Improvement of interfacial adhesion for plasma‐treated aramid fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite and fiber surface aging effects

Interfacial adhesion between the fiber and the matrix in a composite is a primary factor for stress transfer from the matrix to the fiber. In this study, oxygen plasma treatment method was applied to modify the fiber surface for improving interfacial adhesion of aramid fiber‐reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite. Composite interfacial adhesion properties were determined by interlaminar shear strength (ILSS) using a short‐beam bending test. The composite interfacial adhesion mechanism was discussed by SEM. The changes of chemical composition and wettability for plasma‐treated fiber surfaces stored in air as long as 10 days were investigated by XPS and dynamic contact angle analysis (DCAA), respectively. Results indicated that oxygen plasma treatment was an effective method for improving interfacial adhesion; plasma‐treated fiber surface suffered aging effects during storage in air. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation of sulfonated poly(phthalazinone ether sulfone ketone) composite nanofiltration membrane

Thin film composite (TFC) membranes were prepared from sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) as a top layer coated onto poly(phthalazinone ether sulfone ketone) (PPESK) ultrafiltration (UF) support membranes. The effects of different preparation conditions such as the SPPESK concentration, organic additives, solvent, degree of substitution (DS) of SPPEK and curing treatment temperature and time on the membrane performance were studied. The SPPESK concentration in the coating solution was the dominant factor for the rejection and permeation flux. The TFC membranes prepared from glycerol as an organic additive show better performance then those prepared from other additives. The rejection increased and the flux decreased with increasing curing treatment temperatures. The salt rejections of the TFC nanofiltration (NF) membranes increased in the order MgCl₂ < MgSO₄ < NaCl < Na₂SO₄. TFC membranes showed high water flux at low pressure. SPPESK composite membranes rejections for a 1000 mg L⁻¹ Na₂SO₄ feed solution was 82%, and solution flux was 68 L m⁻² h⁻¹ at 0.25 MPa pressure.     

Hydrophobic modification of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber composite membranes were obtained by surface-coated modification method.     

Sulfonated carbon nanotubes/sulfonated poly(ether sulfone ether ketone ketone) composites for polymer electrolyte membranes

A series of composite membranes consisting of sulfonated carbon nanotubes (sCNTs) and sulfonated poly(ether sulfone ether ketone ketone) were successfully fabricated via the solution casting method. The chemical structure, as well as the long‐term stability of the sCNTs in different solvents, was investigated by Fourier transform infrared (FTIR) analysis and solubility experiment, respectively. The morphology, tensile strength, proton conductivity, and methanol permeability of the composite membranes were also investigated. The scanning electron microscope (SEM) observation indicated the good dispersion of the carbon nanotubes in polymer matrix as well as the strong interfacial bonding between the sulfonated poly(ether sulfone ether ketone ketone) (SPESEKK) matrix and sCNTs. The addition of either pristine carbon nanotubes or modified carbon nanotubes significantly enhanced the tensile strength of the SPESEKK membrane. The proton conductivity of the SPESEKK membrane increased while the methanol permeability decreased as the sCNTs content increased, showing a strong interaction between the modified nanotubes and SPESEKK. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrophobic modification of poly（phthalazinone ether sulfone ketone） hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly（phthalazinone ether sulfone ketone） （PPESK） hollow fiber composite membranes were obtained by surface-coated modification method.     

Hydrophobic modification of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber composite membranes coated with silicone rubber and with sol–gel polytrifluoropropylsiloxane were obtained by surface-coated modification method. The effects of coating time, coating temperature and the concentration of silicone rubber solution on the vacuum membrane distillation (VMD) properties of silicone rubber coated membranes were investigated. It was found that high water permeate flux could be gotten in low temperature and low concentration of silicone rubber solution. When the coating temperature is 60 °C, the coating time is 9 h and the concentration of silicone rubber solution is 5 g L⁻¹ the water permeate flux of the silicone rubber coated membrane is 3.5 L m⁻² h⁻¹. The prepolymerization time influence the performance of polytrifluoropropylsiloxane coated membranes, and higher prepolymerization time decrease the water permeate flux of the membrane. The water permeate flux and the salt rejection was 3.7 L m⁻² h⁻¹ and 94.6%, respectively in 30 min prepolymerization period. The VMD performances of two composite membranes during long-term operation were studied, and the results indicated that the VMD performances of two composite membranes are quite stable. The salt rejection of silicone rubber coated membrane decreased from 99 to 95% and the water permeate flux fluctuated between 2.0 and 2.5 L m⁻² h⁻¹. The salt rejection of polytrifluoropropylsiloxane coated membrane decreased from 98 to 94% and the water permeate flux fluctuated in 1 L m⁻² h⁻¹ range.     

Thermostable ultrafiltration and nanofiltration membranes from sulfonated poly(phthalazinone ether sulfone ketone)

Modification of poly(phthalazinone ether sulfone ketone) (PPESK) by sulfonation with concentrated or fuming sulfuric acid was carried out in order to prepare thermally stable polymers as membrane materials having increased hydrophilicity and potentially improved fouling-resistance. The sulfonated poly(phthalazinone ether sulfone ketone)s (SPPESK) were fabricated into ultrafiltration (UF) and nanofiltration (NF) asymmetric membranes. The effects of SPPESK concentration and the type and concentration of additives in the casting solution on membrane permeation flux and rejection were evaluated by using an orthogonal array experimental design in the separation of polyethyleneglycol (PEG12000 and PEG2000) and Clayton Yellow (CY, MW 695). One UF membrane formulation type had a 98% rejection rate for PEG12000 and a high pure water flux of 867 kg m⁻² h⁻¹. All the NF membranes made in the present study had rejections of ≥96%, and one had a high water flux of 160 kg m⁻² h⁻¹. Several of the NF membrane formulation types had ∼90% rejection for CY. When the membranes were operated at higher temperatures (80°C), the rejection rates declined slightly and pure water flux was increased more than two-fold. Rejection and flux values returned to previous values when the membranes were operated at room temperature again. Mono- and divalent salt rejections and fluxes were studied on an additional NF membrane set.     

Synthesis and characterization of quaternized poly（phthalazinone ether sulfone ketone） for anion-exchange membrane

Chloromethylated poly(phthalazinone ether sulfone ketone) (CMPPESK) was prepared from poly(phthalazinone ether sulfone ketone) (PPESK) using chloromethyl octyl ethers (CMOE) with lower toxicity as chloromethylated regent.CMPPESK was soluble in N-methyl-2-pyrrolidone (NMP),N,N-dimethylacetamide (DMAc) and chloroform.Quatemized poly(phthalazinone ether sulfone ketone) (QAPPESK) was prepared from CMPPESK by quaternization.QAPPESK had excellent solvent resistance, which was only partly soluble in sulfuric acid (98%) and swollen in N,N-dimethylformamide (DMF).The vanadium redox flow battery (V-RFB) using QAPPESK anion-exchange membrane had better performance with 88.3% of overall energy efficiency.     

Modified poly(phthalazinone ether ketone) membranes for direct methanol fuel cell

Sulfonated poly(phthalazinone ether ketone)s (SPPEK)s were synthesized by the modification of poly(phthalazinone ether ketone) (PPEK) with 98% concentrated sulfuric acid or 98% concentrated sulfuric acid and chlorosulfonic acid mixture at 80–100°C. The presence of sulfonic acid groups in SPPEKs was confirmed by Fourier transform infrared (FTIR) analysis and nuclear magnetic resonance (NMR), and the DSs were determined by Energy Dispersive X‐Ray (EDX). A blend membrane of No. 21 SPPEK and phosphotungstic acid (PWA) was prepared. The methanol permeabilities of SPPEK and blend membranes were about 20 times lower than that of Nafion117 at room temperature. The direct methanol fuel cell (DMFC) test of 2 M methanol solution and air breathing showed that the blend membrane had a better performance than that of the Nafion117. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of sulfone/ketone in poly(phthalazinone ether sulfone ketone) on the gas permeation of their derived carbon membranes

A series of copolymer, poly(phthalazinone ether sulfone ketone)s (PPESKs) with the sulfone over ketone unit (S/K) ratio varying from 20/80, 50/50 to 80/20, were used as precursors to prepare carbon membranes. The effects of chemical structure as S/K ratio of PPESKs on the microstructure and gas separation performance of their derived carbon membranes were mainly investigated. The properties of PPESKs were detected in terms of density, fractional free volume, char yield, interlayer distance and glass transition temperature. During the formation process of carbon membranes (i.e., stabilization and pyrolysis), the changes in functional groups, microstructural parameters and gas permeation were monitored by FTIR, X-ray diffraction, TEM and single gas permeation techniques. The results have shown that the microstructure and gas permeation of obtained carbon membranes are significantly affected by the S/K ratio in precursor PPESKs. Carbon membranes exhibit higher selectivity and lower permeability when prepared at low pyrolytic temperature (i.e., 650 °C and 800 °C) and from PPESKs with S/K ratio equaling 50/50, followed with 20/80 and 80/20. As for carbon membranes prepared at high pyrolytic temperature (i.e., 950 °C), the selectivity order of them is well in accordance with S/K mole ratio in precursor PPESKs: 20/80 > 50/50 > 80/20, and vice versa for permeability.     

Surface characteristic of poly(p‐phenylene terephthalamide) fibers with oxygen plasma treatment

Oxygen plasma is widely employed for modification of polymer surfaces. Plasma treatment process is a convenient procedure that is also environmentally friendly. This study reports the effects of oxygen plasma treatment on the surface properties of poly(p‐phenylene terephthalamide) (PPTA) fibers. The surface characteristics before and after oxygen plasma treatment were analyzed by XPS, atomic force microscopy (AFM) and dynamic contact angle analysis (DCAA). It was found that oxygen plasma treatment introduced some new polar groups (O? C?O) on the fiber surface, increased the fiber surface roughness and changed the surface morphologies obviously by plasma etching and oxidative reactions. It is also shown that the fiber surface wettability was improved significantly by oxygen plasma treatment. Copyright © 2008 John Wiley & Sons, Ltd.     

磺化聚醚砜酮树脂的催化活性

采用磺酸化的方法制备得到了一种新型的磺化聚醚砜酮树脂催化剂（S-PPESK）,并采用滴定法对这种催化剂进行了表征.在异丁烯的低聚反应中,对这种新型树脂催化剂的催化活性进行了细致的研究，磺化聚醚砜酮树脂催化剂在反应中表现出了很好的催化活性和优良的二聚选择性.实验结果显示，当催化剂的磺化度（S.D.）增加时，即催化剂的酸量增加时，异丁烯的转化率和三聚物的选择性也增加，但二聚物的选择性降低，四聚物的选择性则几乎没有变化.     

Preparation and characterization of monovalent cation selective sulfonated poly(ether ether ketone) and poly(ether sulfone) composite membranes

Highly charged cation permeable composite membranes were prepared by blending of sulfonated poly(ether sulfone) (SPES) with sulfonated poly(ether ether ketone) (SPEEK) in 0 to 90% weight ratio, to adjust the hydrophobic properties and ion selective nature. Extent of sulfonation was confirmed by 1H NMR and ion exchange capacity and degree of sulfonation depending on blending composition. These membranes were characterized as a function of weight fraction of SPEEK by recording ion-exchange capacity, water uptake, thermogravimetric analysis, membrane conductivity and membrane potential in equilibration with different electrolytic solutions. Membrane permselectivity and solute flux were estimated using these data on the basis of non-equilibrium thermodynamic principles and for observing the selectivity of different membranes for mono- or bivalent counter-ions. It was observed that relative selectivity for monovalent in comparison to bivalent counter-ions were increased with the decrease in SPEEK content in the composite membrane matrix. The range of SPEEK content in the blend from 60 to 80% appears the most suitable for the selective separation of monovalent ions from bivalent ions. Furthermore, highly charged nature and stabilities of these membranes extend their applications for the electro-assisted separations of similarly charged ions as well as other electro-membrane processes.     

热稳定性能良好的磺化聚醚砜酮催化剂

采用磺酸化的方法制备了一种热稳定性能良好的新型固体酸树脂催化剂——磺化聚醚砜酮树脂(S-PPESK),并应用在异丁烯的低聚反应中.S-PPESK在较低的温度条件下对异丁烯的低聚反应表现出了很高的催化活性和二聚反应选择性.对S-PPESK的热稳定性能采用预处理的方法进行了测试,结果显示它的预处理温度高达180 ℃,与商业磺酸树脂的预处理温度相比高出约40 ℃. S-PPESK在异丁烯的低聚反应中表现出了良好的催化活性、优良的二聚反应选择性和很好的热稳定性能,其应用前景广泛.     

Preparation of poly(phthalazinone ether sulfone ketone) asymmetric ultrafiltration membrane: II. The gelation process

Formation kinetics of the poly(phthalazinone ether sulfone ketone) (PPESK) asymmetric membrane via wet phase-inversion process has been studied experimentally. The membrane morphology has been observed using an online optical microscope–CCD camera experimental system. The precipitation front movement, X, has been measured. Three different linear correlations between the value of X² and the gelation time, t, have been identified. This observation is different from a commonly accepted conclusion which assumed a single linear correlation between X² and t for the whole gelation process. Compared to the morphology evolution of the membrane, it is realized that these three correlations correspond to the three consecutive gelation steps: formation of the top layer, formation of the transition layer and formation of the support layer. The effect of two additives, PEG1000 and Tween80, on the formation kinetics as well as the membrane flux has also been studied. The results present here may provide better understanding of the asymmetric membrane formation process.     

Synthesis and characterization of trimethoxysilyl-functionalized poly(phthalazinone ether ketone)

A novel alkoxysilyl-functionalized poly(phthalazinone ether ketone)(PPEK)was prepared for the boundary lubricant application in micro-electro-mechanical system(MEMS).The synthesis of functionalized PPEK was started from the hydro- xylation of PPEK,then following with the corresponding ring-opening reaction of 3-glycidoxypropyltrimethoxysilane(GPTMS). The structures of the functional PPEK were confirmed by FTIR,~1H NMR,~(29)Si NMR,and UV-vis spectrum.     

Probing the tribological behaviors in water of novel poly(phthalazione ether sulfone ketone) and its composites based on the state of aggregation and the microstructure

In this paper, novel poly(phthalazione ether sulfone ketone) (PPESK) and its composites reinforced with carbon fibers (CFs) were prepared, and their tribological behaviors in pure and sea water were comparatively investigated. Affected by the noncoplanar twisted aromatic structure in the molecular skeleton, the aggregation of the macromolecular chain in PPESK was amorphous, resulting in very high water absorption of PPESK matrix. The invading water molecules led to a sharp decrease in the hardness of PPESK surface, resulting in very high wear rate of PPESK in water. Although CF/PPESK composites had higher water absorption than pure PPESK, their wear processes in water were no longer dominated by high water absorption but by the load‐carrying effect of CFs, ascribed to the good CF/PPESK interfacial adhesion. Therefore, CF/PPESK composites exhibited very low wear rates in the order of 10^?7 mm³/Nm in water, which decreased with the CF content increasing until the content of CFs reached 50%. The results revealed that the most critical factor determining the wear behavior of a fiber‐reinforced polymer composite sliding in water is the fiber/matrix interface but not the water absorption of the polymer matrix. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis and characterization of novel poly（aryl ether sulfone ketone）s containing phthalazinone and biphenyl moieties

A novel series of poly（aryl ether sulfone ketone）s （PPESKs） containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were between 38,330 and 67,900. The glass transition temperatures （Tg） and 5% decomposition temperatures were ranged in 253-269 ℃ and 488-500 ℃, respectively, The structures of these copolymers were confirmed by FT-IR and ^1H NMR. Moreover, all the resultant copolymers were amorphous determined by wide angle X-ray diffraction （WAXD）.     

Synthesis of copolymers of poly(ether sulfone ether ketone ketone) and poly(ether ketone diphenyl ketone ether ketone ketone) by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl(BPOBDP), was synthesized via a two‐step synthetic procedure. A series of novel poly(ether sulfone ether ketone ketone)/poly(ether ketone diphenyl ketone ether ketone ketone) copolymers were prepared by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of 4,4′‐diphenoxydiphenylsulfone (DPODPS) and 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers with 10–50 mol% DPODPS are semicrystalline and have remarkably increased T_gs over commercially available PEEK and PEKK. The copolymers with 40–50 mol% DPODPS had not only high T_gs of 170–172°C, but also moderate T_ms of 326–333°C, which are extremely suitable for melt processing. These copolymers have tensile strengths of 96.5–108.1 MPa, Young's moduli of 1.98–3.05 GPa, and elongations at break of 13–26% and exhibit excellent thermal stability and good resistance to acidity, alkali, and common organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.