Ionic conductivity and morphology of semi‐interpenetrating‐type polymer electrolyte entrapping poly(siloxane‐g‐allyl cyanide)

We prepared a semi‐IPN (interpenetrating network)‐type solid polymer electrolyte (SPE) using poly (ethylene glycol)dimethacrylate (PEGDMA) as a polymer matrix containing a monocomb‐type poly(siloxane‐g‐allyl cyanide) and poly(ethylene glycol)dimethylether (PEGDME) for the lithium secondary battery. The poly(siloxane‐g‐allyl cyanide)s were prepared by a hydrosilation reaction of poly (methyl hydrosiloxane) with allyl cyanide and characterized by ¹H NMR and FTIR. The semi‐IPN‐type electrolyte was prepared by thermal curing, and conductivities of samples were measured by impedance spectroscopy using an indium tin oxide (ITO) electrode. The ionic conductivity of the semi‐IPN‐polymer electrolyte was about 1.05 × 10^?5 S cm^?1 with 60 wt % of the poly(siloxane‐g‐allyl cyanide) and 6.96 × 10^?4 S cm^?1 with 50 wt % of the PEGDME and 10 wt % of the poly(siloxane‐g‐allyl cyanide) at 30°C. The SEM morphology of the cross section of the semi‐IPN‐polymer electrolyte film was changed from discontinuous network to continuous network as increasing the PEGDME content and decreasing the poly(siloxane‐g‐allyl cyanide) content. The mechanical stability was also enhanced when increasing the PEGDME content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermoresponsive poly(ϵ‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) graft copolymers prepared by a combination of ring‐opening polymerization and sequential azide–alkyne click chemistry

A straightforward strategy is described to synthesize poly(?‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) (PCL‐g‐PNIPAAm) amphiphilic graft copolymers consisting of potentially biodegradable polyester backbones and thermoresponsive grafting chains. PCL with pendent chlorides was prepared by ring‐opening polymerization, followed by conversion of the pendent chlorides to azides. Alkyne‐terminated PNIPAAm was synthesized by atom transfer radial polymerization. Then, the alkyne end‐functionalized PNIPAAm was grafted onto the PCL backbone by a copper‐catalyzed azide–alkyne cycloaddition. PCL‐g‐PNIPAAm graft copolymers self‐assembled into spherical micelles comprised of PCL cores and PNIPAAm coronas. The critical micelle concentrations of the graft copolymers were in the range 7.8–18.2 mg L^?1, depending on copolymer composition. Mean hydrodynamic diameters of micelles were in the range 65–135 nm, which increased as the length of grafting chains grew. PCL‐g‐PNIPAAm micelles were thermosensitive and aggregated upon heating. © 2014 Society of Chemical Industry     

Ammonia‐functionalized particulate poly(glycidyl methacrylate‐co‐ethylene dimethacrylate)‐based polymers as stationary phase for protein retention

A poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) polymeric matrix was synthesized, amino‐functionalized and packed to be tested for protein retention and separation. Functionalization was carried out by reacting the epoxy groups with 30% ammonia solution to provide amino groups for anion exchange with proteins. Physical characterization of the particulate material showed that the functionalized polymer is macroporous and exhibits a unimodal pore size distribution. The resin presents good thermal stability. Chromatographic characterization using bovine serum albumin (BSA) and α‐lactalbumin as model proteins showed good retention properties for the amino‐functionalized matrix. The values obtained for the equilibrium constant (K) were around 3 for BSA, both in batch reactor and column‐packed operation mode. The K values for α‐lactalbumin were even higher, 8.01 and 4.65 for the batch and column‐packed experiments, respectively. Finally, axial dispersion coefficients were obtained, with a constant value of 0.0141 cm²s^?1 for BSA. Higher values were obtained for α‐lactalbumin, but in this case the axial dispersion coefficient was not constant and its values were dependent on the flows used. © 2001 Society of Chemical Industry     

Crosslinked hydroxyl‐conductive copolymer/silica composite membranes based on addition‐type polynorbornene for alkaline anion exchange membrane fuel cell applications

Crosslinked hydroxyl‐conductive copolymer/silica composite membranes based on addition‐type polynorbornene, poly(dodoxymethylene norbornene‐co‐norbornene‐3‐(trimethylpropyl ammonium)‐functionalized silica (QP(DNB/NB‐SiO₂), were prepared by a sol–gel method. Copolymer composite membranes with different degree of quaternary ammonium functional silica, designated as QP(DNB/NB‐SiO₂‐X) (X = 5, 10, 15 and 25 wt%, respectively), displayed good dimensional stabilities with low in‐plane swelling rate of 1.32–3.7%, good mechanical properties with high elastic modulus of 605.4–756.8 MPa and high tensile strength of 13.2–20 Mpa. The achieved copolymer composite membranes could self‐assemble into a microphase‐separated morphology with randomly oriented long‐range aliphatic chain/cylinder ionic channels that were imbedded in the hydrophobic PNB matrix. Among these membranes, the QP(DNB/NB‐SiO₂‐25) showed the parameter with ionic conductivity of 9.33 × 10^?3S cm^?1, methanol permeability of 2.89 × 10^?7cm² s^?1, and ion‐exchange capacity(IEC) of 1.19 × 10^?3 mol g^?1. A current density of 82.3mA cm^?2, the open circuit voltage of 0.65 V and a peek power density of 32 mW cm^?2 were obtained. POLYM. ENG. SCI., 58:13–21, 2018. © 2017 Society of Plastics Engineers     

Novel nanocomposite of poly(acrylonitrile‐co‐glycidyl methacrylate) crosslinked with Jeffamine‐functionalized multiwalled carbon nanotubes as gel polymer electrolytes

Multiwalled carbon nanotubes (MWCNTs) were functionalized with α,ω‐diamino poly(propylene oxide) (Jeffamine) of different molecular weights and crosslinked with poly(acrylonitrile‐co‐glycidyl methacrylate) [P(AN‐GMA)] to prepare a novel nanocomposite for applications in gel polymer electrolytes (GPEs). The synthesized copolymer was characterized by ¹H‐NMR, Fourier transform infrared, and thermal analysis. Scanning electron microscope observation revealed that the Jeffamine‐functionalized MWCNTs distributed uniformly in the nanocomposite membrane. The mechanical behaviors of the nanocomposite membranes were investigated. It was found that the crosslinked nanocomposite membranes of P(AN‐GMA) and Jeffamine‐functionalized MWCNTs exhibited much higher mechanical strength than the counterpart nanocomposite obtained by physical blending. Moreover, the weight content and molecular weights of Jeffamine had an effect on the mechanical properties of the nanocomposites. Differential scanning calorimeter measurements showed that the crosslinked nanocomposite membranes were amorphous. GPEs based on the nanocomposite were prepared and characterized by complex impedance measurements. The GPE based on the nanocomposite of P(AN‐GMA) crosslinked with 6 wt % of MWCNTs functionalized by Jeffamine D400 showed an ionic conductivity of about 3.39 × 10^?4 S cm^?1 at 25°C, which is much higher than the counterpart nanocomposite of physically blended P(AN‐GMA) and MWCNTs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microwave‐assisted in situ polymerization of polycaprolactone/boron nitride composites with enhanced thermal conductivity and mechanical properties

Polycaprolactone/boron nitride (PCL/BN) composites were prepared by microwave‐assisted ring‐opening polymerization of ε‐caprolactone (ε‐CL). In order to improve the dispersibility and interfacial interaction between BN fillers and PCL matrix, hydroxyl functional BN (mBN) was first prepared to be used as a macroinitiator for ε‐CL. Then BN grafted PCL (BN‐g‐PCL) copolymers were obtained via the in situ method, which acted as in situ compatibilizers in the PCL/BN composites. Various techniques were applied to characterize the mBN and PCL/BN composites. The Fourier transform infrared spectroscopy results confirm the structure of the BN‐g‐PCL copolymer. Field emission SEM graphs exhibit that, for the PCL/mBN composites, the mBN presents a homogeneous dispersion in the matrix and interfacial adhesion between the PCL and mBN is improved. These are beneficial for enhancing the thermal conductivity of the PCL/mBN composites. Notably, the PCL/mBN composite with 5 wt% mBN loading achieves the highest thermal conductivity of 0.55 W m^?1 K^?1, which is 2.75 times higher than that of pure PCL, 0.20 W m^?1 K^?1. This indicates that the excellent dispersion and interfacial adhesion could lead to the construction of continuous thermal conductive paths at a low BN loading and reduce the heat loss caused by phonon scattering in the interface. Furthermore, mBN could help to improve the mechanical properties of the composite. On adding 5 wt% mBN, the tensile strength and tensile modulus of the composite are 1.58 and 2.05 times higher, respectively, than those of PCL. © 2020 Society of Chemical Industry     

Grafting of sulfonated monomer onto an amino‐silane functionalized 2‐aminoterephthalate metal − organic framework via surface‐initiated redox polymerization: proton‐conducting solid electrolytes

A post‐polymerization method for metal–organic frameworks (MOFs) has been developed to produce super‐acidic solid nanoparticles. Thus, the NH₂MIL‐53(Al) MOF was functionalized with (3‐aminopropyl)triethoxysilane (APTES) from amine groups to yield active site anchored MOF nanoparticles. Then, sulfonated polymer/MOF hybrid nanoparticles were prepared by redox polymerization of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (MOF‐g‐PAMPS), initiated onto the surfaces of aminopropyl‐functionalized NH₂MIL‐53(Al) nanoparticles. The synthesis and modification of NH₂MIL‐53(Al) nanoparticles were characterized by Fourier transform infrared (FTIR) spectroscopy and TGA. FTIR and TGA results indicated that APTES modifier agent and AMPS monomer were successfully grafted onto the MOF nanoparticles. The grafting efficiency of PAMPS polymer onto the MOF nanoparticles was estimated from TGA thermograms to be 33%. Also, sulfonated polymer/MOF hybrid nanoparticles showed a proton conductivity as high as 4.9 × 10^?5 S cm^?1. Nitrogen adsorption of modified NH₂MIL‐53(Al) showed also a decrease in pore volume. The morphology and crystalline structure of MOF nanoparticles before and after the modification processes were studied by SEM and XRD, respectively. © 2015 Society of Chemical Industry     

Synthesis and characterization of novel urethane‐siloxane copolymers with a high content of PCL‐PDMS‐PCL segments

Novel polyurethane copolymers derived from 4,4′‐methylenediphenyl diisocyanate (MDI), 1,4‐butanediol (BD) and α,ω‐dihydroxy‐[poly(caprolactone)‐poly (dimethylsiloxane)‐poly(caprolactone)] (α,ω‐dihydroxy‐(PCL‐PDMS‐PCL); = 6100 g mol^?1) were synthesized by a two‐step polyaddition reaction in solution. In the synthesis of the polyurethanes, the PCL blocks served as a compatibilizer between the nonpolar PDMS blocks and the polar comonomers, MDI and BD. The synthesis of thermoplastic polyurethanes (TPU) with high soft segment contents was optimized in terms of the concentrations of the reactants, the molar ratio of the NCO/OH groups, and the time and temperature of the polyaddition reaction. The structure, composition, and hard MDI/BD segment length of the synthesized polyurethane copolymers were determined by ¹H, ¹³C‐NMR, and two‐dimensional correlation (COSY, HSQC, and HMBC) spectroscopy, while the hydrogen bonding interactions in the copolymers were analyzed by FT‐IR spectroscopy. The influence of the reaction conditions on the structure, molecular weight, thermal, and some physical properties was studied at constant composition of the reaction mixture. A change in the molar ratio of the NCO/OH groups and the reaction conditions modified not only the molecular weight of the synthesized polyurethanes, but also the microstructure and therefore the thermal and physical properties of the copolymers. It was demonstrated that only PCL segments with high soft segment contents crystallize, thereby showing spherulitic morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of hyaluronan/chitosan scaffold cross‐ linked by 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide

A novel biocompatible scaffold was prepared by cross‐linking hyaluronan (HA) and chitosan (CS). The carboxyl groups of HA were activated by 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide (EDC) and then cross‐linked with amino groups of CS by forming amide bonds. The HA/CS scaffold thus prepared was characterized using Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and differential scanning calorimetry. FTIR spectra showed that the absorbance of the amide (1550 cm^?1) and carbonyl (1633 cm^?1) bond in the cross‐linked scaffold was stronger than that in HA or CS. SEM micrographs showed that the cross‐linked scaffold produced at low EDC concentration had an intertwisted ribbon‐like microstructure, while the product prepared at higher EDC concentration had a porous structure. The concentration of EDC in the reaction system greatly affected the structure and properties of the HA/CS scaffold. The prepared scaffold could strongly resist degradation by hyaluronidase, free radicals in vitro and stress. Copyright © 2007 Society of Chemical Industry     

Nanoporous Low Dielectric Cyclosiloxane Bearing Polysilsesquioxane Thin Films Templated by Poly(ε‐caprolactone)

Summary: Dielectric cyclosiloxane bearing polysilsesquioxanes (CS‐PSSQs) were prepared by acid catalyzed polymerization using 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The molecular weight, and content of the functional end‐groups of the CS‐PSSQs were found to be dependent on the process parameters, such as the molar ratio of water and catalyst to the ? OCH₃ group of the silane monomer, the amount of solvent, and the poly(ε‐caprolactone) (PCL) content, etc. Based on these CS‐PSSQ prepolymers, nanoporous organic/inorganic hybrid thin films were fabricated by spin‐coating mixtures of these prepolymers with star‐shaped PCL on the silicon substrate, and subsequently heating them at 150 and 250 °C for 1 minute each and then at 420 °C for 1 hour. A dielectric constant as low as 2.28 was achieved for the nanoporous PCL/CS‐PSSQ (3:7 v/v) film, along with low moisture absorption in ambient and water conditions, primarily due to the presence of hydrophobic moieties such as ethylene and methyl groups of the polymer and nano‐sized hydrophobic pores inside the matrix, resulting in the film having stable dielectric properties. Moreover, the PCL/CS‐PSSQ (3:7 v/v) nanohybrid film revealed a nanoporous structure containing ca. 1.52 nm of average‐sized mesopores, as measured by the N₂ adsorption method. The CS‐PSSQ‐only film showed high mechanical strengths having an elastic modulus and hardness of 6.64 and 0.88 GPa, respectively, for the 7 500 Å thick film and 2.41 and 0.38 GPa, respectively, for the PCL/CS‐PSSQ (3:7 v/v) film. In addition, the crack velocity of the CS‐PSSQ‐only film was found to be ca. 10^?11 m · s^?1 in ambient conditions and an aqueous environment, probably due to the enhanced hydrophobicity and mechanical toughness of the incorporated methyl group, siloxane unit and ethylene moieties in the polymer matrix.

     

Synthesis of chitosan‐graft‐poly[2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate] copolymer from a novel monomer,prepared using a Morita–Baylis–Hillman reaction,and characterization of its antimicrobial activity

A novel method has been developed to modify the natural polymer chitosan. The process utilizes a monomer prepared by employing a Morita–Baylis–Hillman (MBH) reaction. Specifically, the vinyl monomer 2‐[hydroxy(pyridin‐3‐yl)methyl]acrylonitrile (HPA) was synthesized using a high‐yielding MBH reaction of acrylonitrile with pyridine‐3‐carboxaldehyde in the presence of 1,4‐diazabicyclo[2.2.2]octane. Conversion of HPA to 2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate (CPA) was then carried out by reaction of acryloyl chloride. The highly functionalized monomer CPA was grafted onto chitosan through a reaction in 2% acetic acid containing a persulfate and a sulfite (K₂S₂O₈/Na₂SO₃) as redox promoter. An optimal grafting percentage of 123% is obtained when the grafting process is conducted at 60 °C for 4 h employing a 1:0.5 ratio of K₂S₂O₈ and Na₂SO₃ at a concentration of 2.5 × 10^?3 mol L^?1. Chitosan‐graft‐poly[2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate] graft copolymers, having various grafting percentages, were characterized using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies, X‐ray diffraction, thermogravimetric analysis and scanning electron microscopy. Finally, the results of studies probing the antimicrobial activities of the polymers against selected microorganisms show that the graft copolymers display higher growth inhibition activities against bacteria and fungi than does chitosan. © 2014 Society of Chemical Industry     

Synthesis,characterization and crosslinking of functional star‐shaped poly(ε‐caprolactone)

Star‐shaped low molecular weight poly(ε‐caprolactone)s (PCLs) were synthesized and functionalized with crosslinkable terminal groups for subsequent crosslinking. The ε‐caprolactone (CL) prepolymers were polymerized by ring‐opening in the presence of polyglycerine (PGL) as an initiator (1, 3 and 5 mol%) and Sn(II)2‐ethylhexanoate as a catalyst. Characterization of the prepolymer by ¹³C/¹H nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) revealed a six‐armed star‐shaped structure for the prepolymer with the molecular weight controlled by the ratio of PGL and CL. Functionalization of the hydroxyl‐terminated prepolymer was carried out with maleic or itaconic anhydride. In both cases, the characterization of the functionalized prepolymer showed that the hydroxyl groups were completely substituted. The functionalized PCLs were successfully crosslinked through the reaction of double bonds. The crosslinking was induced either thermally with organic peroxide or photochemically with a photosensitive initiator. Characterization of the crosslinked PCLs by Soxhlet extraction, DSC and FTIR showed that the itaconic double bond was much more reactive in thermal crosslinking than the maleic double bond. Thus, the crosslinked prepolymers that were functionalized with itaconic double bonds achieved a gel content of about 90%. A gel content of 100% was achieved with several compositions where crosslinking agents were employed. © 2002 Society of Chemical Industry     

Synthesis and thiol–ene photopolymerization of (meth)allyl‐terminated polysulfides

Thiol‐terminated polysulfides (PS) are cured by mixing with an oxidant, resulting in limited shelf‐ and/or pot‐life, depending on whether formulated as a one‐ or two‐component system. Mixtures of thiol‐ and alkene‐terminated polysulfides offer the potential for an on‐demand curing process through thiol–ene photopolymerization. Thiol end groups of commercial polysulfides, PS‐1 (1000 g/mol) and PS‐2 (3000 g/mol), were converted to alkene by reaction with (meth)allyl bromide. Photopolymerizations were performed by irradiating films of equimolar thiol:ene mixtures at 320–500 nm (30 mW/cm²) in the presence of 5 wt % 2,2‐dimethoxy‐2‐phenyl‐acetophenone (DMPA). Reaction kinetics were measured using real‐time FTIR by monitoring absorbances at 3075 cm^?1 (alkene) or 2550 cm^?1 (thiol). In the absence of any reactive diluent, mixtures of thiol and alkene polysulfides failed to gel notwithstanding high reaction conversion (>90%). Partial or total replacement of the thiol polysulfide component with pentaerythritol tetrakis(3‐mercaptopropionate) (PETMP) yielded solid elastomeric films and ultimate reaction conversions of 80–96% after 5 min irradiation. Crosshatch adhesion measured on glass, aluminum, and steel was very poor (0B) for (meth)allyl PS‐1/PETMP and poor (2B) for (meth)allyl PS‐2/PETMP without adhesion promoters. (3‐Mercaptopropyl)trimethoxysilane (1 wt %) significantly improved adhesion of (meth)allyl PS‐2/PETMP on all substrates (4B) but yielded no improvement for (meth)allyl‐terminated PS‐1/PETMP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45523.     

Synthesis and characterization of bis‐triethoxysilane endcapped polyurethane/urea

A type of bistriethoxysilane endcapped polyurethane/ureas (SPU) with well‐defined structure was synthesized from bis(triethoxysiylpropyl) amine and purified prepolymers, which were obtained from the reaction of 2,4‐toluene diisocyanate (TDI) and polyoxyethylene glycol (PEG) with different molecular weight. Then, fourier transform infrared spectroscopy (FTIR), hydrogen nuclearmagnetic resonance (¹H‐NMR) and standard dibutylamine back‐titration method were used to confirm the structures of prepolymers and SPUs. Moreover, the properties of SPU were investigated by wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), and percentage of water uptake. Results indicated that these polyurethanes were amorphous, and the percentage of water uptake and thermal stability of these polyurethanes went up with the increase of M _n of SPU, accompanying with the glass transition temperature (T_g) values decreased with the increase of M _n. This study provides us with a method to synthesize well‐defined end‐functionalized polyurethane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Solubilization of graphene flakes through covalent modification with well‐defined azido‐terminated poly(ε‐caprolactone)

A well‐defined poly(ε‐caprolactone) (PCL) with terminal azido group was prepared. Grafting‐on reaction between the azido‐terminated PCL (N₃? PCL) and ultrasonication‐assisted exfoliated graphene flakes (GF) was carried out to obtain PCL‐grafted‐GF (PCL‐g‐GF) which showed good dispersibility in a wide variety of organic solvents. Gel permeation chromatography, ¹H NMR, IR, Raman, UV‐vis, and TEM measurements indicated that PCL macromolecules were covalently introduced on the surface of GF without disrupting the structure of GF. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41569.     

Synthesis of ZSM‐5 by hydrothermal method with pre‐mixing in a stirred‐tank reactor

This work proposed a synthesis route of ZSM‐5 via the hydrothermal method with premixing in a stirred tank reactor (STR). Effects of various operating conditions, including pre‐mixing time, molar ratio of SiO₂/Al₂O₃, TPAOH (organic template agents) concentration, NaCl (alkali metal cations) concentration, crystallization temperature, and crystallization reaction time, on the average particle size (PS) and particle size distribution (PSD) were investigated. It was found that the pre‐mixing time in the STR significantly affect the formation of proto‐nuclei in premixing process and crystal growth in hydrothermal reaction process, and consequently influence the PS and PSD of the prepared ZSM‐5. ZSM‐5 with good thermal stability, a PS of 380 nm, PSD of 0.17–0.9 µm, pore diameter of 2.31 nm, pore volume of 0.19 cm³ · g^?1 and specific surface area of 337.25 m² · g^?1 were obtained under the optimal conditions of a crystallization reaction time of 24 h, a crystallization temperature of 130 °C, a molar ratio of SiO₂/Al₂O₃ of 200, a TPAOH concentration of 3.5 mol · L^?1, NaCl concentration of 0.3 mol · L^?1, and a pre‐mixing time of 5 h. This work indicated that the operating conditions including premixing time have a significant effect on its PS and PSD.     

Phosphorylcholine end‐capped poly‐ε‐caprolactone: A novel biodegradable material with improved antiadsorption property

In this study, the synthesis, characterization, and properties of a novel biodegradable polymer with improved hemocompatibility were introduced. It was synthesized by end‐capping poly‐ε‐caprolactone (PCL) with phosphorylcholine (PC) groups. The polyester backbone provided the mechanical stability and biodegradability, while the PC‐end groups improved its hemocompatibility. The obtained polymer was characterized using ¹H NMR, ³¹P NMR, FTIR, and GPC, its crystallization behavior was studied by DSC. Compared with original PCL, the resulting polymer (PC‐PCL) showed a lower crystallization capability and a faster degradation rate in PBS. The degradation rate of the polymer blends of PCL/PC‐PCL increased with increasing PC‐PCL content. The results of water contact angle measurements revealed a more hydrophilic surface property of PC‐PCL than neat PCL. The hemocompatibility of PC‐PCL was estimated using rabbit platelet‐rich plasma, a better resistance to platelet adhesion and activation was observed. During the human blood plasma contacting process, PC‐PCL showed a prolonged activated partial thromboplastin time over neat PCL. Material–cell interaction was evaluated with human umbilical vein endothelial cell, the result indicated that PC‐PCL may to some extent have an antihyperplasia property, compared with neat PCL. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 989–997, 2007     

Poly(ϵ‐caprolactone)‐functionalized carbon nanofibers by surface‐initiated ring‐opening polymerization

Carbon nanofibers (CNFs) were covalently functionalized with biodegradable poly(?‐caprolactone) (PCL) by in situ ring‐opening polymerization (ROP) of ?‐caprolactone in the presence of stannous octoate. Surface oxidation treatment of the pristine CNFs afforded carboxylic CNFs (CNF‐COOH). Reaction of CNF‐COOH with excess thionyl chloride (SOCl₂) and glycol produced hydroxyl‐functionalized CNFs (CNF‐OH). Using CNF‐OH as macroinitiator, PCL was covalently grafted from the surfaces of CNFs by ROP, in either the presence or absence of sacrificial initiator, butanol. The grafted PCL content was achieved as high as 64.2 wt %, and can be controlled to some extent by adjusting the feed ratio of monomer to CNF‐OH. The resulting products were characterized by FTIR, NMR, Raman spectroscopy, TGA, DSC, SEM, TEM, HRTEM, and XRD. Core–shell nanostructures were observed under HRTEM for the PCL‐functionalized CNFs because of the thorough grafting. The PCL‐grafted CNFs showed different melting and crystallization behaviors from the mechanical mixture of PCL and CNF‐OH. This approach to PCL‐functionalized CNFs opens an avenue for the synthesis, modification, and application of CNF‐based nanomaterials and biomaterials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of high‐density polyethylene/rGO‐CNT‐Fe nanocomposites with outstanding magnetic and electrical properties

Semi‐conducting polyethylene (PE) nanocomposites with outstanding magnetic properties at room temperature were synthesized. These exceptional properties, for a diamagnetic and insulating matrix as PE, were obtained by polymerizing ethylene in the presence of a catalytic system formed by a metallocene catalyst supported on a mixture of reduced graphene oxide (rGO) and carbon nanotubes with encapsulated iron (CNT‐Fe). It was used a constant and very low amount of CNT‐Fe, obtained by vapor chemical deposition using ferrocene. The percolation threshold, to achieve conductivity, was obtained using a variable amount of rGO. The nanocomposites were semiconductors with the addition of 2.8 wt % and 6.0 wt % of the filler, with electrical conductivities of 4.99 × 10^?6 S cm^?1 and 7.29 × 10^?4 S cm^?1, respectively. Very high coercivity values of 890–980 Oe at room temperature were achieved by the presence of only 0.04–0.06 wt % of iron in the nanocomposites. The novelty of this work is the production of a thermoplastic with both, magnetic and electric properties at room temperature, by the use of two fillers, that is rGO and CNT‐Fe. The use of a small amount of CNT‐Fe to produce the magnetic properties and variable amount of rGO to introduce the electrical conductivity in PE matrix let to balance both properties. The encapsulation strategy used to obtain Fe in CNT, protect Fe from easy oxidation and aggregation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45382.     

Preparation and characterization of proton exchange membrane based on polyphosphoric acid modified by PVDF‐HFP

A polyphosphoric acid functionalized proton exchange membrane (PEM) was prepared by a ring opening reaction using the epoxycyclohexylethyltrimethoxysilane (EHTMS) and amino trimethylene phosphonic acid (ATMP) as raw materials and was modified by poly(vinylidene fluoride)–hexafluoro propylene (PVDF‐HFP). The structure of the membranes was characterized by Fourier transform infrared and scanning electron microscopy. The X‐ray photoelectron spectroscopy explores the content of the elements in the membrane related to the ion exchange capacity value. The membranes’ properties including water uptake, swelling ratio, proton conductivity, and hydrolysis stability were studied. Performance tests show that when ATMP/EHTMS = 1/5, conductivity of the PVDF‐HFP modified PEMs increased from 0.83 × 10^?4 S cm^?1 at 20 °C to 9.53 × 10^?3 S cm^?1 at 160 °C, the swelling ratio of membranes decreased from 2.71% to 2.13%. The results indicate that the introduction of F atoms is beneficial to increase the proton conductivity and the dimensional stability. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46737.