聚苯硫醚砜的合成及表征

探索了聚苯硫醚矾树脂在常压下的合成方法，得到了优化的合成工艺条件。在原材料的量之比0．98—1．02、反应温度160—220℃、时间2—8h的条件下制得的高摩尔质量聚合物，其粘数可达到35mL／g；并通过元素分析、红外光谱、紫外光谱、X—衍射和热分析对其结构和性能进行了表征，证明合成的高聚物为线型非晶性聚苯硫醚矾树脂，是一种具有极高热稳定性和耐化学腐蚀性的高性能材料。     

Crystallization and melting behavior of poly(p‐phenylene sulfide) in blends with poly(ether sulfone)

Crystallization and melting behaviors of poly(p‐phenylene sulfide) (PPS) in blends with poly(ether sulfone) (PES) prepared by melt‐mixing were investigated by differential scanning calorimetry (DSC). The blends showed two glass transition temperatures corresponding to PPS‐ and PES‐rich phases, which increased with increasing PES content, indicating that PPS and PES have some compatibility. The cold crystallization temperature of the blended PPS was a little higher than that of pure PPS. Also, the heats of crystallization and melting of the blended PPS decreased with increasing PES content, indicating that the degree of crystallinity decreased with an increase of PES content. The isothermal crystallization studies revealed that the crystallization of PPS is accelerated by blending PPS with 10 wt % PES and further addition results in the retardation. The Avrami exponent n was about 4 independent on blend composition. The activation energy of crystallization increased by blending with PES. The equilibrium melting point decreased linearly with increasing PES content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1686–1692, 1999     

Studies on the thermal properties of poly(phenylene sulfide amide)

Thermal properties of poly(phenylene sulfide amide) (PPSA) prepared using sodium sulfide, sulfur, and thiourea as sulfur sources which reacted with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure, were studied. The glass transition temperature (T_g), melting point temperature (T_m), and melting enthalpy (ΔH_m) of the related polymers were obtained by use of differential scanning calorimetry analysis. The results are: T_g = 103.4–104.5°C, T_m = 291.5–304.7°C, and ΔH_m = 104.4–115.4 J/g. Thermal properties such as thermal decomposition temperature and decomposition kinetics were investigated by thermogravimetric analysis under nitrogen. The initial and maximum rate temperatures of degradation were found to be 401.5–411.7°C and 437–477°C, respectively. The parameters of thermal decomposition kinetics of PPSAs were worked out to be: activation energy of degradation was 135 to 148 kJ/mol and the 60-s half-life temperature was 360 to 371°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1227–1230, 1997     

Poly(hydroxyether sulfone) and its blends with poly(ethylene oxide): miscibility, phase behavior and hydrogen bonding interactions

Poly(hydroxyether sulfone) (PHES) was synthesized through polycondensation of bisphenol S with epichlorohydrin. It was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy and differential scanning calorimetry (DSC). The miscibility in the blends of PHES with poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. DSC showed that the PHES/PEO blends prepared by casting from N,N-dimethylformamide (DMF) possessed single, composition-dependent glass transition temperatures (T_gs), indicating that the blends are miscible in amorphous state. At elevated temperatures, the PHES/PEO blends underwent phase separation. The phase behavior was investigated by optical microscope and the cloud point curve was determined. A typical lower critical solution temperature behavior was observed in the moderate temperature range for this blend system. FTIR studies indicate that there are the competitive hydrogen bonding interactions upon adding PEO to the system, which was involved with the intramolecular and intermolecular hydrogen bonding interactions, i.e. -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO between PHES and PEO. In terms of the infrared spectroscopic investigation, it is judged that from weak to strong the strength of the hydrogen bonding interactions is in the following order: -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO.     

Miscibility and phase behavior in blends of phenolphthalein poly(ether sulfone) and poly(hydroxyether of bisphenol A)

Miscibility and phase behavior in the blends of phenolphthalein poly(ether sulfone) (PES-C) with poly(hydroxyether of bisphenol A) (PH) were investigated by means of differential scanning calorimetry (DSC), high resolution solid state nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FTIR). It was found that the homogeneity of the as-prepared blends depended on the solvents used; N,N-dimethylformamide (DMF) provided the segmental mixing for PH and PES-C, which is confirmed by the behavior of single, composition-dependent glass transition temperatures (T_g's). To examine the homogeneity of the blends at the molecular level, the proton spin-lattice relaxation times in the rotating frame T_1ρ(H) were measured via ¹³C CP/MAS NMR spectroscopy as a function of blend composition. In view of the T_1ρ(H) values, it is concluded that the PH and PES-C chains are intimately mixed on the scale of 20-30 Å. FTIR studies indicate that there were the intermolecular specific interactions in this blends, involved with the hydrogen-bonding between the hydroxyls of PH and the carbonyls of PES-C, and the strength of the intermolecular hydrogen bonding is weaker than that of PH self-association. At higher temperature, the PH/PES-C blends underwent phase separation. By means of thermal analysis, the phase boundaries of the blends were determined, and the system displayed the lower critical solution temperature behavior. Thermogravity analysis (TGA) showed that the blends exhibited the improved thermal stability, which increases with increasing PES-C content.     

Physical aging of epoxy resin blended with poly(ether sulfone): Effect of poly(ether sulfone) molecular weight

The physical aging process of 4-4′-diaminodiphenylsulfone (DDS) cured diglycidyl ether bisphenol-A (DGEBA) blended with various molecular weights of poly(ether sulfone) (PES; M_n = 28,600, 10,600, and 6,137) was studied by DSC. For DGEBA/DDS system blended with a low MW PES-3 (M_n = 6,137), no phase separation of the polymer blend and only one enthalpic relaxation process due to physical aging was observed. Since the high MW PES-1 (M_n = 28,600) had a T_g close to that of fully cured DGEBA/DDS, the fully cured DGEBA/DDS/PES-1 blend had a broader glass transition than a neat DGEBA/DDS system. However, the DSC results showed two enthalpic relaxation processes due to the physical aging of PES-rich and cured epoxy-rich phases as the material was aged at 155 °C (30 °C below T_g). Since the T_gs of PES-1-rich and epoxy-rich phases overlapped with each other, the enthalpic relaxation processes corresponding to each phase coupled to each other in the earlier stage of physical aging. The medium MW PES-2 (M_n = 10,600) has a much lower T_g than that of fully cured DGEBA/DDS, two well separated T_gs were observed for the cured DGEBA/DDS/PES-2 blend, indicating the cured epoxy was immiscible with PES. Aging the polymer blend at 155 °C (24 °C below T_g1 of the PES-2-rich phase and 53 °C below T_g2 of the epoxy-rich phase) produced two well separated relaxation processes due to PES-2-rich and epoxy-rich phases. The experimental results suggested that aging the polymer blend at a suitable temperature would improve the phase separation between PES-1-rich and epoxy-rich phases.     

Incorporation of different crystallizable amide blocks in segmented poly(ester amide)s

High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of dimethyl adipate, 1,4-butanediol and a symmetrical bisamide-diol based on ε-caprolactone and 1,2-diaminoethane or 1,4-diaminobutane. FT-IR and WAXD analysis revealed that segmented poly(ester amide)s based on the 1,4-diaminobutane (PEA(4)) give an α-type crystalline phase whereas polymers based on the 1,2-diaminoethane (PEA(2)) give a mixture of α- and γ-type crystalline phases with the latter being similar to γ-crystals present in odd-even nylons. PEA(2) and PEA(4) polymers with a hard segment content of 25 or 50 mol% have a micro-phase separated structure with an amide-rich hard phase and an ester-rich flexible soft phase. All polymers have a glass transition temperature below room temperature and melt transitions are present at 62-70 °C (T_m,1) and at 75-130 °C (T_m,2) with the latter being highest at higher hard segment content. The two melt transitions are ascribed to melting of crystals comprising single ester amide sequences and two or more ester amide sequences, respectively. These polymers have an elastic modulus in the range of 159-359 MPa, a stress at break in the range of 15-25 MPa combined with a high strain at break (590-810%). The thermal and mechanical properties are not influenced by the different crystalline structures of the polymers, only by the amount of crystallizable hard segment present.     

Synthesis and characterization of poly(ester amide)s containing crystallizable amide segments

High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of 1,4-butanediol, dimethyl adipate and a preformed bisamide-diol based on 1,4-diaminobutane and ε-caprolactone. By varying the ratio of the bisamide-diol and 1,4-butanediol, a series of polymers was obtained with a hard segment content between 10 and 85 mol%. FT-IR and WAXD analysis revealed that the poly(ester amide)s crystallize in an α-type phase similar to the α-phase of even-even nylons. These polymers all have a micro-phase separated structure with an amide-rich hard phase and an ester-rich flexible soft phase. The polymers have a low and a high melt transition, corresponding with the melting of crystals comprising single ester amide sequences and two or more ester amide sequences, respectively. The low melt transition is between 58 and 70 °C and is independent of polymer composition. By increasing the hard segment content from 10 to 85 mol% the high melt transition increased from 83 to 140 °C while the glass transition temperature increased from −45 to −5 °C. Likewise, the elastic modulus increased from 70 to 524 MPa, the stress at break increased from 8 to 28 MPa while the strain at break decreased from 820 to 370%. Thermal and mechanical properties can thus be tuned for specific applications by varying the hard segment content in these segmented polymers.     

Gas foaming of segmented poly(ester amide) films

Biodegradable segmented poly(ester amide)s, based on dimethyl adipate, 1,4-butanediol and N,N′-1,2-ethanediyl-bis[6-hydroxy-hexanamide], with two distinct melting transitions were gas foamed using carbon dioxide (CO₂). Polymer films were saturated with CO₂ at 50 bar for 6 h after which the pressure was released. The samples were immersed in octane at the desired temperature after which foaming started immediately. Just above the lower melt transition the polymers retain adequate mechanical properties and dimensional stability, while the chain mobility increased sufficiently to nucleate and expand gas cells during the foaming process. In this way semi-crystalline poly(ester amide)s can be gas foamed below the flow temperature.Two poly(ester amide)s with 25 mol% (PEA2,5-25) and 50 mol% (PEA2,5-50) of bisamide segment content were foamed at 70 and 105 °C, respectively. The storage modulus (G′) of both pure polymers at the onset foaming temperature is 50-60 MPa. Closed-cell foams were obtained with a maximum porosity of ∼90%. The average pore size of PEA2,5-25 ranges from 77 to 99 μm. In contrast, the average pore size of PEA2,5-50 is in between 2 and 4 μm and can be increased to 100 μm by lowering the CO₂ saturation pressure to 20 bar. The porosity of PEA2,5-50 foams using this saturation pressure decreased to 70%.     

聚苯硫醚砜及其复合材料的特性与应用

介绍了聚苯硫醚砜(PPSS)在国内外的发展概况，综述了PISS及其复合材料的物理力学性能、改性技术和成型工艺；着重介绍了PPSS／GF、PPSS／PPS以及PPSS／聚酯共混物的性能，介绍了PISS膜的研究进展并展望了其发展应用前景。     

Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

Poly(ether ether sulfone amide)s as a new category of processable heat-resistant polymers

The aim of study was to prepare novel polyamides with improved solubility and processability without sacrifice of their thermal and mechanical properties. Polyamides containing ether and sulfone units were obtained via condensation of a special diamine with various diacid chlorides. Poly(ether ether sulfone amide)s were obtained in good inherent viscosities ranging from 0.72 to 0.84 dL/g. All the polyamides were amorphous and readily soluble in polar solvents and swelled in CH₂Cl₂ and tetrahydrofuran. Flexible films of polymers were obtained by solution casting. Polyamide films exhibited good mechanical and thermal stability including the temperature for 10% weight loss of 449–476 °C.     

聚芳醚砜酮纤维的热性能

采用DSC、TG测定了含联苯结构聚芳醚砜酮 (PPESK)纤维的热性能 ,结果表明 ,纤维的玻璃化温度随砜酮比的增大而提高 ,纤维的起始分解温度大于 463℃。当砜酮比为 15 / 85 ,5 0 / 5 0 ,75 / 2 5时 ,纤维的玻璃化温度分别为 2 5 7.62 ,2 78.64 ,2 79.71℃ ;热分解活化能分别为 15 0 .8,2 19.9,195 .5kJ/mol;热分解反应级数分别为 1,1.76,1级     

Side-chain phenol-functionalized poly(ether sulfone) and its contribution to high-performance and flexible epoxy thermosets

We prepared a side-chain phenol-functionalized poly(ether sulfone) (P1) from a one-pot reaction of a 4,4′-dihydroxybenzophenone (DHBP)-based poly(ether sulfone), poly(oxy-1,4-phenylenecarbonyl-1,4-phenyleneoxy-1,4-phenylene-sulfonyl-1,4-phenylene (DHBP-PES)), with 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and phenol in the presence of sulphuric acid. The phenol linkages of P1 act as reacting sites for epoxy resins. Subsequently, flexible and light-yellow transparent films of epoxy thermosets can be achieved from the curing of P1 with cresol novolac epoxy (CNE) and diglycidyl ether of bisphenol A (DGEBA). The thermoset based on P1 and CNE (P1/CNE) shows a high T_g value (241 °C), a low coefficient of thermal expansion (44 ppm/°C), and flame retardancy (VTM-0). The moderate-to-high molecular weight of P1 is responsible for the characteristics high T_g and flexibility, which are rarely seen in epoxy thermosets based on a low-molecular weight curing agent.     

Impact behavior of phenolphthalein poly(ether sulfone)/ultrahigh molecular weight polyethylene blends

This work presents the structure and impact properties of phenolphthalein poly(ether sulfone) blended with ultrahigh molecular weight polyethylene (PES-C/UHMWPE) at different compositions. The addition of UHMWPE can considerably improve the Charpy and Izod impact strength of the blends. The fracture surface is examined to demonstrate the toughening mechanics related to the modified PES-C resin. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 113–118, 1998     

Mechanical and Thermal Properties of Poly(Phthalazinone Ether Sulfone)/Poly(Ether Sulfone) Blends

The mechanical and thermal properties of poly(phthalazinone ether sulfone) (PPES)/poly(aryl ether sulfone) (PES) blends prepared by melt-mixing were investigated by dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). The dynamic mechanical thermal analysis results show that the incorporated PES has a large influence on the heat stability of PPES. The DMTA results display that the blends with a single glass transition temperature, which increases with increasing PPES content, indicates that PPES and PES are completely miscible over the studied composition range. The thermodegradative behavior of PPES/PES blends was used to analyze their thermal stability. The Friedman technique was used to determine the kinetic parameters (i.e., the apparent activation energy and order of reaction of the degradation process). The results indicate that the presence of the PES component influences the thermal stability of the PPES. On the basis of the kinetic data derived from Friedman' approach, the lifetime estimates for pure PPES, pure PES, and the blends generated from the weight loss of 5% were constructed.     

Study on Thermal Properties and Crystallization Behavior of Blends of Poly(phenylene sulfide)/Poly(ether imide)

The thermal behavior of poly(phenylene sulfide) (PPS) blends with poly(ether imide) (PEI) was studied by differential scanning calorimeter (DSC). The crystallization temperature of PPS in blends shifted from 216.8°C to 226.4°C upon addition of 20–70% PEI contents. The heat of crystallization remained unchanged with less than 50% PEI in blends, whereas the heat of fusion decreased with increasing PEI content. The isothermal crystallization indicated that incorporating PEI would accelerate the crystallization rate of PPS. The activation energy of crystallization increased with addition of PEI. The equilibrium melting point of PPS/PEI blends was not changed with compositions.     

Sulfonated poly(arylene ether sulfone) as an electrode binder for direct methanol fuel cell

Sulfonated poly(arylene ether sulfone) (sPAES) is synthesized and characterized for the application to the electrode binder for direct methanol fuel cell (DMFC). The effect of sPAES binder in the electrode on the cell performance is studied. The cell based on sPAES binder showed a good adhesion to the sPAES membrane, while Nafion binder is delaminated from the sPAES membrane after supplying the fuel for a prolonged time. The sPAES binder for electrode is found to be more efficient in achieving long-term stability of the cell performance than the conventional Nafion binder.     

聚苯硫醚砜与聚苯硫醚共混体系的初步探索

采用DSC对聚苯硫醚砜(PPSS)／聚苯硫醚(PPS)合金进行了测试，结果表明，PPSS与PPS的玻璃化温度发生了相互靠拢的现象，说明两组分间产生了部分相容的趋势；对PPSS／PPS(质量比50／50)合金的TG分析也表明，PPSS与PPS产生了部分相容；采用X射线衍射对PPSS／PPS的聚集态结构进行了表征，发现随PPS质量分数增大。结晶峰越来越明显。峰面积也随之增大。     

Synthesis and characterization of hexafluoroisopropylidene bisphenol poly(arylene ether sulfone) and polydimethylsiloxane segmented block copolymers

A series of hexafluoroisopropylidene bisphenol poly(arylene ether sulfone) (BAF PAES) segmented block copolymers with varying fractions of polydimethylsiloxane (PDMS) were synthesized by a condensation reaction of hydroxyl-terminated BAF PAES and dimethylamino endcapped PDMS. The segmented block copolymers have high thermal stability. The BAF PAES homopolymer exhibits a tensile modulus of 1700 MPa and an elongation at break of 16%. Copolymerizing BAF PAES with increasing molecular weight amounts of PDMS results in tensile properties ranging from plastic to elastomeric where the elongation is 417% for a segmented block copolymer with 64 wt% PDMS incorporated. The morphological properties of these segmented block copolymers were characterized by atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). AFM and TEM images show the segmented block copolymers were microphase separated, and comparison with bisphenol A (BA) PAES-b-PDMS segmented block copolymers revealed complex differences between the morphological behavior of the two systems. SAXS data of the segmented block copolymers supports AFM and TEM images, indicating microphase separation but little long-range order.