Glass transition and miscibility in blends of two semicrystalline polymers: Poly(aryl ether ketone) and poly(ether ether ketone)

Binary melt‐blended mixtures of two aryl ether ketone polymers (i.e., a new poly(aryl ether ketone) (code name PK99) and poly(ether ether ketone) (PEEK), have been studied. Polymer miscibility in glassy amorphous (or melt) domains has been demonstrated for the binary blend comprising of two aryl‐ether‐ketone‐type semicrystalline polymers. Composition‐dependent, single T_g was observed within full composition range in the PK99/PEEK blends, and the narrow T_g breadth also suggests that the scale of mixing was fine and uniform. To better resolve any possible overlapping T_g's, physical aging was imposed on a comparison set of blend samples for the purpose of improving detectability of overlapped multiple transitions if existing. The result still showed one single T_g. The relative sharp T_g and lack of cloud point transition suggest that the scale of molecular intermixing is good. Phase homogeneity was further confirmed using optical and scanning electron microscopy. The X‐ray diffractograms suggest that isomorphism does not exist in the PK99/PEEK blends and that the crystal forms of the respective polymers remain distinct and unchanged by the miscibility in the amorphous region. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1485–1494, 1999     

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) and poly(aryl ether ether ketone) containing thioether units

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) with lateral methoxy groups (M-PAEK) and poly(aryl ether ether ketone) containing thioether units (S-PEEK) have been investigated by differential scanning calorimetry (DSC) and polarized light microscopy (PLM) techniques. The results indicate that the composition of the blends has great effect on the phase behavior and morphology. Thin films of pure M-PAEK and S-PEEK crystallized from the melts exhibit typical mosaic and spherulitic structures, respectively. For the blends with higher M-PAEK contents (> 50%), an unusual ring-banded spherulite with structural discontinuity is formed. The bright core and rings of the ring-banded spherulites under PLM are composed of M-PAEK phase, while the dark rings consist mainly of S-PEEK phase. For the 50:50 M-PAEK/S-PEEK blend, the ring-banded spherulites and S-PEEK spherulites coexist, which implies that a partial phase separation between the two components takes place in the melting state. In S-PEEK-rich blends, a volume-filled spherulite is produced. In addition, the effect of isothermal crystallization temperature on the phase behavior, especially the ring-banded spherulite formation in the blends, is discussed.     

Synthesis and characterization of multiblock copolymers based on hydrophilic disulfonated poly(arylene ether sulfone) and hydrophobic partially fluorinated poly(arylene ether ketone) for fuel cell applications

Sulfonated fluorinated multiblock copolymers based on high performance polymers were synthesized and evaluated for use as proton exchange membranes (PEMs). The multiblock copolymers consist of fully disulfonated poly(arylene ether sulfone) and partially fluorinated poly(arylene ether ketone) as hydrophilic and hydrophobic segments, respectively. Synthesis of the multiblock copolymers was achieved by a condensation coupling reaction between controlled molecular weight hydrophilic and hydrophobic oligomers. The coupling reaction could be conducted at relatively low temperatures (e.g., 105 °C) by utilizing highly reactive hexafluorobenzene (HFB) as a linkage group. The low coupling reaction temperature could prevent a possible trans‐etherification, which can randomize the hydrophilic‐hydrophobic sequences. Tough ductile membranes were prepared by solution casting and their membrane properties were evaluated. With similar ion exchange capacities (IECs), proton conductivity and water uptake were strongly influenced by the hydrophilic and hydrophobic block sequence lengths. Conductivity and water uptake increased with increasing block length by developing nanophase separated morphologies. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) experiments revealed that the connectivity of the hydrophilic segments was enhanced by increasing the block length. The systematic synthesis and characterization of the copolymers are reported. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 214–222, 2010     

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007     

Preparation and characterization of branched and linear sulfonated poly(ether ketone sulfone) proton exchange membranes for fuel cell applications

Branched sulfonated poly(ether ketone sulfone)s (Br‐SPEKS) were prepared with bisphenol A, bis(4‐fluorophenyl)sulfone, 3,3′‐disodiumsulfonyl‐4,4′‐difluorobenzophenone, and THPE (1,1,1‐tris‐p‐hydroxyphenylethane), respectively, at 180 °C using potassium carbonate in NMP (N‐methylpyrrolidinone). THPE, as a branching agent, was used with 0.4 mol % of bisphenol A to synthesize branched copolymers. Copolymers containing 10–50 mol % disulfonated units were cast from dimethylsulfoxide solutions to form films. Linear sulfonated poly(ether ketone sulfone)s (SPEKS) were also synthesized without THPE. The films were converted from the salt to acid forms with dilute hydrochloric acid. A series of copolymers were studied by Fourier transform infrared, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion‐exchange capacity (IEC), a measure of proton conductivity, was evaluated. The synthesized Br‐SPEKS and SPEKS membranes exhibit conductivities (25 °C) from 1.04 × 10^?3 to 4.32 × 10^?3 S/cm, water swell from 20.18 to 62.35%, IEC from 0.24 to 0.83 mequiv/g, and methanol diffusion coefficients from 3.2 × 10^?7 to 4.7 × 10^?7 cm²/S at 25 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1792–1799, 2008     

几种甲基取代的聚醚酮酮的合成与表征

聚芳醚酮是一类热、电、机械性能优异的热塑性工程塑料,其合成方法有亲电取代法和亲核取代法．近年来,通过改变主链上醚酮键的比例和次序以及在主链上引入ｓｐ３杂化原子团,如砜基、烷基,对其进行结构上的改性研究已有很多报道［１４］．另一种结构上的改性研究是在...     

Poly(ether ether ketone)/poly(aryl ether sulphone) blends: thermal degradation behaviour

The thermodegradative behaviour of blends of poly(ether ether ketone) (PEEK) and poly(aryl ether sulphone) (PES) was studied by dynamic thermogravimetry in order to analyze their thermal stability. The Freeman-Carrol differential approach was used to determine the kinetic parameters i.e. the apparent activation energy (E_a) and order of reaction (n), of the degradation process. The results indicate that the presence of one component influences the thermal stability of the other. Both, temperature for 5% weight loss (T₅) and E_a for blends show a negative deviation from the linear behaviour, which signifies a lowering of thermal stability compared to homopolymers. The decrease in the thermal stability at low concentration of PES in PEEK has been explained on the basis of chemical interactions of the degradation products of PES, which has lower induction temperature for degradation, with PEEK and also on the reduction of viscosity of the medium. But the decrease in thermal stability at low concentration of PEEK in PES is unusual and at present, without the complete elucidation of degradation mechanism in these blends, is difficult to explain.     

聚醚砜醚酮的合成与性能

以4,4′-二羟基二苯砜和4,4′-二氟二苯酮为单体, 通过溶液缩聚合成了聚醚砜醚酮(PESEK), 其分子结构相当于聚醚砜(PES)与聚醚醚酮(PEEK)的交替共聚物. 在共聚物分子中, 存在砜基、醚基和酮基, 整个结构单元形成了大共轭体系, 聚合物属无定形聚合物, 玻璃化转变温度(Tg)为198 ℃, 介于PEEK和PES的Tg之间, 其热稳定性和加工性能优于PES, 而力学性能与PES接近.     

Glass transition,crystallization, and morphology relationships in miscible poly(aryl ether ketones) and poly(ether imide) blends

The relationships among glass transition, crystallization, melting, and crystal morphology of poly(aryl ether ketone) (PAEK)/poly(other imide) (PEI) blends was studied by thermal, optical and small-angle x-ray scattering (SAXS) methods. Two types of PAEK were chosen for this work: poly(aryl ether ether ketone), PEEK, and poly(aryl ether ketone ketone), PEKK, which have distinctly different crystallization rates. Both PAEKs show complete miscibility with PEI in the amorphous phase. As PAEK crystallizes, the noncrystallizable PEI component is rejected from the crystalline region, resulting in a broad amorphous population, which was indicated by the broadening and the increase of T_g over that of the purely amorphous mixture. The presence of the PEI component significantly decreases the bulk crystallization and crystal growth rate of PAEK, but the equilibrium melting temperature and crystal surface free energies are not affected. The morphology of the PEI segregation was investigated by SAXS measurements. The results indicated that the inter(lamellar-bundle) PEI trapping morphology was dominant in the PEEK/PEI blends under rapid crystallization conditions, whereas the interspherulitic morphology was dominant in the slow crystallizing PEKK/PEI blends. These morphologies were qualitatively explained by the expression δ=D/G, where G was the crystal growth rate and D was the mutual diffusion coefficient. © 1993 John Wiley & Sons, Inc.     

聚醚醚酮/聚醚醚酮酮共混体系的熔融和等温结晶行为

采用熔融共混方法制备了聚醚醚酮和聚醚醚酮酮的共混物,用DSC对共混物的熔融行为和等温结晶行为进行了研究.结果表明,共混物熔点随聚醚醚酮含量增加而降低,但与聚醚醚酮酮有相同的平衡熔点,二者共混没有改变其结晶的成核与生长机制.     

新型多氯取代聚芳醚酮砜的合成与表征

新型多氯取代聚芳醚酮砜的合成与表征;聚芳醚酮砜;四氯对苯二甲酰氯;低温溶液缩聚;无规共聚物     

Cross‐linked poly(aryl ether sulfone) membranes for direct methanol fuel cell applications

Partially sulfonated poly(aryl ether sulfone) (PESS) was synthesized and methacrylated via reaction with glycidyl methacrylate (PESSGMA) and cross‐linked via radical polymerization with styrene and vinyl‐phosphonic acid (VPA). The chemical structures of the synthesized pre‐polymers were characterized via FTIR and ¹H NMR spectroscopic methods and molecular weight was determined via GPC. Membranes of these polymers were prepared via solution casting method. The crosslinking of the PESS polymer reduced IEC, proton conductivity, swelling in water, and methanol permeability of the membranes while increasing the modulus and the glass transition temperature. However, the introduction of the VPA comonomer increased the proton conductivity while maintaining excellent resistance to methanol cross‐over, which was significantly higher as compared with both PESS and the commercial Nafion membranes. Membranes of PESSGMA copolymers incorporating VPA, exhibited proton conductivity values at 60 °C in the range of 16–32 mS cm⁻¹ and methanol permeability values in the range of 6.52 × 10⁻⁹ – 1.92 × 10⁻⁸ cm² s⁻¹. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 558–575     

Dynamic Rheological Characterization of A Thermotropic Liquid Crystalline Poly (aryl ether ketone)

Poly(aryl ether ketone)s (PAEKs) have been widely used as advanced materials in applications because of their excellent thermal stabilities and good chemical resistance1. The high melt viscosity is one of the major drawbacks in processing them. The synthesis of thermotropic liquid crystalline PAEKs has shed light on the solving of this problem2 because they have been proved to have melt viscosities significantly lower in nematic state than those of the isotropic PAEKs and can be melt proce…     

Isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

The isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) are investigated by differential scanning calorimetry over two temperature regions. The Avrami equation describes the primary stage of isothermal crystallization kinetics with the exponent n ≈ 2 for both melt and cold crystallization. With the Hoffman–Weeks method, the equilibrium melting point is estimated to be 406 °C. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter (K_g) of the isothermal melt and cold crystallization is estimated. In addition, the K_g value of the isothermal melt crystallization is compared to those of the other poly(aryl ether ketone)s. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1992–1997, 2000     

(夹)二氧蒽改性聚芳醚酮酮

共聚物;合成;(夹)二氧蒽改性聚芳醚酮酮     

Poly(aryl ether ketone) composite membrane as a high‐performance lithium‐ion batteries separator

We described the design and synthesis of a modified poly(aryl ether ketone) bearing phenolphthalein and allyl groups (P‐PAEK) via nucleophilic polycondensation. A new kind of composite separator, crosslinked P‐PAEK/polyvinylidene fluoride (c‐P‐PAEK/PVDF) membrane was successfully prepared using phase separation, phase inversion method, and UV crosslinking technique. As a separator of lithium‐ion battery, c‐P‐PAEK/PVDF membrane demonstrates high porosity and uniform distribution of pores with interconnected pathways. Low thermal shrinkage, distinct shut‐down effect, high liquid electrolyte uptake capacity, and exciting liquid electrolyte wettability of the prepared c‐P‐PAEK/PVDF membrane have been revealed through comprehensive study. Moreover, the c‐P‐PAEK/PVDF membrane was applied to assemble a conventional Li/LiFePO₄ coin cell, which exhibited hopeful cell performance. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2714–2721     

聚醚醚酮酮结晶度研究

聚醚醚酮酮结晶度研究刘天西，王尚尔，张宏放，莫志深（中国科学院长春应用化学研究所高分子物理联合开放研究实验室长春１３００２２）那辉，王军佐，吴忠文（吉林大学化学系长春）关键词聚醚醚酮酮，广角Ｘ射线衍射，结晶度新型特种工程塑料聚醚醚酮酮（ＰＥＥＫＫ）具...     

Poly(ether ketone)–polyisobutylene block copolymers: Synthesis and phase behavior

Telechelic poly(ether ketone)s (PEKs) and polyisobutylenes (PIBs) were combined to form PIB? PEK? PIB triblock copolymers and (PIB? PEK)_n multiblock copolymers via the formation of urea linkages. Monovalent and bivalent amino telechelic PIBs were prepared quantitatively from allyl telechelic PIBs by a newly developed reaction sequence featuring nucleophilic reaction steps. Telechelic PEK? NCO polymers were prepared from the corresponding amino telechelic PEKs via a reaction with diphosgene. The highly reactive PEK? NCO and PIB? NH₂ telechelics formed PEK? PIB block copolymers only quantitatively when appropriately reactive primary amino groups were present on the amino telechelic PIBs. The obtained block copolymers were microphase‐separated and featured mostly lamellar structures, as determined by small‐angle X‐ray scattering (SAXS). Temperature‐dependent SAXS measurements revealed ordered polymers in the melt up to 210 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 188–202, 2005     

聚醚醚酮醚酮的合成与表征

聚醚醚酮（ＰＥＥＫ）自工业化以来［１］，由于其优异的性能已在机械、航天等领域得到广泛应用．各种聚芳醚酮类聚合物相继被开发出来．但以亲电缩聚路线制备聚醚醚酮醚酮（ＰＥＥＫＥＫ）的报道较少［２］．本文以二苯醚和４－氟苯甲酰氯为主要反应试剂，采取付氏酰基化...     

The double-melting behavior of poly(ether diphenyl ether ketone)

Poly(ether diphenyl ether ketone) (PEDEK) synthesized by the nucleophilic route has the following chemical structure: At some given temperatures for a given time isothermally crystallized PEDEK sample exhibits two endothermic peaks which are similar to PEEK and PEEKK. The melting behavior of PEDEK crystallized from the glassy state is investigated through differential scanning calorimeter (DSC). We consider that the high-melting peak is related to the perfect crystals and the low-melting peak is associated with a few imperfect crystals. © 1997 John Wiley & Sons, Inc.