Preparation of polysiloxane phosphonic acid doped polybenzimidazole high‐temperature proton‐exchange membrane

Polysiloxane phosphonic acid doped polybenzimidazole (PBI) high‐temperature membranes were fabricated in this study. Polysiloxane phosphonic acid instead of phosphoric acid was used as a proton conductor to prevent acid from leaking. The membrane samples with different amounts of PBI were prepared and characterized with respect to the structure, thermal properties, oxidative stability, proton conductivity, and mechanical properties. The Fourier transform infrared results show that hydrogen bonds formed between PBI and polysiloxane phosphonic acid. Thermal analysis confirmed that the temperature at which membrane experienced 10% weight loss was above 230°C. None of the membrane samples broke into pieces after Fenton reagent testing. The proton conductivity of the membrane samples with 5% PBI was up to 0.034 S/cm at 140°C under nominally anhydrous conditions. The tensile strength of the membrane samples with 10% PBI was 18.3 MPa. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42956.     

Synthesis of hyperbranched polymers by free radical addition‐coupling polymerization with A3/B2 and A2A′/B2 approaches

Two tribromide compounds, 1,3‐(propanoic acid, 2‐bromo‐)‐2‐(2‐bromo‐1‐oxopropylamino)propyl ester (A 1 ) and trimethylolpropane tris(2‐bromopropionate) (A 2 ), were synthesized. By Cu/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (PMDETA)‐mediated radical addition‐coupling polymerization (RACP) of 2‐methyl‐2‐nitrosopropane (MNP) with the tribromide compounds, two types of hyperbranched polymers were synthesized under mild conditions, respectively. Polymerization degrees of the polymers increased with time gradually, which is in line with a step‐growth polymerization mechanism. By tracing the polymerization process by gel permeation chromatography and NMR analysis, proper reaction conditions to get hyperbranched polymers was obtained. Based on the results of NMR analysis on the polymer chain structure, mechanism of forming hyperbranched polymer has been proposed, which includes formation of carbon radicals from the tribromo monomer through single electron transfer, their reaction with MNP to form nitroxide radicals, and cross‐coupling reaction of the nitroxide radicals with other carbon radicals. The gelation point of the A 2 ‐MNP system is larger than that of the A 1 ‐MNP system, indicating that probability of intramolecular cyclization in A 2 ‐MNP RACP system is higher than the A 1 ‐MNP system. The reactivity of —NHCOCH(CH₃)Br group of A 1 is lower than its two —OCOCH(CH₃)Br groups, and this resulted in longer distance between two adjacent branch points in the hyperbranched polymer of A 1 ‐MNP than the A 2 ‐MNP system. It is possible to adjust the chain structure of RACP‐based hyperbranched polymer by changing the reactivity of the functional groups in A₃ monomer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41972.     

Surface modification and PEGylation of branched polyethyleneimine for improved biocompatibility

In this article, we report the surface modification of branched polyethyleneimine (PEI) for improved biocompatibility. PEIs with different surface functionalities were synthesized via covalent modification of the PEI amines, including neutralized PEI modified with acetic anhydride, negatively charged PEI modified with succinic anhydride, hydroxylated PEI modified with glycidol, and PEI–poly(ethylene glycol) (PEG) conjugates modified with both PEG and acetic anhydride. The modified PEI derivatives were characterized with ¹H‐NMR, Fourier transform infrared spectroscopy, and ζ‐potential measurements. An in vitro cytotoxicity assay of mouse fibroblasts revealed that the biocompatibility of PEI was significantly improved after these modifications. The neutral and negatively charged PEIs were nontoxic at concentrations up to 200 μg/mL, whereas the pristine PEI was toxic to cells at concentrations as low as 10 μg/mL. The successfully modified PEIs with different surface charges and functionalities may provide a range of opportunities for various biomedical applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of biomimetic hyperbranched zwitterionic polymers as targeting drug delivery carriers

Novel biomimetic hyperbranched copolymers that synthesized by polymerization of zwitterionic monomer (CBB) on the surface of a hyperbranched poly(3‐ethyl‐3‐(hydroxymethyl)oxetane) (HBPO) core and used as a drug delivery carrier have been investigated by analysis of protein‐adsorption‐resistance, cytotoxicity and cell type‐specific targeting properties. The as‐synthesized biomimetic hyperbranched copolymers showed low toxicity, favorable protein resistant properties and were ultrastable in 100% fetal bovine serum. Folic acid and rodiamin‐B were conjugated to the surface of synthesized micelles to endow it with target drug delivery and fluorescence activity, respectively. Intracellular uptake and in vitro cytotoxicity of HBPO‐poly(carboxybetaine) micelles were investigated. Doxorubicin was used as a model drug for Hela cells during the experiment. All results show that the biomimetic hyperbranched copolymer is a candidate carrier for target drug delivery. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The structure and application of amine‐terminated hyperbranched polymer shale inhibitor for water‐based drilling fluid

Amine‐terminated hyperbranched polymer (HBP‐NH₂), as an inhibitor in water‐based drilling fluid, is prepared by the polycondensation of diamine AB₂ monomers. The primary amine and secondary amide structures are confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy. Through time of flight mass spectrometry, the molecular weight of HBP‐NH₂ is mainly distributed in the range of 200–1400. Also, the quasi‐spherical shape and the high temperature resistance (200 °C) performance of HBP‐NH₂ are, respectively, certified through the environmental scanning electron microscope and the thermogravimetric analysis. In the inhibition performance test, the linear expansion rate of sodium bentonite in 3 wt % HBP‐NH₂ aqueous solution is only 11.42%, which is lower than other inhibitors (KCl, FA‐367, and HPAM). Zeta potential analysis shows that HBP‐NH₂ has a strong ability to inhibit the hydration and dispersion of sodium bentonite by protonated primary amine groups. Compared with the base slurry, the absolute value of zeta potential is reduced by 25.5 mV in the slurry containing 3 wt % HBP‐NH₂ at 180 rpm. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45466.     

Synthesis of UV‐curable hyperbranched polyurethane (meth)acrylate oligomers via thiol‐ene “click” chemistry

First, the second‐generation hyperbranched poly(amine‐ester) (G2‐OH) was successfully prepared by thiol‐ene “click” chemistry. Subsequently, a series of photosensitive hyperbranched oligomers (G2‐ORs) were synthesized by facile modifications of the G2‐OH with acryloyl chloride, methacryloyl chloride, IPDI‐HEA, and IPDI‐HEMA, respectively. The structures of hyperbranched oligomers were characterized by element analysis, FT‐IR, ¹H NMR, GPC and viscosity measurement. It was shown that these synthesized oligomers have narrow molecular weight distribution and low intrinsic viscosity at 30°C. UV–vis spectra results showed that the G2‐ORs had sharp absorption bands at around 202 nm. The results of photosensitivities measurement indicated that the G2‐Macr shows the highest photosensitive than other hyperbranched oligomers in the absence of photoinitiator. In addition, these UV‐cured photosensitive G2‐ORs had good thermal properties. The solubilities of the synthesized hyperbranched oligomers were also examined. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a branched photosensitive copolymer and its application for negative‐type photoresists

Novel branched copolymers, poly(styrene‐alt‐maleic anhydride) (BPSMA), were synthesized through mercapto chain‐transfer polymerization with styrene, maleic anhydride (MA), and 4‐vinyl benzyl thiol (VBT). Then, the hydroxyl of hydroxyethyl methacrylate was reacted with MA to synthesize branched photosensitive copolymers, p‐BPSMAs. Fourier transform IR spectroscopy and ¹H‐NMR indicated that the synthesis was successful. Gel permeation chromatography indicated that the molecular weight decreased with increasing content of VBT. The thermal properties were characterized by thermogravimetric analysis; the results show that the thermal decomposition temperature of the BPSMAs was greatly enhanced. Real‐time IR was used to evaluate the UV‐curable kinetics of the p‐BPSMAs; the results show that the p‐BPSMAs could rapidly photopolymerize under UV irradiation in the presence of photoinitiators. Moreover, the photoresist based on the p‐BPSMAs exhibited improved photosensitivity when the VBT content increased, and the photoresist with 12 mol % VBT content had a low value of the dose that retained 50% of the original film thickness (10 mJ/cm²), and a 50‐μm resolution could be achieved compared to a linear photoresist. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42838.     

Aging properties and hydrophilicity of maize starch plasticized by hyperbranched poly(citrate glyceride)

Hyperbranched poly(citrate glyceride)s (HBPETs) as plasticizers were mixed with maize starch (S) via cooking and film formation. The structure, aging properties, and hydrophilicity of the plasticized starches were studied by means of Fourier transform infrared spectroscopy, X-ray diffraction, tension testing, contact angle testing, solubility measurements, moisture absorption, and water vapor permeability (WVP). Compared with a glycerol–S plasticized film, the HBPET–S composite films had better mechanical properties in terms of both strength and elongation at break, better aging resistance, less moisture absorption, less WVP, and more hydrophobicity on the film surface. The mechanisms behind the performances resulted from stronger and more stable H bonds between the abundant active end groups of HBPET and hydroxyls of starch and the high branching degree of the HBPETs; this was helpful for effectively inhibiting the recrystallization of starch. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46899.     

Nanofibrous nonwovens based on dendritic‐linear‐dendritic poly(ethylene glycol) hybrids

Dendritic‐linear‐dendritic (DLD) hybrids are highly functional materials combining the properties of linear and dendritic polymers. Attempts to electrospin DLD polymers composed of hyperbranched dendritic blocks of 2,2‐bis(hydroxymethyl) propionic acid on a linear poly(ethylene glycol) core proved unsuccessful. Nevertheless, when these DLD hybrids were blended with an array of different biodegradable polymers as entanglement enhancers, nanofibrous nonwovens were successfully prepared by electrospinning. The pseudogeneration degree of the DLDs, the nature of the co‐electrospun polymer and the solvent systems used for the preparation of the electrospinning solutions exerted a significant effect on the diameter and morphology of the electrospun fibers. It is worth‐noting that aqueous solutions of the DLD polymers and only 1% (w/v) poly(ethylene oxide) resulted in the production of smoother and thinner nanofibers. Such dendritic nanofibrous scaffolds can be promising materials for biomedical applications due to their biocompatibility, biodegradability, multifunctionality, and advanced structural architecture. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45949.     

Effect of generation number on properties of fluoroalkyl-terminated hyperbranched polyurethane latexs and its films

The 1–3 generations of hyperbranched polyesters (HBPE-1/2/3) were synthesized from trimethylolpropane (TMP) and 2,2-dimethylol propionic acid (DMPA) by “quasi-one-step method.” Then, isophorone diisocyanate (IPDI), polybutylene adipate (CMA-1044), DMPA and 1,4-butanediol (BDO) were utilized to prepare the urethane prepolymer (PU), which was reacted with HBPE to synthesize hyperbranched polyurethanes (HBPU). Finally, 1–3 generations of fluoroalkyl-end-capped hyperbranched polyurethanes (FHBPU) latexes were obtained by the reaction of perfluorohexyl ethanol (S104) and HBPU as well as the self-emulsification process. Structure of the products, the properties of different FHBPU emulsions and its films were investigated by FTIR, ¹H NMR, TEM, DLS, TGA, XPS, XRD, SEM, AFM and static contact angle measuring instrument. Results showed that the particle size of FHBPU latexes increased gradually with the increase of generation number. SEM and XRD results verified that an amount of the crystal particles was increased with the increase of generation number. XPS and AFM demonstrated that degree of microphase separation and film roughness was increased with the increase of branching degree. Static water contact angles could attain 95.9°, 100.3°, and 107.0°, respectively on the 1–3 generations of FHBPU films, compared to that on PU (75.1°).     

Six‐arm star‐shaped polymer with cyclophosphazene core and poly(ε‐caprolactone) arms as modifier of epoxy thermosets

A six‐arm star‐shaped poly(ε‐caprolactone) (s‐PCL) based on cyclophosphazene core was obtained by presynthesis of a hydroxy‐teminated cyclophosphazene derivative and subsequent initiation of the ring‐opening polymerization of ε‐caprolactone, and its use in different proportions as toughening modifier of diglycidylether of bisphenol A/anhydride thermosets was studied. The star‐shaped polymer was characterized to have approximately 30 caprolactone units per arm. Differential scanning calorimetry revealed a nonsignificant influence on the curing process of the epoxy‐anhydride formulation by the addition of s‐PCL. The s‐PCL‐modified epoxy thermosets exhibited a great improvement in both toughness and strength compared with the neat resin, as the result of a joint effort by the internal rigid core and the external ductile polyester chains of s‐PCL. When the addition of the modifier was 3 wt %, an optimal mechanical and thermomechanical performance was achieved. The impact resistance and tensile strength of the cured epoxy resin were enhanced by 150% and 30%, respectively. The glass transition temperature was also increased slightly. Moreover, the addition of the star‐shaped modifier had little harmful effect on the thermal stability of the material. Thus s‐PCL was proved to be a superior toughening agent without sacrificing thermal and mechanical properties of the thermosets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44384.     

Cyclodextrin‐dendrimer functionalized polysulfone membrane for the removal of humic acid in water

Commercial polysulfone (PSf) membranes were crosslinked with a β‐cyclodextrin‐poly (propyleneimine) (β‐CD‐PPI) conjugate which had β‐CD pendant arms using trimesoyl chloride (TMC) by interfacial polymerization. The morphology and physicochemical properties of the nanofiltration membranes were characterized using Fourier transform infrared/attenuated total reflectance (FT‐IR/ATR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cross‐flow filtration system. Water‐contact angle, water‐intake capacity, and rejection capacities of the membranes were evaluated. The β‐CD‐G4 (generation 4)‐PPI‐PSf and β‐CD‐G3 (generation 3)‐PPI‐PSf membranes both exhibited high humic acid rejection of 72% as compared to the commercial PSf which exhibited 57%. The modified membranes were also more hydrophilic (36° to 41°) than PSf (76°). These results suggest that β‐CD‐PPI nanostructures are promising materials for the synthesis of membranes for the removal of humic acid from water. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4428–4439, 2013     

Synthesis and application of hyperbranched poly(urethane‐urea) finishing agent with amino groups

The isocyanate‐terminated linear polyurethane prepolymer (LPPU) was successfully synthesized via step‐by‐step polymerization, with isophorone disocyanate (IPDI) and polytetramethylene ether glycol (PTMG, M_n = 2000 g/mol) used as raw materials, dibutyltin dilaurate (DBTDL) as the catalyst, 1,4‐butanediol (BDO) as the chain extender and anhydrous ethanol (EtOH) as the blocking agent. Then the hyperbranched poly (urethane‐urea) (HBPU) containing amino groups was synthesized by grafting LPPU on amino‐terminated hyperbranched polymers (NH₂‐HBP). The molecular structure of LPPU and HBPU were characterized by means of FT‐IR and ¹H‐NMR. It was founded that LPPU and HBPU were successfully synthesized as anticipated. The thermal stability and crystalline morphology of LPPU and HBPU were characterized and analyzed by TG and XRD. Additionally, it was also found that, after addition of 10% HBPU, the water absorption rate, water vapor transmission rate, and water vapor permeability increased markedly by 162.02%, 400.00%, 260.00%, respectively. The tensile strength of membrane decreased by 24.57% and the elongation at break increased by 26.92%. Compared with the leather finished by commercial PU finishing agent, the leather finished by HBPU presented better properties. The water vapor permeability of the leather finished by increased by 13.0%, and the dry‐ and wet‐rub resistances and the physical and mechanical performances were excellent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44139.     

Hyperbranched polyhedral oligomeric silsesquioxane (HB‐POSS) nanomaterials for high transmission and radiation‐resistant space and solar applications

Hyperbranched polycarbosiloxanes and polysiloxanes with octafunctional polyhedral oligomeric silsesquioxane (POSS) branchpoints and curable alkoxysilane or silanol end‐groups were formulated with linear polysiloxanes to fabricate transparent and robust nanostructured POSS‐containing materials for use in a range of high performance space and solar applications. The effect of methyl vs. phenyl content, architecture and linear polysiloxane mass on transmission, thermal, physical, and proton, electron and UV radiation resistance properties was determined, and the physical properties of the nanomaterials were tailored to produce adhesives, or rigid or flexible coatings as desired. The methyl formulations showed superior electron resistance relative to a commercial space control material and to a POSS‐free HB polymer control material, even when directly exposed to radiation in coating form, whereas the phenyl formulations were shown to have inferior electron and UV resistance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3849–3861, 2013     

Solid–solid phase‐change materials based on hyperbranched polyurethane for thermal energy storage

A hyperbranched polyol (HBP) was synthesized with poly(ethylene glycol) (PEG) as the core molecule and 2,2‐bis(hydroxymethyl) propionic acid as the chain extender. Then, a series of hyperbranched polyurethane phase‐change materials (HP‐PCMs) with different crosslinking densities was synthesized with isophorone diisocyanate and HBP as a molecular skeleton and PEG 6000 as a phase‐change ingredient. ¹H‐NMR, gel permeation chromatography, and Fourier transform infrared spectroscopy confirmed the successful synthesis of the HBP and HP‐PCMs. The polarization optical microscopy and wide‐angle X‐ray diffraction results show that the HP‐PCM exhibited good crystallization properties, but the crystallinity was lower than that of PEG 6000. The analysis results from differential scanning calorimetry indicated that the HP‐PCMs were typical solid–solid phase‐change materials with suitable phase‐transition temperatures. In addition, HP‐PCM‐3, with an appropriate degree of hyperbranched structure, possessed the highest thermal transition enthalpy of 123.5 J/g. Moreover, thermal cycling testing and thermogravimetric analysis showed that the HP‐PCMs exhibited good thermal reliability and stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45014.     

Crystallization behavior of hyperbranched polyethylenes with different degree of branching

Hyperbranched polyethylenes (HBPEs) with different degree of branching (DB) and similar M_n are used to investigate the effect of branch structure on their crystallization behaviors. The crystal structure, isothermal, and non‐isothermal crystallization kinetics of HBPEs are studied by X‐ray diffraction and differential scanning calorimetry. The isothermal crystallization process is analyzed by the Avrami equation while the non‐isothermal crystallization process is analyzed through the Ozawa and Mo methods. The XRD results indicate that the crystallization ability of HBPEs is weakened with the introduction of branch structure, i.e., the crystallinity of HBPEs decreases with the increase of DB, and even tends to zero. The kinetics results of isothermal and non‐isothermal crystallization verify the peculiar effects of DB on the crystallization process of HBPEs. In detail, a little of branch structure can accelerate the crystallization process of HBPEs, however a large number of branch can inhibit it. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44127.     

Lipase-catalyzed synthesis of hyperbranched polyester improved by autocatalytic prepolymerization process

This work developed a facile and environmentally friendly route for lipase-catalyzed synthesis of a hyperbranched polyester by introducing an autocatalytic prepolymerization of comonomers. Trimethylolpropane, 1,8-octanediol, and adipic acid as comonomers for synthesizing the hyperbranched polyester were first prepolymerized via the automatic catalytic effect of the reactants themselves to obtain an appropriate reaction substrate for further lipase-catalyzed polymerization, where immobilized lipase Novozym 435 was used as a biocatalyst. The acidity and fluidity of optimized oligomers after the autocatalytic prepolymerization provide a benign reaction substrate for the retention of enzymatic activity in the subsequent lipase-catalyzed esterification, which is crucial for the enzymatic polymerization. The optimum reaction temperature and reaction time for prepolymerization were determined to be 120 °C and 150 min. The molecular weight (M _w) of the prepared polyester was approximately 26,300 g/mol. Quantitative analysis of ¹H-NMR and inverse-gated ¹³C-NMR spectra confirmed the hyperbranched structure of the resulting polyester with a branching degree of 31.3%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47221.     

Synthesis of hyperbranched polybenzoxazoles and their molecular composites with epoxy resins

Hyperbranched aromatic polymers have attracted great attention recently because they combined the processability of hyperbranched polymers and the high‐level performance of aromatic polymers. Here, a one‐pot strategy for the synthesis of hyperbranched Polybenzoxazoles (HBPBOs) by polycondensation of 2,2‐Bis (3‐amino‐4‐hydroxyphenyl) hexafluoropropane and 1,3,5‐benzenetricarboxylic acid in Polyphosphoric acid was reported. The HBPBOs exhibited good solubility in organic solvents because of the branched structure and the flexible hexafluoropropane groups in main chains. The structure and terminal functional groups could be tailored by adjusting the molar ratio of two monomers. FT‐IR, NMR and XRD measurements confirmed the structure of HBPBOs, while thermogravimetric analysis (TGA), UV‐vis, and photoluminescence spectra, combined with the comparison with linear PBOs demonstrated the intriguing optical properties and good thermal stabilities of HBPBOs. The good solubility of HBPBOs also permitted their usage as molecular reinforcement for polymer composites as demonstrated in this study of HBPBOs/epoxy composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41942.     

Thiol-terminated hyperbranched polymer for DLP 3D printing: Performance evaluation of a low shrinkage photosensitive resin

In order to lower the volume shrinkage of the DLP 3D printing photosensitive resins during printing, a thiol-terminated hyperbranched polymer (T-HBP) was synthesized and introduced into the bisphenol A epoxy acrylate (EA) based photosensitive resin system. The obtained T-HBP was characterized by FTIR and ¹H NMR spectra, and the grafting rate of sulfhydryl was determined. The mechanical properties of the photosensitive resins were measured by tensile and impact strength measurement. The glass transition temperature of the photosensitive resins was analyzed by DSC and the impact fracture surface was observed by SEM. T-HBP exhibited a much lower viscosity than its linear counterparts, and the addition of thiol improved the curing speed of the photosensitive resins. When the amount of T-HBP added was 20 wt%, the shrinkage of the photosensitive resins was reduced by about 45.5% and the impact strength increased by 33.9% compared with the control. The macromolecular spherical structure of T-HBP effectively reduced the functional group density of the photosensitive resins. In addition, the thiol-acrylate photopolymerization introduced by T-HBP further reduced the volume shrinkage of the photosensitive resins.