Crystallization of poly(aryl ether ketone ketone) copolymers containing terephthalate/isophthalate moieties

In a previous study, we have investigated the structure, crystallization, and morphology of poly(aryl ether ketone ketone), PEKK, copolymers prepared from diphenyl ether (DPE), terephthalic acid (T), and isophthalic acid (I) with T/I ratios from 100/0 to 50/50. These materials were considered as having -DPE-T-DPE-T- (TT) and/or -DPE-T-DPE-I- (TI) “phthalate diads.” In this work, we continue the study of this copolymer series with six different T/I ratios (40/60, 30/70, 20/80, 15/85, 10/90, and 0/100), which are viewed as having TI and/or -DPE-I-DPE-I- (II) “diads.” The I moieties (1,3-linked isomers) were always found to be incorporated in the crystals and acted as “entropy or symmetry” defects that effectively decreased the equilibrium melting temperature T_m^o and the rate of crystallization. However, the retardation of crystallization in PEKK 0/100 (the homopolymer with pure II diads) was significantly less than expected, which was attributed to the segregation of I moieties between the chains leading to a reduction of total entropy in the unit cells. The evidence of segmental segregation in PEKK 0/100 was seen in x-ray diffraction patterns, where several extra reflections were seen that could only be indexed by the published unit cell modified with a larger c-axis dimension (3.048 nm, corresponding to the length of six phenyl residues or 1.524 nm, the length of three phenyl residues). The composition of 15/85 was found to have the lowest value of T_m^o and the slowest crystallization rate. Upon heating, the “II” crystals (T/I from 30/70 to 0/100) exhibited the conventional double-melting behavior rather than the triple-melting behavior as in the “TI” crystals (50/50 to 40/60). No indication of the second polymorph form 2 was found in “II” crystals. © 1994 John Wiley & Sons, Inc.     

磺化聚醚酮酮的合成和表征

研究了以硫酸为磺化剂由聚醚酮酮来合成磺化聚醚酮酮的方法，探讨了硫酸浓度、反应温度、反应时间和聚醚酮酮在硫酸中的浓度等因素对聚醚酮酮的磺化度和离子交换容量的影响，制得了磺化度为１５５ｍｍｏｌ／ｇ、离子交换容量为１５７ｍｍｏｌ／ｇ的磺化聚醚酮酮．用红外光谱表征了其结构，用Ｘ 射线进行了结晶度的分析，用ＤＳＣ进行了热分析     

Relationship between morphology and glass transition temperature in solvent-crystallized poly(aryl ether ketones)

The relationship between semicrystalline morphology and glass transition temperature has been investigated for solvent-crystallized poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK). Solvent-crystallized specimens of both PEEK and PEKK displayed a sizeable positive offset in T_g compared to quenched amorphous specimens as well as thermally crystallized specimens of comparable bulk crystallinity; the offset in T_g for the crystallized samples reflected the degree of constraint imposed on the amorphous segments by the crystallites. Small-angle X-ray scattering studies revealed markedly smaller crystal long periods (d) for the solvent-crystallized specimens compared to samples prepared by direct cold crystallization. The strong inverse correlation observed between T_g and interlamellar amorphous thickness (l_A) based on a simple two-phase model was in excellent agreement with data reported previously for PEEK, and indicated the existence of a unique relationship between glass transition temperature and morphology in these poly(aryl ether ketones) over a wider range of sample preparation history and lamellar structure than was previously reported. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 65–73, 1998     

Non-Linear response of a long,discontinuous fiber/melt system in elongational flows

The authors investigated the transient elongational behavior of a highly-aligned 600% volume fraction long, discontinuous fiber filled poly-ether-ketone-ketone melt with a computer-controlled extensional rheometer at 370°C. Prior experiments at controlled strain rate and stress produced _E ⁺ (t, ) and ^– (t, _E) similar to a shear dominated flow of a non-linear viscoelastic fluid. Stress relaxation following steady extension showed nonlinear effects in the change in stress decay rate with increasing strain rate. Continuous relaxation spectra showed a shift in the spectral peak to smaller values of with increasing strain rate. The Giesekus nonlinear constitutive relation modeled the elongation and stress relaxation with shearing rate at the fiber surface set by a strain rate magnification factor. Suitable for elongation, the model produced insufficient shift in the stress relaxation spectrum to account for the large change in stress decay rate exhibited in the experiments.English alphabet a _r aspect ratio of the fibers or l/d - A ₀ initial uniform cross-section area of the specimen - d fiber diameter - f fiber volume fraction - H() relaxation spectrum found by the method of Ferry and William l length of the fiber - L(t) time function specimen length - L ₀ initial specimen length - r radial coordinate across the shear cell - R _i fiber radius and inner cell dimension - R _o outer cell radius - t time in s - t _max duration of the extension - T _g glass transition temperature of the polymer - v velocity of the moving end of the test specimen - x axial position where is calculated Greek alphabet nonlinearity parameter in the Giesekus relation - axial mass distribution along the specimen major axis - shear strain rate - strain tensor - ₍₁₎ first convected derivative of the strain tensor - ₍₂₎ second convected derivative of the strain tensor - average strain at the end of extension as determined from - extension strain rate - average extension strain rate determined from - ^– transient strain rate under controlled stress, creep, test - _E elongational viscosity - _Eapp apparent elongational viscosity determined from - _E ⁺ transient elongational viscosity - ₀ zero shear rate viscosity - relaxation parameter - ₁ relaxation parameter in either Jeffrey's or Giesekus fluid - ₂ retardation parameter in either Jeffrey's or Giesekus fluid - _max relaxation value at which 99.9% of the H spectrum had occurred - _p relaxation value at which H reaches a maximum - volumetric composite density - _E elongational stress - _E ⁺ transient elongational stress - _E ^– controlled elongational stress, creep stress - _E ^y peak elongational stress in controlled experiment - shear stress at surface of the fiber in a shear cell - _yx simple shear component of the strain rate tensor - stress tensor - ₁ first convected derivative of the stress tensor     

Original Preparation of PEKK Dispersion for Coating by Transfer from a Chloroform Stable Dispersion to an Aqueous Stable Dispersion,by Emulsion/Solvent Evaporation

In this work, aqueous dispersions of PolyEtherKetoneKetone (PEKK) oligomers were obtained by an emulsion/dispersion solvent evaporation technique. The PEKK oligomers were synthesized by a Friedel–Crafts acylation with a number average degree of polymerization of 4. The synthesized PEKK oligomers had very good thermal stability and spontaneously formed a stable dispersion of swollen micrometric fibers in chloroform. After sonication of the chloroform dispersion in water in the presence of sodium dodecyl sulfate (SDS) and evaporation, we obtained aggregated particles with a mean diameter between 120 and 160 nm, decreasing linearly with the PEKK concentration. The most stable dispersions were obtained with 0.5% wt of surfactant and, at a fixed concentration of SDS, the stability decreased when the PEKK concentration was increased. The different dispersions of PEKK in water were very stable and, after water evaporation, formed homogeneous films for high-performance coating.     

Influence of blend miscibility on the proton conductivity and methanol permeability of polymer electrolyte blends

The influence of miscibility on the transport properties of polymer electrolyte blends composed of a proton conductor and an insulator was investigated. The proton‐conductive component in the blends was sulfonated poly(ether ketone ketone) (SPEKK), while the nonconductive component was either poly(ether imide) (PEI) or poly(ether sulfone) (PES). The phase behavior of PEI‐SPEKK blends was strongly influenced by the sulfonation level of the SPEKK. At low sulfonation levels (ion‐exchange capacity (IEC) = 0.8 meq/g), the blends were miscible, while at a slightly higher level (IEC = 1.1 meq/g), they were only partially miscible and for IEC ≥ 1.4 meq/g they were effectively immiscible over the entire composition range. The PES‐SPEKK blends were miscible over the entire range of SPEKK IEC considered in this study (0.8–2.2 meq/g). At high IEC (2.2 meq/g) and at low mass fractions of SPEKK (<0.5), the miscible blends (PES‐SPEKK) had higher proton conductivities and methanol permeabilities than the immiscible ones (PEI‐SPEKK). The opposite relationship was observed for high mass fractions of SPEKK (>0.5). This behavior was explained by the differences in morphology between these two blend systems. At low IEC of SPEKK (0.8 meq/g), where both PEI‐SPEKK and PES‐SPEKK blend systems exhibited miscibility, the transport properties were not significantly different. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2253–2266, 2006