Fabrication by photoinitiated polymerization and characterization of millimeter‐size poly(divinyl benzene) hollow foam shells

In this study, millimeter‐size compound droplets were prepared easily by a one‐step microfluidic method. We varied the diameter and wall thickness of the shells over a wide range by setting the flow rate. Poly(divinyl benzene) (PDVB) shells with a 3–4.8 mm diameter were fabricated through photopolymerization and supercritical drying. The gel point of photopolymerization was monitored by a rotational rheometer. Moreover, the influence of the oil‐soluble photoinitiator phenyl bis(2,4,6‐trimethyl benzoyl) phosphine oxide (BAPO) on the properties of the foam shell were investigated by transmission electron microscopy, scanning electron microscopy, and nitrogen sorption measurements. Significant differences in the mechanical properties and porous features were obtained for different BAPO concentrations. The surface areas of the foam shells decreased, and the densities of the foam shells increased with increasing BAPO concentration. In addition, the nonconcentricity and out‐of‐roundness values were mainly less than 7 and 3%, respectively, for most of the shells. The results indicate that the PDVB hollow foam shells are a promising inertial fusion energy target. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41625.     

Effect of poly(ethylene glycol) on the properties and foaming behavior of macroporous poly(lactic acid)/sodium chloride scaffold

In this study, we prepared poly(lactic acid) (PLA)/poly(ethylene glycol) (PEG)/sodium chloride (NaCl) blends by melt blending with a triple‐screw dynamic extruder. The effects of PEG on the thermal property, mechanical property, and morphology of blends were investigated in detail. It was found that the incorporation of PEG and NaCl significantly improved the crystallization rate, elongation at break, surface adhesion, and reduced viscoelasticity of PLA. The blends were further batch‐foamed at different temperatures with supercritical carbon dioxide to study the foaming properties. The results of PLA/PEG/NaCl (50 : 10 : 40 wt %) composites after foaming and particle leaching revealed that an interconnected bimodal porous scaffold with the highest porosity of 89% could be achieved. Furthermore, the addition of PEG can significantly reduce the water contact angle so as to enhance the wetting ability of the scaffolds. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41181.     

Preparation and gel properties of poly(ether ether ketone) with pendent sulfonimide groups

Poly(ether ether ketone) with pendent sulfonimide groups (B‐SPEEK) was prepared from poly(ether ether ketone), sulfuric acid, thionyl chloride, para‐toluene sulfonate, and pyridine. The prepared B‐SPEEK was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, and thermogravimetric analysis. The swelling of the gels was examined in N,N‐dimethylacetamide (DMAC), N,N‐dimethylformamide (DMF), 1‐methyl‐2‐pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), and a DMSO/water mixture. The gel showed extremely high swelling in DMSO, DMF, DMAC, and NMP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1058‐1063, 2013     

Swelling behavior of butyl and chloroprene rubber composites with poly(sodium acrylate) showing high water uptake

Water-swellable rubber (WSR) comprises super absorbent polymer (SAP) embedded in a rubber matrix and has been commonly used as sealants and caulks, in which high water uptake and sufficient mechanical strength are required. In this work, we investigated the swelling behavior and mechanical properties of rubber composites comprising SAP powders. A reinforcement effect is caused by the SAP particles, which are described using a modified Guth–Gold equation up to the semi-dilute region. The complex modulus shows upper deviation at high SAP content owing to network formation between SAP particles. The swelling force of the WSR is explained by the amount of SAP particles in the surface layer of the matrix up to the semi-dilute region. The formation of the SAP network leads to an appreciable increase in the swelling force of WSR, as SAP particles embedded in the matrix also contribute to the swelling of WSR. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48535.     

Preparation and pH‐responsive performance of silane‐modified poly(methylacrylic acid)

The poly(methylacrylic acid) modified by silane [poly(methylacrylic acid‐co‐vinyl triethoxylsilane) (PMAA)] was prepared via free‐radical polymerization with different mass ratios of methylacrylic acid to vinyl triethoxylsilane (VTES). The swelling performance of the prepared PMAA in different solutions with various pH values, salt species (NaCl and CaCl₂), and concentrations was investigated in detail. The results indicated that the introduction of silane boosted the stability of the obtained PMAA in aqueous solutions in the presence of an increased quantity of VTES additive. Meanwhile, the different swelling ratios of PMAA in various pH solutions showed a high pH responsivity. In addition, we found that when the PMAA underwent a number of swelling–deswelling cycles, it demonstrated the good reversibility properties when the pH value of the swelling medium was changed from 9.0 to 1.4. Moreover, the swelling mechanism of PMAA in different solutions with different pH values was investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40403.     

In situ injectable poly(γ‐glutamic acid) based biohydrogel formed by enzymatic crosslinking

Enzymatic crosslinking was developed to prepare in situ forming poly(γ‐glutamic acid) (γ‐PGA) based hydrogel in this study. First, the precursor of poly(γ‐glutamic acid)–tyramine (γ‐PGA–Ty) was synthesized through the reaction of carboxyl groups from a γ‐PGA backbone with tyramine. The structure of the grafted precursor was confirmed by ¹H‐NMR and Fourier transform infrared spectroscopy. After that, the crosslinking of the phenol‐containing γ‐PGA–Ty precursor was triggered by horseradish peroxidase in the presence of H₂O₂; this resulted in the formation of the γ‐PGA–Ty hydrogels. The equilibrium water content, morphology, enzymatic degradation rate, and mechanical properties of the hydrogels were characterized in detail. The data revealed that the well‐interconnected hydrogels had tunable water contents, mechanical properties, and degradability through adjustments of the composition. Furthermore, cell experiments proved the biocompatibility of the hydrogels by 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay. These characteristics provide an opportunity for the in situ formation of injectable biohydrogels as potential candidates in cell encapsulation and drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42301.     

Color change of an iodinated poly(vinyl alcohol) film by physical deformation

The color change of an iodinated poly(vinyl alcohol) (PVA) film caused by physical deformation was investigated in this study. The color of a PVA film soaked in an aqueous potassium iodide (KI)/I₂ solution was light yellow, but it turned light blue when the film was physically deformed. The ultraviolet–visible absorption spectrum of the iodinated PVA film extended uniaxially in air was measured at various extension levels. Without deformation, the film showed UV absorption bands at 210, 290, and 360 nm. However, under deformation, the film showed new visible light absorption bands at 440 and 620 nm. From the UV–vis absorption spectra of several iodinated solutions, we found that the absorption wavelength of iodine was affected by the cohesive energy of the solvents. The KI/I₂ diethyl ether solution showed an absorption band at 460 nm, and this provided a clue to understanding the color change of the PVA–iodine complexes caused by physical deformation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43036.     

In‐process thermochemical analysis of in situ poly(ethylene glycol methacrylate‐co‐glycidyl methacrylate) monolithic adsorbent synthesis

Thermomolecular mechanisms associated with the synthesis of polymethacrylate monoliths are critical in controlling the physicochemical and binding characteristics of the adsorbent. Notwithstanding, there has been limited reported work on probing the underlining synthesis mechanism essential in establishing the relationship between in‐process polymerization characteristics and the physicochemical properties of the monolith for tailored applications. In this article, we present a real‐time thermochemical analysis of polymethacrylate monolith synthesis by free‐radical polymerization to probe the effects on the physicochemical characteristics of the adsorbent. The experimental results show that an increase in the crosslinker monomer concentration from 30 to 70% resulted in a peak temperature increase from 96.3 to 114.3 °C. Also, an increase in the initiator (benzoyl peroxide) concentration from 1 to 3% w/v resulted in a temperature increase from 90.7 to 106.3 °C. A temperature buildup increases the kinetic rate of intermolecular collision associated with microglobular formation and interglobular interactions. This reduces the structural homogeneity and macroporosity of the polymer matrix. A two‐phase reactive crystallization model was used to characterize the rate of monomeric reaction after initiation and microglobular formation from the liquid monomeric phase to formulate the theoretical framework essential for evaluating the kinetics of the polymer formation process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43507.     

Synthesis and properties of waterborne poly(urethane urea)s containing polydimethylsiloxane

To obtain flexible waterborne poly(urethane urea) (WBPU) coatings with functionalities such as shape recovery and water resistance, we synthesized a series of WBPUs by a prepolymer mixing process from hexamethylene diisocyanate, polyol, 2,2‐bis(hydroxymethyl) propionic acid, ethylenediamine, and triethylamine with polyol blends [hydroxyl‐terminated polydimethylsiloxane (PDMS) with a number‐average molecular weight of ≈ 550 and poly(tetramethylene oxide) glycol (PTMG) with a number‐average molecular weight of 650] of different molar ratios. The effects of the PDMS content in PDMS/PTMG on the dynamic thermal and mechanical properties, hardness, tensile properties, water resistance (water absorption, contact angle, and surface energy), and shape‐memory properties of WBPU films were investigated. As the molar percentage of PDMS in WBPUs increased, the storage modulus, tensile strength and modulus, elongation at break, hardness, and shape‐retention rate (30–15%) decreased; however, the water resistance and shape‐recovery rate (80–90%) increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

In vitro hydrolysis and magnesium release of poly(d,l‐lactide‐co‐glycolide)‐based composites containing bioresorbable glasses and magnesium hydroxide

Magnesium is important for both bone growth and cartilage formation. However, the postoperative intake of antibiotics such as quinolones may cause a reduction in magnesium levels in tissue. The addition of magnesium to scaffolds may therefore be beneficial for the regeneration of osteochondral defects. In this study, porous composite scaffolds were produced by gas foaming of poly(d ,l ‐lactide‐co‐glycolide) (PLGA) rods with magnesium‐containing bioresorbable glasses and magnesium hydroxide as fillers. The in vitro hydrolytical degradation of the composite scaffolds in Tris buffer was followed over a 10‐week period. Mg²⁺ was released in a controlled manner from the scaffolds with varying release profiles between the different materials. Higher glass content resulted in a reduced mass loss compared to scaffolds with lower glass content. As a result of the foaming method, the scaffolds shrank initially, without evidence that the addition of hydrophilic fillers would decrease the initial shrinkage. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42646.     

Dynamic mechanical properties of semi‐interpenetrating polymer network‐based on nitrile rubber and poly(methyl methacrylate‐co‐butyl acrylate)

In this article, semi‐interpenetrating polymer network (Semi‐IPNs) based on nitrile rubber (NBR) and poly(methyl methacrylate‐co‐butyl acrylate) (P(MMA‐BA)) were synthesized. The structure and damping properties of the prepared Semi‐IPNs blends were characterized and by fourier transform infrared spectrum (FTIR), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), thermogravimetric analysis (TGA/DTG), and tensile mechanical properties. The results showed that interpenetrating network based on P(MMA‐BA) and NBR was successfully obtained, which showed the improved thermal stability compared to NBR/P(MMA‐BA)‐based two‐roll mill blends. Furthermore, Semi‐IPNs showed significantly better the dynamic mechanical properties than that of the two‐roll mill system. With the increasing feed ratio of BA and MMA during the preparation of Semi‐IPNs, the loss peak position for P(MMA‐BA) in NBR/PMMA IPNs shifted to a lower temperature from 20°C to ?17°C, and when NBR in Semi‐IPNs was accounted for 40 wt %, the dynamic mechanical thermal analysis showed that much more advanced damping material with wider temperature range (?30°C < T < 80°C) as tan δ > 0.45 can be achieved. Therefore, it was expected as a promising way to obtain the excellent damping materials with good oil‐resisted properties according the Semi‐IPNs system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40217.     

Lead(II)‐ion removal by ethylenediaminetetraacetic acid ligand functionalized magnetic chitosan–aluminum oxide–iron oxide nanoadsorbents and microadsorbents: Equilibrium,kinetics, and thermodynamics

Novel nanosized and microsized chitosan–Al₂O₃–Fe₃O₄ (CANF and CAMF, respectively) adsorbents were functionalized with ethylenediaminetetraacetic acid (EDTA) ligands and applied to the removal of Pb(II) ions. The prepared adsorbents were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller analysis, and their adsorption potentials were investigated with Pb(II) as a target metal under various experimental conditions. Our results show that the EDTA functionalization of CANF and CAMF increased their adsorption capacities about 31.5 and 38 times, respectively. The optimum dosage obtained was 1.0 g/L for both EDTA‐functionalized adsorbents, and the maximum adsorption took place at pH = 5.3. The kinetic results revealed that the adsorption obeyed the pseudo‐second‐order model and that the pore diffusion process played a key role in the adsorption kinetics. Also, the results of equilibrium isotherms indicate the good fit of the experimental data by the Langmuir isotherm model under the studied concentration and temperature ranges, and the adsorptions of Pb(II) ions from aqueous solution followed the monolayer coverage of the adsorbents. The maximum Pb(II)‐ion adsorption capacities of EDTA–CANF and EDTA–CAMF were 160 and 157 mg/g, respectively. These metal‐loaded adsorbents could be readily recovered from aqueous solution by magnetic separation and reused. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44360.     

Biocomposites based on poly(lactic acid) and superabsorbent sodium polyacrylate

In this research work, biocomposites based on crosslinked particles of sodium polyacrylate, commonly used as superabsorbent polymer, and poly(l ‐lactic acid) (PLLA) were developed to obtain superabsorbent thermoplastic products, and to elucidate the role of this type of filler (i.e., polymeric crosslinked particles) on their overall physical‐mechanical behavior. Samples prepared by melt‐blending components with different ratios showed a biphasic system with a uniform distribution of particles, with diameters up to about 50 μm, within the PLLA polymeric matrix. The polymeric biphasic system, coded PLASA, that is, superabsorbent PLLA, showed excellent swelling properties, demonstrating that crosslinked particles retain their superabsorbent ability even if distributed in a thermoplastic polymeric matrix. The thermal characteristics of the biocomposites evidenced enhanced thermal stability in comparison with neat PLLA and also mechanical properties are markedly modified by addition of crosslinked particles, revealing a regular stiffening effect. Furthermore, in aqueous environments the particles swell and are leached from PLLA matrix generating very high porosity. These new open‐pore foams coded PLASAW, that is, PLASA after water treatment, produced in absence of organic solvents and chemical foaming agents, with good physicomechanical properties appear very promising for several applications, for instance in tissue engineering for scaffold production. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45655.     

Rheology,morphology, and mechanical properties of HMSPP/POE blends and its alternate layered foam

In this article, the multilayered foaming sheet with alternate layered structure was successfully prepared through multilayer co‐extrusion. The high melt strength polypropylene (HMSPP)/poly (ethylene‐co‐octene) (POE) blend and POE were designed as foaming layers and film layers, respectively. POE was added into HMSPP to reduce the crystalline degree and improve the processing performance. The rheological results indicated that the addition of POE had a little effect on relaxation process and the strain hardening behavior of HMSPP when the POE content was lower than 50%. The results of the foam morphology showed that the cell size and its distribution of the multilayered foaming sheet with alternate layers were better than that with single layer. In addition, the cell size reduced and the cell density increased with increasing the number of layers from 4 to 32. The mechanical properties of the multilayered foaming sheet with alternate layers also could be improved through assembling of foaming layers and film layers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41339.     

Fabrication of co‐continuous poly(ε‐caprolactone)/polyglycolide blend scaffolds for tissue engineering

The apparent inability of a single biomaterial to meet all the requirements for tissue engineering scaffolds has led to continual research in novel engineered biomaterials. One method to provide new materials and fine‐tune their properties is via mixing materials. In this study, a biodegradable powder blend of poly(ε‐caprolactone) (PCL), polyglycolide (PGA), and poly(ethylene oxide) (PEO) was prepared and three‐dimensional interconnected porous PCL/PGA scaffolds were fabricated by combining cryomilling and compression molding/polymer leaching techniques. The resultant porous scaffolds exhibited co‐continuous morphologies with ～50% porosity. Mean pore sizes of 24 and 56 μm were achieved by varying milling time. The scaffolds displayed high mechanical properties and water uptake, in addition to a remarkably fast degradation rate. The results demonstrate the potential of this fabrication approach to obtain PCL/PGA blend scaffolds with interconnected porosity. In general, these results provide significant insight into an approach that will lead to the development of new composites and blends in scaffold manufacturing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42471.     

A novel foaming approach to prepare porous superabsorbent poly(sodium acrylic acid) resins

A system composed of surfactant and foam stabilizer is used in preparing porous superabsorbent resins (SARs) of poly(sodium acrylic acid) (PAA‐Na), which is obtained by free‐radical solution polymerization of partially neutralized acrylic acid with mechanical agitation of eggbeater. Different types of surfactant, including anionic surfactant sodium n‐dodecyl benzene sulfate (SDBS), cationic surfactant cetyltrimethyl ammonium bromide, and nonionic surfactant alkylphenols poly(oxyethylene) (OP‐10), are used as blowing agent to produce pores by mechanical agitation, and triethanolamine (TEA) is used to act as foam stabilizer agent. The results show that a synergistic effect of SDBS with TEA is obtained and the packing density is decreased, which could be proved by the clearly porous morphology, and the water absorbing capacity of SARs is enhanced. As a result, such method can get PAA‐Na SARs without any organic solvents, which provides an environmentally beneficial way to prepare SARs for hygiene and biomedical products. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41298.     

Self‐healing hydrogel of poly(vinyl alcohol)/graphite oxide with pH‐sensitive and enhanced thermal properties

Supramolecular hydrogel is a fascinating polymeric material composed of three‐dimensional noncovalent networks with many outstanding properties, especially reversible relevant performances. A self‐healing supramolecular hydrogel of poly(vinyl alcohol)/graphite oxide, with reversible pH responsiveness and good thermal stability, was prepared. The morphology, functional group changes, swelling performance, thermal stability, rheological performance, and self‐healing property of the PVA/GO hydrogel were investigated. A probable mechanism between the components and potential applications were also examined in our study. The experimental results show that the PVA/GO hydrogel was not only self‐healable without external stimulus or addition of any healing agents, but also pH sensitive and with good thermal stability. Green ingredients (PVA and GO) and a simple synthesis method (a freezing/thawing treatment) may pose little threat to the environment and also promote the production of such hydrogels. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46143.     

Thermal and mechanical behavior of poly(vinyl butyral)‐modified novolac epoxy/multiwalled carbon nanotube nanocomposites

The effects of poly(vinyl butyral) (PVB) and acid‐functionalized multiwalled carbon nanotube modification on the thermal and mechanical properties of novolac epoxy nanocomposites were investigated. The nanocomposite containing 1.5 wt % PVB and 0.1 wt % functionalized carbon nanotubes showed an increment of about 15°C in the peak degradation temperature compared to the neat novolac epoxy. The glass‐transition temperature of the novolac epoxy decreased with increasing PVB content but increased with an increase in the functionalized carbon nanotube concentration. The nanocomposites showed a lower tensile strength compared to the neat novolac epoxy; however, the elongation at break improved gradually with increasing PVB content. Maximum elongation and impact strength values of 7.4% and 17.0 kJ/m² were achieved in the nanocomposite containing 1.5 wt % PVB and 0.25 wt % functionalized carbon nanotubes. The fractured surface morphology was examined with field emission scanning electron microscopy, and correlated with the mechanical properties. The functionalized carbon nanotubes showed preferential accumulation in the PVB phase beyond 0.25 wt % loading. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43333.     

Catalytic behavior of Co(II) complexes with 2‐(benzimidazolyl)‐6‐(1‐(arylimino)ethyl)pyridine ligands on isoprene stereospecific polymerization

Polymerization behaviors of isoprene under different polymerization conditions with 2‐(1‐methyl‐2‐benzimidazolyl)‐6‐(1‐(arylimino)ethyl) pyridine cobalt(II) dichloride and ethylaluminum sesquichloride or diethylaluminum chloride catalyst system were evaluated. The effects of temperature, solvents, [Al]/[Co] molar ratio, and the structure of cocatalysts on the catalyst activity and the characteristics of polyisoprenes (PIs) were investigated and optimum conditions for synthesizing stereoselective PIs were obtained. The results showed that pre‐catalyst activity was strongly influenced by polymerization temperature, [Al]/[Co] molar ratio and solvents, and the kinds of solvents and cocatalysts affected the microstructures of PIs greatly. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39703.     

Secondary dopants modified PEDOT‐sulfonated poly(imide)s for high‐temperature range application

Poly(3,4‐ethylenedioxythiophene) (PEDOT) was polymerized using sulfonated poly(amic acid)s templates (SPAA1 and SPAA2) by batch operation. The new method was invented to enhance conductivities (ca. 100 ‐ to 2000‐fold) and with less reaction time from previous work (7 days vs. 3 days). Moreover, to increase the conductivity, many dopants were introduced as secondary doping compared with DMF, D ‐sorbitol, and surfynol that were previously used. After annealing at 180°C for 10 min, PEDOT‐SPAA1 and PEDOT‐SPAA2 doped with benzo‐1,4‐dioxan and quinoxaline showed the increase in conductivity by higher percentage than any other systems, especially doped with D ‐sorbitol and surfynol. These showed the promising tendency to develop the annealing activated superior conductivity materials after further modifying the conducting film forming processes. However, PEDOT‐SPAAs doped with benzo‐1,4‐dioxan, imidazole and quinoxaline via annealed at 180°C for 10 min were found to be more conductive than doped with DMF, but still lower conductive than doped with D ‐sorbitol and surfynol. In terms of particle size, the stable aqueous dispersions of conducting polymers prepared were comparable to polystyrene sulfonate template. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013