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     

Nucleation effect of hydroxyl‐purified multiwalled carbon nanotubes in poly(p‐phenylene sulfide) composites

To investigate the nucleation effect of hydroxyl‐purified multiwalled carbon nanotubes (MWNTs‐OH) in poly(p‐phenylenesulfide) (PPS), a series of composites were prepared by blending PPS with MWNTs‐OH at 1, 2, and 3 wt %, respectively. Under SEM observation MWNTs‐OH were found homogeneously dispersed in the PPS matrix. DSC thermograms revealed that the enthalpy (ΔH_c) of the composites increased with increasing MWNT‐OH content, whereas the crystallization temperature (T_c) decreased progressively. The decrease in T_c was in accordance with the smaller crystallite size determined with WXRD characterization, and the increase in ΔH_c was evidenced by FTIR and XPS analyses. The higher ΔH_c shows that MWNTs‐OH serves as a nucleating agent, providing sufficiently multiplied sites for crystal growth. The lowering of T_c was attributed not only to MWNTs‐OH network hindrance to PPS chain fusing rearrangement, but also to a poorer affinity between MWNTs‐OH and PPS; both effects coordinately govern T_c of PPS/MWNTs‐OH composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of sulfuric acid bath on morphological structure and mechanical properties of poly(p‐phenylene‐1,3,4‐oxadiazole) fibers

Poly(p‐phenylene‐1,3,4‐oxadiazoles) (p‐PODs) spinning solution was prepared by one‐step polycondensation, and p‐POD fibers were obtained by wet spinning method using dilute sulfuric acid as coagulation bath. The morphology and mechanical properties of p‐POD fibers under different coagulating conditions, such as bath concentration and temperature, were qualitatively and quantitatively studied by microscopes, ultrasonic orientation measurement, WAXD, and other traditional methods. The microscopic observation indicated that the p‐POD fibers were of three‐layer structure which consisted of outer skin, inner skin, and the core. The skin‐core structure and surface feature of the fibers were greatly affected by the coagulating conditions. At the same time, the results of WAXD and ultrasonic orientation measurement demonstrated that the crystallinity and orientation of the fibers also varied with the change of bath conditions. The tests of mechanical properties showed that the tensile strength, elongation at break, and maximum draw ratio of the p‐POD fibers were determined by their solid‐phase structures, which were largely influenced by coagulation conditions. According to the structure analysis and the mechanical tests, the optimal coagulation parameters were chosen to obtain p‐POD fibers with denser and more regular structure and better mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

超支化聚苯硫醚与线性聚苯硫醚的对比表征

以2,4-二氯苯硫酚为原料,采用一步法合成超支化聚苯硫醚。笔者运用红外光谱、拉曼光谱、荧光光谱、示差扫描量热分析、热重分析、广角X-射线衍射、溶解实验等分析手段,对超支化聚苯硫醚和线性聚苯硫醚的基本性能进行了对比。由于两者结构上的差异,使得两者表现出不同的特性。超支化聚苯硫醚具有三取代苯结构,具有很强的荧光效应、完全的不结晶、溶于有机溶剂、热降解温度低于线性聚苯硫醚约60℃等特性。广角X-射线衍射谱图也和结晶、无定型线性聚苯硫醚有很大不同。     

Shear flow behaviors of poly(p‐phenylene benzobisoxazole) spinning dope

In this study, the shear flow properties of Poly(p‐phenylene benzobisoxazole) (PBO)/poly(phosphoric acid) (PPA) spinning dope were studied by means of capillary rheometer. The effect of shear stress, temperature, PBO concentration, and PBO molecular weight on the apparent viscosity of PBO/PPA dope was discussed. The results showed that the apparent viscosity of the dope decreased with the increase of the shear stress and the temperature. The flow behavior index increased with the increase of temperature, which indicated that the non‐Newtonian behavior of the dope became weaker at high temperature. Moreover, it was also found that at high shear stress, the apparent viscosity of the dope was insensitive to the temperature, PBO molecular weight, and PBO concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The evolution of structure and properties of poly(p‐phenylene terephthalamide) during the hydrothermal aging

The evolution of structure and properties of poly(p‐phenylene terephthalamide) (PPTA) with different hydrothermal aging temperatures were systematically investigated. The cooperative change in tensile strength and reduced viscosity upon aging time indicated a direct chemical structure‐property correlation. The linear relationship between tensile strength and reduced viscosity was explored. Wide angle X‐ray diffraction measurements disclosed the crystal structure of aramid fibers was stable with aging time and temperature. Fiber exhibited skin and core structure in different ways. Cracks and microfilbrils were observed in the core after hydrothermal aging, while the structure was unchanged in the skin. Fourier transform infrared spectroscopy also proved that the chemical structure of the skin was not affected by degradation. The results elucidated the hydrolysis of amide function happened in amorphous or bundles between microfibrils in the core rather than in skin of the fiber. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Superstructure and mechanical properties of poly(ethylene terephthalate) fibers zone‐drawn under critical necking tension

The superstructure and mechanical properties of poly(ethylene terephthalate) fibers zone‐drawn under a critical necking tension (σ_c) were studied. σ_c was defined as the minimum tension needed to generate a neck at a given drawing temperature (T_d) and was measured over a temperature range of 70–120°C. The σ_c value increased rapidly with decreasing T_d in the temperature range below 85°C, but the temperature dependence of σ_c was small above 85°C. The neck profile relied on T_d, becoming more shapely with decreasing T_d. A neck with a gradual decrease in diameter was observed in the fibers drawn at 100°C and above. The draw ratio increased significantly with increasing T_d above 90°C, but birefringence decreased. Density decreased gradually with increasing T_d, and fiber drawn at 120°C had a density of 1.347 g/cc. Wide‐angle X‐ray diffraction photographs of the fibers drawn at 100°C and below showed reflections due to crystallites, but a photograph of the fiber obtained at 120°C showed a ring‐like amorphous halo. The storage modulus (E′) at 25°C increased progressively with decreasing T_d, and the fiber drawn at 70°C had the maximum E′ value among the fibers drawn at a series of T_d's. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 179–185, 2002     

Synthesis,structure and properties of carbon nanotube/poly(p‐phenylene benzobisoxazole) composite fibres

Carbon nanotube/poly(p‐phenylene benzobisoxazole) (CNT/PBO) composite fibres were prepared by in situ polymerization and dry‐jet wet spinning. The structure and properties of the CNT/PBO fibres were investigated. FTIR and viscosity measurements showed that the functional groups on the CNT surface took part in the polymerization and affected the chemical structure and molecular weight of the composite. CNT/PBO composites with high molecular weight could be obtained by controlling the amount and addition time of CNTs. Compared with PBO fibres containing no CNTs prepared under the same conditions, the thermal resistance of the CNT (2 wt%)/PBO fibres was higher and the tensile strength was also improved by 20–50%. WAXD and SEM measurements indicated that the orientation degree of the CNT (2 wt%)/PBO fibres was smaller than that of PBO fibres. The fracture surfaces of these two fibres were also different. CNT dispersion in the CNT (2 wt%)/PBO fibres was examined by TEM. A model of the interactions between CNTs and PBO is proposed, based on these results. Copyright © 2006 Society of Chemical Industry     

Kinetics of thermal degradation of poly(p‐phenylene benzobisoxazole)

The kinetics of thermal degradation of poly (p-phenylen benzobisoxazole) (PBO) were studied by thermogravimetric analysis (TG) in dynamic nitrogen gas at four different heating rates: 5, 10, 15, 20°C/min. The activation energy calculated by Kissinger Method was 352.19 kJ/mol, and the mean value of activation energies evaluated by Flynn-Wall-Ozawa Method was 338.32 kJ/mol. The degradation kinetic model of PBO followed the mechanism of random scission of weak bonds of PBO molecule and impact of the active groups obtained from the broken bonds, Mampel Power equation with integral form G(α) = α^3/2 and differential form . And the mathematical equation of kinetic compensation effect was ln A = 0.1365 E_a − 1.4102. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3675–3679, 2007     

Micropatterning of poly(p‐phenylene vinylene) by femtosecond laser induced forward transfer

Conjugated polymers are important materials for optical applications, among which poly(p‐phenylene vinylene) (PPV) has a major role due to its applicability in sensors, organic light‐emitting diodes and large area displays. Despite advances on the synthesis of PPV‐based polymers and the improvements of their properties, its printing process, in particular involving the solid phase, remains unsuitable for the development of electro‐optical microcircuits. This paper demonstrates the printing of PPV from the solid phase in 2D micropatterns. Such an achievement was performed using laser induced forward transfer with femtosecond pulses, which allows area‐selective deposition within reduced scales as thin as ca 100 nm and 5 µm wide. Raman, fluorescence and electrochemical impedance spectroscopies confirm that the printed PPV micropatterns have the same structure, emission spectrum and conductivity as the target material, revealing the conservation of their original properties even after laser irradiation. The printing process was carried out using PPV films, overcoming the insolubility issue of this material. The optical and electrical characterization of the transferred PPV demonstrates the potential of this method for the patterning of electro‐optical microdevices, since luminescence and electrical conductivity were preserved. © 2018 Society of Chemical Industry     

In situ polymerization and photophysical properties of poly(p‐phenylene benzobisoxazole)/multiwalled carbon nanotubes composites

Poly(p‐phenylene benzobisoxazole)/multiwalled carbon nanotubes (PBO‐MWCNT) composites with different MWCNT compositions were prepared through in situ polymerization of PBO in the presence of carboxylated MWCNTs. The nanocomposite's structure, thermal and photophysical properties were investigated and compared with their blend counterparts (PBO/MWCNT) using Fourier transform infrared spectra, Raman spectra, Wide‐angle X‐ray diffraction, thermogravimetric analysis, UV‐vis absorption, and photoluminescence. The results showed that MWCNTs had a strong interaction with PBO through covalent bonding. The incorporation of MWCNTs increased the distance between two neighboring PBO chains and also improved the thermal resistance of PBO. The investigation of UV‐vis absorption and fluorescence emission spectra exhibited that in situ PBO‐MWCNT composites had a stronger absorbance and obvious trend of red‐shift compared with blend PBO/MWCNT composites for all compositions. This behavior can be attributed to the efficient energy transfer through forming conjugated bonding interactions in the PBO‐MWCNT composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Molecular weight determination of poly(phenylene sulfide ether)

Poly(phenylene sulfide ether) and poly(phenylene sulfoxide ether sulfide ether) (PPSOESE) were successfully prepared and their structures were proved by several analytical techniques in the present work. The molecular weight (MW) of PPSOESE, a soluble polymer in common organic solvent at room temperature, was determined by gel permeation chromatography. Based on the conversion reaction of the two polymers, the MW of PPSE was calculated and correlated with its intrinsic viscosity. As a result, the Mark‐Houwink equation for PPSE was concluded. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanism of degradation of poly(p‐phenylene benzobisoxazole) under hydrolytic conditions

Poly(p‐phenylene benzobisoxazole) (PBO) fiber has received great interest because of its excellent mechanical properties and good thermal stability. The objective of this study was to expose degradation mechanism of PBO under neutral and acidic conditions by molecular mass and Fourier transform infrared (FTIR) spectroscopy. Results were not consistent with the classic degradation mechanism, which indicates that degradation should occur through the ring opening and chain scission of the benzoxazole ring. The FTIR absorption spectra of PBO suggested that the o‐hydroxy amide linkage (the open ring structure) was present in the PBO molecule chain to some extent because of the incomplete polymerization. Further investigation showed that hydrolysis might occur in the open ring section during hydrolytic degradation. Based on the experimental data, a new degradation mechanism was proposed. It suggests that, in the early and middle stages, hydrolysis occurred primarily in the o‐hydroxy amide linkage of the open ring. The concentration of the o‐hydroxy amide structure determined the speed of degradation of PBO. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The characteristics of carbon nanotube‐reinforced poly(phenylene sulfide) nanocomposites

Multiwall carbon nanotube reinforced poly (phenylene sulfide) (PPS) nanocomposites were successfully fabricated through melt compounding. Structural, electrical, thermal, rheological, and mechanical properties of the nanocomposites were systematically studied as a function of carbon nanotube (CNT) fraction. Electrical conductivity of the polymer was dramatically enhanced at low loading level of the nanotubes; the electrical percolation threshold lay between 1 and 2 wt % of the CNTs. Rheological properties of the PPS nanocomposites also showed a sudden change with the CNT fraction; the percolation threshold was in the range of 0–0.5 wt % of CNTs. The difference in electrical and rheological percolation threshold was mainly due to the different requirements needed in the carbon nanotube network in different stages. The crystallization and melting behavior of CNT‐filled PPS nanocomposites were studied with differential scanning calorimetry; no new crystalline form of PPS was observed in the nanocomposites, but the crystallization rate was reduced. The thermal and mechanical properties of the nanocomposites were also investigated, and both of them showed significant increase with CNT fraction. For 5 wt % of CNT‐filled PPS composite, the onset of degradation temperature increased by about 13.5°C, the modulus increased by about 33%, and tensile strength increased by about 172%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polymerization characteristics and thermal degradation study of poly(phenylene sulfide ketone)

Poly(phenylene sulfide ketone) (PPSK) was synthesized by the reaction of sodium sulfide with 4,4′‐dichlorobenzophenone in N‐methyl‐2‐pyrrolidinone through the Phillips process. The effect of water hydration of sodium sulfide in solution, polymerization temperature, polymerization time, and stoichiometric ratio of monomers on the polymerization behavior of PPSK were investigated with respect to inherent viscosity and yield. Thermal degradation parameters of PPSK synthesized were investigated by dynamic thermogravimetry. To determine thermal degradation energy, Kissinger, Ozawa, and Friedman methods were used and activation energies were 202.3, 233.6, and 232.2 kJ/mol, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1329–1337, 2000     

High‐resolution thermogravimetry of poly(phenylene sulfide) film under four atmospheres

The thermal degradation of poly(phenylene sulfide) (PPS) film is investigated in air, nitrogen, helium, and argon with different physical and reactive characteristics at room temperature to 790°C as ascertained by high‐resolution thermogravimetry (TG) at a variable heating rate in response to the changes in the sample's weight‐loss rate. Only a one‐step degradation process of the PPS is observed in nitrogen and argon, but a two‐step degradation process of PPS is found in helium. A four‐step degradation process of the PPS, which is hardly ever revealed by traditional TG, is found in this investigation, especially in air. The initial thermal degradation temperature and temperature at the first maximum weight‐loss rate of the PPS increase in the following order: helium < nitrogen < argon < air. The first maximum weight‐loss rate also increases with the variation of the atmosphere in the order nitrogen < air < argon < helium. The char yield at 700°C increases in the order air < helium < nitrogen < argon. The activation energy of the major degradation process of PPS, as calculated based on the high‐resolution TG data, is very high and increases in the order nitrogen < argon < helium < air. The thermal decomposition parameters of the PPS determined by the high‐resolution TG are systematically compared with those by traditional TG at a constant heating rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1940–1946, 2002     

Synthesis and characterization of poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers by combined ring‐opening polymerization and cross‐coupling processes

2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene was used as initiator in ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate (Sn(Oct)₂) catalyst. The resulting poly(ε‐caprolactone) (PCL) macromonomer, with a central 2,5‐dibromo‐1,4‐diphenylene group, was used in combination with 1,4‐dibromo‐2,5‐dimethylbenzene for a Suzuki coupling in the presence of Pd(PPh₃)₄ as catalyst or using the system NiCl₂/bpy/PPh₃/Zn for a Yamamoto‐type polymerization. The poly(p‐phenylenes) (PPP) obtained, with PCL side chains, have solubility properties similar to those of the starting macromonomer, ie soluble in common organic solvents at room temperature. The new polymers were characterized by ¹H and ¹³C NMR and UV spectroscopy and also by GPC measurements. The thermal behaviour of the precursor PCL macromonomer and the final poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry analyses and compared. Copyright © 2004 Society of Chemical Industry     

New functional bicomponent fibers with core/sheath‐configuration using poly(phenylene sulfide) and poly(ethylene terephthalate)

Bicomponent fibers using the high‐performance polymer poly(phenylene sulfide) (PPS) together with poly(ethylene terephthalate) (PET) were melt‐spun. Both possibilities of using PPS, either as core or as sheath material, were realized to provide special functionalities like improved thermobonding capability, flame retardancy, or chemical resistance. Parameters that guarantee stable processing of PPS and PET during coaxial extrusion with different core/sheath volume ratios were explored. Microscopic studies of the cross‐sections showed holes and cavities, which were formed at the interface between PPS and PET. Possible mechanisms for cavity formation were evaluated. Results of thermal and mechanical characterization by means of TGA, DSC, and tensile testing revealed a strong influence of the processing parameters, namely draw ratio and core/sheath volume ratio, on the crystallization and the tensile strength of the drawn fibers. By changing the core/sheath volume ratio from 2 to 0.5 in the PPS/PET fiber, the crystallinity of the PET‐component was switched from 10 to 50%, whereas the crystallinity of the PPS dropped from 68 to 7%. It was determined that bicomponent fibers can exceed the strength of monocomponent fibers up to 28%. The flammability and chemical resistance of the new developed fibers were characterized. In contrary to what was expected, the encasing of PET with PPS reduced the flame retardancy, though PPS has a higher flame resistance than PET. The chemical resistance of the PET core against hydrolysis was imparted by coextruding a PPS sheath. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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