Synthesis and characterization of novel polyurethanes based on fluorine‐containing polyphosphazene

Fluorine‐containing poly[bis‐(2,2,3,3,4,4,5,5‐octafluoro‐1‐pentanol)_1.6 (4‐hydroxybutaneoxy)_0.4 phosphazene] (OFHBP) was synthesized and characterized by Fourier transform infrared (FTIR) spectra, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The obtained OFHBP was used as a cross‐linker to prepare a series of novel polyurethanes (PUPFs). The composition of the PUPFs was confirmed by FTIR and elemental analysis (EA). The crystalline structure and microstructure of the PUPFs were examined by X‐ray diffraction (XRD) and atomic force microscopy (AFM). The thermal and tensile properties of the PUPFs were characterized by differential scanning calorimetry (DSC) and tensile testing. In addition, the surface energy of the PUPFs was also evaluated by contact angle measurements (CA). The results showed that glass transition temperature of the PUPF‐4 was decreased by 15°C, elongation at break was improved by 61% and a 41% decrease in surface energy in comparison with conventional polyurethane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and mechanical properties of fluorine‐containing glycidyl azide polymer‐based energetic binders

A novel energetic polymer, fluorine‐containing glycidyl azide polymer (FGAP ), was developed via an initial cationic copolymerization of epichlorohydrin and 1,1,1‐trifluoro‐2,3‐epoxypropane, followed by azidation. The structure of FGAP was confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies. The molecular weight and the thermal behavior of FGAP were characterized using gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. FGAP had a molecular weight of 2845 g mol^?1, and the glass transition temperature and decomposition temperature were found to be ?47.8 and 253 °C, respectively. FGAP ‐based polyurethane networks were further prepared using triphenylmethane‐4,4,4‐triisocyanate as the crosslinking agent. In comparison with GAP , FGAP ‐based polyurethane networks exhibited better mechanical behaviors (a tensile strength of 1.5 MPa and an elongation at break of 81.6%). The results demonstrated that FGAP might be a promising polymeric binder for future propellant formulations. © 2017 Society of Chemical Industry     

Studies of fluorine‐containing bismaleimide resins part I: Synthesis and characteristics of model compounds

A series of fluorine‐containing bismaleimide (FBMI) monomers are synthesized by a 3‐step reaction for using as the applications of low‐k materials. The synthesized FBMI monomers are characterized by the ¹H, ¹³C, ¹⁹F nuclear magnetic resonance (NMR) spectroscopy and element analysis. These FBMI monomers react with free radical initiator or self‐cure to prepare FBMI‐polymers. All the self‐curing FBMI resins have the glass transition temperatures (T_g) in the range of 128–141°C and show the 5% weight loss temperatures (T_5%) of 235–293°C in nitrogen atmosphere. The higher heat resistance of self‐curing FBMI resin relative to FBMI‐homopolymer is due to its higher crosslinking density. The FBMI resins exhibit improved dielectric properties as compared with commercial bismaleimide (BMI) resins with the dielectric constants (D_k) lower than 2.49, which is related to the low polarizability of the C? F bond and the large free volume of CF₃ groups in the polymers. Besides, the flame retardancy of all these FBMI resins could be enhanced via the introduction of Br‐atom. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dielectric and thermal behaviors of fluorine‐containing dianhydride‐modified polybenzoxazine: A molecular design flexibility

Fluorine‐containing copolybenzoxazines were successfully prepared by reacting bisphenol‐AF/aniline‐based benzoxazine resin (BAF‐a) with 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA) in N,N‐dimethylacetamide solvent. The dielectric and thermal properties as well as flexibility of the resulting copolymer films were investigated. The incorporation of fluorine groups into polybenzoxazine was found to substantially decrease the dielectric constant of the resulting copolybenzoxazine to as low as 2.6. The formation of ester linkages between the hydroxyl groups in the poly(BAF‐a) and the carbonyl groups in the 6FDA resulted in substantially enhanced flexibility of the copolybenzoxazines. Moreover, the copolymers showed superior degradation temperature and significant improvement in char yield, up to 464 °C and 56%, respectively. The glass‐transition temperature of the copolybenzoxazines was increased with increasing dianhydride content and exhibited a maximum value of 290 °C at 2.5/1 mole ratio of poly(BAF‐a) to 6FDA. Therefore, the fluorine‐containing dianhydride‐modified polybenzoxazines are appropriate for applications as polymeric films for coatings and as a good electrical insulation material with high thermal resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45204.     

Fabrication of fluorescent poly(l‐lactide‐co‐caprolactone) fibers with quantum‐dot incorporation from emulsion electrospinning for chloramphenicol detection

The on‐site rapid detection of antibiotic residues deposited in food or beverage still remains a challenge in daily life. In this study, cadmium tellurium (CdTe) quantum dots (QDs) were incorporated into poly(l ‐lactide‐co‐caprolactone) (PLLACL) fibers with emulsion electrospinning. Water‐soluble CdTe QDs were used as fluorescence agents, and PLLACL was used as filament materials, respectively. A variety of experiments were performed to characterize the structure and properties of the fibrous composite. Ultraviolet–visible and photoluminescence spectra of the fibers showed similar characteristic absorption and emission properties to those of the CdTe QDs. The fibrous QD–PLLACL composite showed stable fluorescence over 30 days at room temperature and could be used to detect chloramphenicol through fluorescence quenching caused by resonance energy transfer. This approach provides a facile shortcut for fabricating fluorescent fibers that simultaneously inherit the mechanical behavior of PLLACL fibers and the fluorescence properties of CdTe QDs for the detection of antibiotics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44584.     

Synthesis and gas permeability of ABA‐type triblock copolymers derived from fluorine‐containing polyimide with polyhedral oligomeric silsesquioxane

ABA‐type triblock copolymers derived from 4,4'‐(hexafluoroisopropylidene)diphthalicanhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and methacryl phenyl polyhedral oligomeric silsesquioxane (MPPOSS) were synthesized by atom transfer radical polymerization. The chemical structure of the synthesized ABA‐type triblock copolymer was confirmed by ¹H NMR, ¹³C NMR, ²⁹Si NMR and Fourier transform infrared analyses. The ratios of 6FDA‐TeMPD and MPPOSS determined by TGA were 94/6, 85/15, 77/23, 68/32, 57/43 and 31/69. The film density of the ABA‐type triblock copolymer films did not conform to the mixing rule because of polyimide (PI) chain aggregation. Based on contact angle and water uptake analyses, the hydrophobicity of the ABA‐type triblock copolymer film was determined to be higher than the theoretical value because of POSS cage effects and PI chain aggregation. The gas permeability coefficient of the ABA‐type triblock copolymer decreased compared with that of PI because of aggregation of PI chains and inhibition of solubility decreases by substitutes with high affinity. ABA‐type triblock copolymer CO₂/H₂ separation performance increased compared with that of PI. The ABA‐type triblock copolymer derived from PI and MPPOSS can be described as a polymer material with higher hydrophobicity and higher CO₂/H₂ selectivity than PI. © 2015 Society of Chemical Industry     

Effects of addition orders on the properties of fluorine‐containing copolyimides

A series of fluorine‐containing copolyimides were synthesized by three different orders of addition of monomers. The fluorine‐containing copolyimides were prepared by the reaction of 4,4′‐diaminodiphenylmethane (DDM) with 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), and pyromellitic dianhydride (PMDA). The synthesis reactions of the copoly(amic acid)s (PA) were carried out by three different orders of addition of the monomers with different molar ratios of 6FDA to PMDA. The viscosity of the PA solution obtained by DDM–(6FDA+PMDA), that is, 6FDA and PMDA added simultaneously to DDM in N‐methyl‐2‐pyrrolidinone (NMP), was higher than the other two addition orders (i.e., DDM–6FDA–PMDA and DDM–PMDA–6FDA). The viscosity decreased as the relative amount of 6FDA to PMDA increased. The copolyimides formed by different addition orders but the same 6FDA‐to‐PMDA molar ratios contained different properties, such as dielectric constant, moisture absorption, contact angle, and optical transparency. All of these copolyimides were insoluble in common organic solvents, such as NMP and tetrahydrofuran. Thermogravimetric analysis showed that the onset temperature of 8% weight loss decreased slightly as [6FDA] : [PMDA] increased. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3252–3258, 2000     

Gas transport and optical properties of ABA‐type triblock copolymers designed using fluorine‐containing polyimide macroinitiators with methyl methacrylate

4,4'‐(Hexafluoroisopropylidene) diphthalic anhydride 2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) polyimide macroinitiator was synthesized and reacted with poly(methyl methacrylate) (PMMA) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The effect of the ABA‐type triblock copolymer structure on solid, thermal, optical and gas transport properties was systematically investigated and compared with the physical blend polymer. The blend polymer was cloudy, whereas the triblock copolymer was colorless and transparent. The PMMA component decomposition temperature for the triblock copolymer slightly shifted to higher temperature, while its gas barrier property was higher than the blend polymer. The refractive index and the gas permeability decreased while maintaining the heat resistance by a high nanoscale distribution of both polymer components. The 6FDA‐TeMPD/PMMA ABA‐type triblock copolymer can be described as a polymer material with high heat resistance, high gas barrier property and low refractive index amongst existing polymers. © 2013 Society of Chemical Industry     

Preparation and properties of fluorine‐containing polysiloxanes obtained via ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane catalyzed by rare earth solid superacid SO$_{4}^{2-}$/TiO2/Ln3+

Traditional catalysts such as (CH₃)₄NOH, NaOH, KOH, n‐BuLi and CF₃SO₃H can catalyze the copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane to afford fluorine‐containing polysiloxanes. However, use of these catalysts poses significant difficulties in handling and separation. In this work, fluorine‐containing polysiloxanes were synthesized through a novel and environmentally friendly method: ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane catalyzed by rare earth solid superacid SO /TiO₂/Ln³⁺. The effects of reaction conditions were examined in detail. The yield sequence of various rare earth catalysts is Nd ～ La ～ Y ～ Sm > Gd, while the number‐average molecular weight sequence is Nd > La > Y > Sm > Gd. The optimum conditions for the ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane are as follows: [Nd³⁺] = 0.05 mol L^?1 and mol L^?1 in the immersing solution, SO /TiO₂/Nd³⁺ calcined at 500 °C and the copolymerization conducted at 80 °C for 40 min. Structures of resulting copolymers were characterized using size exclusion chromatography, ¹H NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and contact angle measurements. According to the copolymerization features, a cationic equilibrium reaction mechanism is proposed. Copyright © 2012 Society of Chemical Industry     

Study on microemulsion polymerization of N‐butyl maleimide

By using sodium dodecyl sulfate (SDS) as an emulsifier, polymerization of N‐butyl maleimide (NBMI) was carried out in ternary oil‐in‐water microemulsion, initiated with potassium persulfate (KPS). The kinetics of microemulsion polymerization were measured by dilatometry. The effects of initiator concentration, polymerization temperature, monomer concentration, and emulsifier concentration on polymerization kinetics were investigated. On this basis, the polymerization kinetics were discussed. The experiment result showed that the microemulsion polymerization kinetics of N‐butyl maleimide were almost consistent with the prediction of the Smith‐Ewart theory in conventional emulsion polymerization, except that the emulsifier showed a special effect on polymerization. At the same time, the polymer was characterized by IR, ¹H‐NMR, DSC, and TGA. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 805–809, 2000     

Dye‐affinity microbeads for removal of phenols and nitrophenols from aquatic systems

Alkali Blue 6B attached poly(2‐hydroxyethyl methacrylate) (PHEMA) microbeads were investigated as dye‐affinity adsorbents for the removal of phenol and nitrophenols (i.e., 2‐nitrophenol, 4‐nitrophenol, and 2,4‐dinitrophenol) from aqueous solutions. PHEMA microbeads were prepared by radical‐suspension polymerization of HEMA in the presence of azobisisobutyronitrile as the initiator. These microbeads with a swelling ratio of 55% and carrying 23.6 μmol Alkali Blue 6B/g polymer were then used in the removal of phenol and nitrophenols from aqueous media. The adsorption was fast in all cases (20‐min equilibrium time). The maximum adsorptions of phenols onto the microbeads carrying Alkali Blue 6B were 145.2 μmol/g for phenol, 87.8 μmol/g for 2,4‐dinitrophenol, 112.6 μmol/g for 4‐nitrophenol, and 104.3 μmol/g for 2‐nitrophenol. The affinity order was phenol > 4‐nitrophenol > 2‐nitrophenol > 2,4‐dinitrophenol. The adsorption of nitrophenols decreased with increasing pH. Desorption of nitrophenols was achieved using a 30% (v/v) methanol solution. The microbeads carrying Alkali Blue 6B are suitable for repeated use for more than five cycles without a noticeable loss of adsorption capacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2411–2418, 2002     

Effect of topological structure on photoluminescence of PbSe quantum dot‐doped borosilicate glasses

Borosilicate glasses doped with PbSe quantum dots (QDs) were prepared by a conventional melt‐quenching process followed by heat treatment, which exhibit good thermal, chemical, and mechanical stabilities, and are amenable to fiber‐drawing. A broad near infrared (NIR) photoluminescence (PL) emission (1070‐1330 nm) band with large full‐width at half‐maximum (FWHM) values (189‐266 nm) and notable Stokes shift (100‐210 nm) was observed, which depended on the B₂O₃ concentration. The PL lifetime was about 1.42‐2.44 μs, and it showed a clear decrease with increasing the QDs size. The planar [BO₃] triangle units forming the two‐dimensional (2D) glass network structure clearly increased with increasing B₂O₃ concentration, which could accelerate the movement of Pb²⁺ and Se^2? ions and facilitate the growth of PbSe QDs. The tunable broadband NIR PL emission of the PbSe QD‐doped borosilicate glass may find potential application in ultra‐wideband fiber amplifiers.     

Microencapsulation and application of fluorine‐free water repellent agent‐AH102

Fluorine‐free water repellent agent, AH102, was microencapsulated by interfacial polymerization with polyurethane as shell material to restrict its hydrolysis and improve its dispersibility in water. The appearance of the resultant microcapsules was characterized with optical microscope and scanning electron microscope. Chemical structure of microcapsules was identified with Fourier‐transforming infrared spectrometer. The size and size distribution of the microcapsules were determined by laser particle size analyzer. The thermal property of the microcapsules was investigated by thermogravimetric analysis. The stability and dispersibility of the microcapsules in aqueous medium were characterized by evaluating the static water contact angles of the treated cotton fabrics with the emulsions of unencapsulated and microencapsulated AH102 at different storage intervals. The results showed that AH102 was successfully encapsulated and its stability and dispersibility in water were greatly improved. As expected, the emulsion of the microencapsulated AH102 became more stable than that of the unencapsulated one at water repellence to cotton fabric with increasing storage intervals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dye‐ligand column chromatography: Albumin adsorption from aqueous media and human plasma with dye‐affinity microbeads

Cibacron Blue F3GA was covalently coupled with poly(ethylene glycol‐dimethacrylate‐2‐hydroxyethylmethacrylate) [poly(EGDMA‐HEMA)] microbeads via the nucleophilic substitution reaction between the chloride of its triazine ring and the hydroxyl groups of the HEMA molecules under alkaline conditions. The affinity sorbent carrying 16.5 μmol Cibacron Blue F3GA/g polymer was then used for bovine serum albumin (BSA) adsorption from aqueous protein solutions and from human plasma in a packed‐bed column. The BSA adsorption capacity of the microbeads decreased with an increase in the recirculation rate. High adsorption rates were observed at the beginning, then equilibrium was gradually achieved in about 60 min. The BSA concentration in the mobile phase was also effective on adsorption. BSA adsorption was first increased with BSA concentration, then reached a plateau that was about 57.3 mg BSA/g. Higher BSA adsorption was observed at lower ionic strength. The maximum adsorption was observed at pH 5.0, which is the isoelectric pH of BSA. Higher human serum albumin adsorption was achieved from human plasma (109.6 mg HSA/g). High desorption ratios (over 94% of the adsorbed albumin) were achieved by using 1.0M NaSCN (pH 8.0) in 30 min. It was observed that albumin could be repeatedly adsorbed and desorbed without a significant loss in adsorption capacity. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2803–2810, 1999     

Fabrication of surface‐modified CdSe quantum dots by self‐assembly of a functionalizable comb polymer

A facile approach is proposed for the fabrication of surface‐modified CdSe quantum dots (QDs) with compatibility with various media and better dispersibility by self‐assembly of a functionalizable comb polymer. The comb polymer was prepared from the reaction between the acyl chloride groups in poly(acryloyl chloride) and the hydroxyl groups in 1‐octadecanol. With the combination of the compatibility and entanglement of the aliphatic chain in 1‐octadecanol and similar aliphatic chain in oleic acid ligand of QDs, the comb polymer could cap on the QDs and thus endow them with functional groups. The structure of such a polymer was investigated using Fourier transform infrared spectroscopy. According to the reactivity of remaining acyl chloride groups in the comb polymer, the polymer ligands could be tailored to be various structures, and then lipophilic, hydrophilic and functional QDs were obtained. The fluorescence properties of the surface‐modified QDs were investigated, and the morphologies and dispersions of different kinds of surface‐modified QDs were characterized using transmission electron microscopy. Finally, homogeneous and stable dispersions of QDs in various media could be realized by adjusting the structure of the comb polymer. Copyright © 2010 Society of Chemical Industry     

Small‐Protein‐Stabilized Semiconductor Nanoprobe for Targeted Imaging of Cancer Cells

Recently, semiconductor nanoparticles such as quantum dots (QDs) have attracted significant attention for bioimaging. Complex chemical functionalization, surface modification, and bioconjugation chemistry are generally required to tag biomolecules to QDs for imaging of different biomarkers. In this study, we report a simple method for production of QDs stabilized by the small protein, Affibody (AF‐QDs) for fluorescent imaging of the human epidermal growth factor receptor type 2 (HER2) in human A549 lung cancer cells. This one‐pot synthesis of AF‐QDs avoids complex chemical conjugation procedures and demonstrates a promising approach for the preparation of fluorescent nanoprobes for imaging of cancer targets.     

Metal chelating properties of Cibacron Blue F3GA‐derived poly(EGDMA‐HEMA) microbeads

Metal chelating properties of Cibacron Blue F3GA‐derived poly(EGDMA‐HEMA) microbeads have been studied. Poly(EGDMA‐HEMA) microbeads were prepared by suspension copolymerization of ethylene glycol dimethacrylate (EGDMA) and hydroxy‐ethyl methacrylate (HEMA) by using poly(vinyl alcohol), benzoyl peroxide, and toluene as the stabilizer, the initiator, and the pore‐former, respectively. Cibacron Blue F3GA was covalently attached to the microbeads via the nucleophilic substitution reaction between the chloride of its triazine ring and the hydroxyl groups of the HEMA, under alkaline conditions. Microbeads (150–200 μm in diameter) with a swelling ratio of 55%, and carrying 16.5 μmol Cibacron Blue F3GA/g polymer were used in the adsorption/desorption studies. Adsorption capacity of the microbeads for the selected metal ions, i.e., Cu(II), Zn(II), Cd(II), Fe(III), and Pb(II) were investigated in aqueous media containing different amounts of these ions (5–200 ppm) and at different pH values (2.0–7.0). The maximum adsorptions of metal ions onto the Cibacron Blue F3GA‐derived microbeads were 0.19 mmol/g for Cu(II), 0.34 mmol/g for Zn(II), 0.40 mmol/g for Cd(II), 0.91 mmol/g for Fe(III), and 1.05 mmol/g for Pb(II). Desorption of metal ions were studied by using 0.1 M HNO₃. High desorption ratios (up to 97%) were observed in all cases. Repeated adsorption/desorption operations showed the feasibility of repeated use of this novel sorbent system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1397–1403, 1999     

Influence of electron beam irradiation on properties of fluorine‐containing poly(aryl ether ketone)s

The influence of electron beam irradiation on the properties of fluorine‐containing poly(aryl ether ketone)s (F‐PEK), derived from 2,3,4,5,6‐pentafluorobenzoic acid, was examined. Irradiation was performed with an electron beam at a dose of 3.63 × 10³ Gy s^?1 for which the corresponding doses were 29.0, 51.0, and 94.5 MGy. Tensile strength at break increased up to a dose of 29.0 MGy and then decreased very slightly with irradiation. Elongation at break was more susceptible to irradiation and decreased drastically to one tenth at a dose of 29.0 MGy. Young's modulus was enhanced by the irradiation. F‐PEKs were changed from elastic materials to strong and brittle materials by irradiation. Relaxation of the viscoelastic property shifted toward higher temperature by irradiation. These tensile and viscoelastic property changes were attributed to the formation of a bulkier and more rigid structure by crosslinking. The fluorine atoms attached to the 1,4‐phenylene moiety in F‐PEKs were surprisingly susceptible to the irradiation and were completely lost at a dose of 29.0 MGy. The π‐electron conjugated aromatic structure was concurrently developed during irradiation. Further, polar functional groups such as carboxyl group and ester group were generated by chain scission and rearrangement. The F‐PEKs retained their good transparency and the thermal stability was significantly improved after irradiation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 157–166, 2004     

Synthesis and characterization of novel fluorine‐containing methacrylate copolymers: Reactivity ratios,thermal properties,and antimicrobial activity

The free‐radical‐initiated copolymerization of 2‐(4‐acetylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (AOEMA) and 2‐(4‐benzoylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (BOEMA) with 2‐[(4‐fluorophenyoxy]‐2‐oxoethyl‐2‐methylacrylate (FPEMA) were carried out in 1,4‐dioxane solution at 65°C using 2,2′‐azobisisobutyronitrile as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR and ¹H‐ and ¹³C‐NMR spectral studies. ¹H‐NMR analysis was used to determine the molar fractions of AOEMA, BOEMA, and FPEMA in the copolymers. The reactivity ratios of the monomers were determined by the application of Fineman‐Ross and Kelen‐Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPEMA, and copolymers formed are statistically in nature. The molecular weights (M _w and M _n) and polydispersity index of the polymers were determined using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of FPEMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPEMA in the copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009