber (SR) has been studied as an approach to preparing semi-interpenetrating polymer network (semi-IPN) of SR and poly(methyl methylacrylate) (PMMA). The SR/PMMA semi-IPNs were characterized by scanning electron microscopy (SEM) and dynamic mechanical analyzer (DMA).

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 ℃.

Influence of Interpenetrating Polymer Networks (IPN) Microstructure on Underwater Acoustic Stealth Performance

According to the configuration and absorption theory of polymer macromolecule materials, a kind of IPN with wider temperature range and higher damping property was designed and synthesized. By using the spectrum of dynamic mechanical thermal analysis （DMTA） and acoustic pulse tube device, the microstructure, phase separation degree, phase size and phase continuity of IPN with different components were analyzed. The experimental results show that the nano size grade of phase, the continuous and homogeneous IPN phase can provide higher absorption coefficient. The absorption coefficient of optimized sample I09 is 0.7 in 2 kHz, and the absorption peak is 0.9 in 4 kHz. Then the underwater acoustic properties of modified IPN filled with mica, micro-balloon and nano-SiO2 were discussed respectively to indicate that the inhomogeneous property of filler-modified IPN can improve the underwater acoustic stealth performance effectively, and the micro size grade of these filler-modified IPN can work well in low frequency acoustic stealth.

Gas Permeability and Free Volume Hole Properties of Interpenetrating Polymer Network Studied by Positrons

A series of polyurethane/epoxy resin interpenetrating polymer networks （PU/ER IPN） were studied by positron annihilation lifetime spectroscopy （PALS）. The effects of epoxy resin type and content on the free volume properties in IPN were investigated. We found that in PU/ER IPN, the free volume hole size and fractional free volume showed a negative deviation due to closer segmental chain packing through some chemical bonding between PU and epoxy resin. Direct relationship between the gas permeability and the free volume has been established based on the free volume theory. Experimental results revealed that the free volume plays an important role in determining the gas diffusion and permeability.