Calorimetric,X-ray and infra-red investigations on poly(hexamethylene adipamide)

Summary In dependence on crystallization conditions three ranges with different crystal structure and heat of fusion were found by DSC,WAXS,and IR for unoriented PA 6.6 samples of densities between 1.10 and 1.17gcm^–3: Range I:_I triclinic, _c ^I =1.225 gcm^–3,H _M ^I = 235 Jg^–1. Range II:_II triclinic, _c ^II =1.165 gcm^–3, H _M ^II =185 Jg^–1. Range III:Continuous variation from _c ^I ,H _M ^I to _c ^II , H _M ^II . _a=1.095 gcm^–3 is independent of crystallization. conditions. The transition between _I and _II is probably due to changes of the chain conformation.     

Heat resistance properties of poly(p-phenylene-2,6-benzobisoxazole) fiber

The high temperature properties of Poly(p-phenylene-2,6-benzobisoxazole) (PBO) fiber are examined and compared with those of the p-Aramid fiber. In particular, the temperature dependence of tensile strength of the PBO fiber is reported for the first time. The PBO fiber has 100°C higher decomposition temperature than the p-Aramid fiber, and the amount of toxic gases in combustion is much smaller than the p-Aramid fiber. Although the relative strength decreased proportionally in the range of room temperature to 500°C, the PBO fiber has 40% of the strength at room temperature even at a temperature of 500°C. After thermal treatment at 500°C for 60 s, the PBO fiber retained 90% of its original strength. The PBO fiber is expected to substitute for asbestos, which is still used as a heat resistant cushion material. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1031–1036, 1997     

Thermal effects in poly(hexamethylene adipamide) and polyoxymethylene at high hydrostatic pressures

The dynamic mechanical properties, transition behavior, and morphology of polycarbonate (PC)-polyurethane (PU) semi-interpenetrating polymer networks (semi-IPNs) and linear blends were studied by means of Rheovibron, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Two glass transition temperatures corresponding to polycarbonate and polyurethane were observed and microphase separation was further evident with TEM. In PC/PU semi-IPNs, two glass transition temperatures were shifted inwardly indicating that the interpenetrating network of polyurethane increases the mutual miscibility of PC and PU. The average phase domain was 500Å in semi-IPNs and the phase domains were in the range 1000–6000 Å in linear blends of the corresponding polymers. The compatibilities of PC and PU were greatly influenced by the molecular weight of polyols in PU prepolymer and the ratio of NCO/OH; lower molecular weight polyols and higher NCO/OH ratio resulted in better compatibility, and finer phase domains in PC and PU linear blends and semi-IPNs.     

聚对苯撑苯并双噁唑纤维改性技术的研究进展

介绍了近年来聚对苯撑苯并双噁唑(PBO)纤维的改性方法,并对今后PBO纤维的改性方向进行了展望。PBO纤维的改性主要是采用碳纳米管、石墨烯等纳米粒子及第三单体对PBO纤维进行共混复合及原位共聚改性,从而提高PBO纤维的力学性能、热学性能、表面性能及耐老化性能等。今后应加强改性体PBO基体的共聚改性机理及改性体对PBO聚合、纺丝过程的影响研究,探索多种改性技术的混合使用或新的改性技术,从而制备出更优异的高性能PBO纤维。     

Characterization of coatings of poly(hexamethylene adipamide) deposited on carbon fibers by interfacial polymerization techniques

Polyamide coatings deposited on carbon fibers by means of an interfacial in situ polymerization technique have been examined. Two different coating processes were used, depending on the length of the carbon fibers (short or long). The effect of the concentration of the monomer reactants on the quantity of coating deposited on the fibers has been determined using thermogravimetric analysis (TGA). Characterization techniques used to identify the nature of the coating process product included Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). Using the above techniques, IR spectra were collected and identified, and important polymer properties, such as morphology, melting point, and the molecular weight of the polymer coating were determined. © 1995 John Wiley & Sons, Inc.     

Poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol based polyurethane elastomers. I. Synthesis and properties

The compatibilizing effect of poly(hexamethylene oxide) (PHMO) on the synthesis of polyurethanes based on α,ω‐bis(6‐hydroxyethoxypropyl) poly(dimethylsiloxane) (PDMS) was investigated. The hard segments of the polyurethanes were based on 4,4′‐methylenediphenyl diisocyanate (MDI) and 1,4‐butanediol. The effects of the PDMS/PHMO composition, method of polyurethane synthesis, hard segment weight percentage, catalyst, and molecular weight of the PDMS on polyurethane synthesis, properties, and morphology were investigated using size exclusion chromatography, tensile testing, and differential scanning calorimetry (DSC). The large difference in the solubility parameters between PDMS and conventional reagents used in polyurethane synthesis was found to be the main problem associated with preparing PDMS‐based polyurethanes with good mechanical properties. Incorporation of a polyether macrodiol such as PHMO improved the compatibility and yielded polyurethanes with significantly improved mechanical properties and processability. The optimum PDMS/PHMO composition was 80 : 20 (w/w), which yielded a polyurethane with properties comparable to those of the commercial material Pellethane™ 2363‐80A. The one‐step polymerization was sensitive to the hard segment weight percentage of the polyurethane and was limited to materials with about a 40 wt % hard segment; higher concentrations yielded materials with poor mechanical properties. A catalyst was essential for the one‐step process and tetracoordinated tin catalysts (e.g., dibutyltin dilaurate) were the most effective. Two‐step bulk polymerization overcame most of the problems associated with reactant immiscibility by the end capping of the macrodiol and required no catalysts. The DSC results demonstrated that in cases where poor properties were observed, the corresponding polyurethanes were highly phase separated and the hard segments formed were generally longer than the average expected length based on the reactant stoichiometry. Based on these results, we postulated that at low levels (∼ 20 wt %) the soft segment component derived from PHMO macrodiol was concentrated mainly in the interfacial regions, strengthening the adhesion between hard and soft domains of PDMS‐based polyurethanes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2026–2040, 2000     

Effects of molecular entanglement on molecular dynamics and phase-separation kinetics of poly(methyl methacrylate)/poly(styrene-co-maleic anhydride) blends

Poly(methyl methacrylate)/poly(styrene-co-maleic anhydride) (PMMA/SMA) blends with various compositions were prepared through solution casting and melt blending. Two preparation routes, solution casting and melt blending, were used to achieve different degrees of molecular entanglement in the samples with solution casting giving rise to a lower degree of entanglement. Therefore, the effect of molecular entanglement on molecular dynamics and phase-separation kinetics of PMMA/SMA blends was investigated by using broadband dielectric spectroscopy and small-angle laser light scattering (SALLS). Molecular entanglement is found to have a pronounced effect on the α-relaxation process. The glass transition temperature (T_g) is related to the degree of entanglement and a higher degree of entanglement can result in a higher T_g which shifts to a higher temperature after annealing. The relaxation time (τ) of the α-relaxation process is lower for lower degrees of entanglement. Neither the dynamics nor the distribution width of the β-relaxation process is affected by degree of entanglement, regardless of the blend composition. The kinetics of phase-separation by spinodal decomposition (SD) in PMMA/SMA blends are however significantly influenced by the degrees of entanglement with decomposition rate being higher at lower degrees of entanglement.     

Molecular weight distribution of fractionated poly (hexamethylene Oxide)

Poly(hexamethylene oxide) obtained by two routes, polycondensation and cationic polymerisation, is fractionated and its molecular weight distribution is analysed by using well known data treatment methods namely those of Beall, Wesslau, Tung and Saiz and Horta. The results are compared and discussed showing that the polycondensated sample has a lower molecular weight and wider distribution than the cationic one.     

Photophysical processes in poly(hexamethylene adipamide)–acid dye complexes: Energetics of nylon 66 phototendering

The mechanism of dye-sensitized photo-oxidative degradation of nylon 66 was investigated. A known phototendering dye, C.I. Acid Blue 40 (1-amino-4-(p-aminoacetanilide)-2-anthraquinone sodium sulfonate), was used for this study. Excitation and emission spectra of the dyed and undyed nylons indicated that a ground-state complex between the dye and the polyamide was formed upon dyeing. The energy level of the complex's electronic states favor triplet–triplet energy transfer from the nylon to the complex. Quenching studies show that the energy transfer occurs efficiently with a rate constant of 45.8 l. mole^?1 sec^?1. An additional energy transfer occurs between the excited free dye and the complex by either a singlet–triplet or a triplet–triplet mechanism. Kinetic analysis of the nylon-complex energy transfer suggests that the triplet energy of nylon migrates 24 to 33 Å along the amide chromophores in an exciton fashion until an energy trapping complex is reached. Energy is then transferred by an exchange mechanism. Photo-oxidative studies verify that the dye–nylon complex sensitizes the polyamide photo-oxidative degradation at its own expense without dye photobleaching.     

Cocrystallization behavior of poly(hexamethylene terephthalate-co-hexamethylene 2,6-naphthalate) random copolymers

A series of poly(hexamethylene terephthalate-co-hexamethylene 2,6-naphthalate) (P(HT-co-HN)) random copolymers were synthesized by melt polycondensation and characterized using ¹H NMR spectroscopy and viscometry. Their cocrystallization behavior was investigated using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) method. Even though the P(HT-co-HN) copolymers synthesized are statistically random copolymers, they show a clear melting and a crystallization peak in DSC thermograms over the entire range of copolymer composition and have a minimum melting temperature in the plot of melting temperature versus copolymer composition. WAXD patterns of all the copolymer samples show sharp diffraction peaks and are largely divided into two groups, i.e. PHT type and PHN type crystals. In addition, WAXD patterns of the PHN type crystals are subdivided into two types of PHN α and PHN β according to the copolymer composition. These facts indicate that the P(HT-co-HN) copolymers show isodimorphic cocrystallization. The composition at which the crystal transition between PHT type and PHN type occurs is equivalent to the eutectic composition (22 mol% HN content) for the melting temperature. When the defect free energies were calculated by using the equilibrium inclusion model proposed by Wendling and Suter, the defect free energies in the case of incorporation of HT units in the PHN α and β crystals were higher than the case of incorporation of HN units in the PHT crystal lattice.     

Poly(m‐xylene adipamide)–kaolinite and poly(m‐xylene adipamide)–montmorillonite nanocomposites

Two clay compounds, montmorillonite (Cloisite 30B) and kaolinite, were dispersed in a poly(m‐xylene adipamide) resin at loading levels of 2 wt % clay. The samples were melt‐compounded and extruded. The extruded samples were injection‐molded into preforms and then blow‐molded into multilayer bottles. Rheology, calorimetry, electron microscopy, and gas‐transport measurements were performed. Both clays were nucleating agents, giving crystallite sizes that did not cause haze. Kaolinite was more difficult to exfoliate than montmorillonite, and under similar processing conditions, kaolinite resulted in a higher degree of crystallinity. Both nanocomposites exhibited improved gas‐barrier properties over the neat resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1377–1381, 2007     

Blends of poly(2,6-dimethyl-1,4-phenylene oxide)/ poly(styrene-co-methacrylic acid)/ poly(ethyl methacrylate-co-4-vinylpyridine)

Summary The miscibility of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with poly(styrene-co-acrylic acid) (SAA) or poly(styrene-co-methacrylic acid) (SMA) containing respectively up to 22 mol % of acrylic or methacrylic acid was studied by Differential Scanning Calorimetry and viscosimetry. All PPO/SAA or PPO/SMA blends containing 60% or less by weight of PPO were miscible and showed only one glass transition temperature (Tg). Above 60% of PPO, two Tg's were however observed for the blends in which the acid content in the SAA or SMA reaches 20% or 12% by mole respectively; the higher Tg is slightly lower than the one of pure PPO, while the lower one corresponds to a miscible blend of lower content of PPO.A DSC study showed that depending on the blend ratio, two or three glass transition temperatures were observed when a copolymer of ethyl methacrylate containing 8 mol % of 4-vinylpyridine (EM4VP-8) was added to miscible PPO/SMA-12 blends. The PPO dissolution in the SMA-12 copolymer was affected by the specific interactions that occurred between this latter copolymer and the EM4VP-8.     

Thermal decomposition of poly(ethylene terephthalate)/mesoporous molecular sieve composites

The nonisothermal and isothermal degradation processes of poly(ethylene terephthalate)/mesoporous molecular sieve (PET/MMS) composites synthesized by insitu polymerization were studied by using thermogravimetric analysis in nitrogen. The nonisothermal degradation of the composite is found to be the first-order reaction. An isoconversional procedure developed by Ozawa is used to calculate the apparent activation energy (E), which is an average value of about 260 kJ/mol with the weight conversion from 0% to 30%, and is higher than that of neat PET. Isothermal degradation results are confirmed with the nonisothermal process, in which PET/MMS showed higher thermal stability than neat PET. The polymer in mesoporous channels has more stability due to the protection of the inorganic pore-wall. These results indicate that mesoporous MMS in PET/MMS composites improve the stability of the polymer. Translated from Polymer Materials Science and Engineering, 2006, 22(1): 64–67 [译自: 高分子材料与工程]     

Poly (alpha-methylstyrene) as a processing aid for rigid poly (vinyl chloride)

Poly (alpha-methylstyrene) (PAMS) is a new approach to process improvement in rigid poly (vinyl chloride) (PVC)—the use of a low molecular weight polymer as a process aid. PAMS can reduce fusion time, melt viscosity and improve heat stability of rigid PVC compounds. The reduced melt viscosity allows the addition of fillers to PVC without adverse effect on extrusion rates. This polymer also improves the resistance to melt fracture and shear “burning” at high shear rates. When used within the optimum concentration range, physical properties such as tensile strength, Izod impact and heat distortion are maintained. In addition, PAMS gives, improved production rates in both pipe extrusion and injection molding processes without sacrifice in properties.     

Compatibility of poly(2,6-dimethyl-1,4-phenylene oxide)/poly(fluorostyrene-co-chlorostyrene) blends

The compatibility of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with random copolymers of ortho- and para-fluorostyrene as well as with ortho- and para-chlorostyrene of various copolymer compositions was examined. The compatibility was studied by DSC and visual observation of film clarity. It was found that copolymers of ortho-fluorostyrene with para-chlorostyrene containing 15–74 mol % p-CIS are compatible with PPO in all proportions. Compatibility of the PPO/poly-(ortho-fluorostyrene-co-ortho-chlorostyrene) system was observed for copolymers containing between 15 and 36 mol % ortho-chlorostyrene. Copolymers of para-fluorostyrene with para-chlorostyrene, as well as copolymers of para-fluorostyrene with ortho-chlorostyrene appear to be incompatible with PPO at 210°C.     

Mechanical criteria for polymer compatibility: Poly(vinylchloride)/post-chlorinated poly(vinylchloride) blends

The compatibility of poly(vinylchloride PVC) with post-chlorinated PVC (CPVC) is investigated with the purpose of relating the mechanical properties of such blends with their compatibility. The effects on compatibility of varying mixing methods, blend composition, molecular weights of components, and chlorine content of CPVC are studied. Experimental methods include comparison of the glass transition temperatures (Tgs) of blends and homopolymers using dynamic mechanical analysis, Differential Scanning Calorimetry (DSC), and comparison of the mechanical properties of blends and homopolymers. Experimental results indicate marginal compatibility between PVC and CPVC. Blends in which CPVC is the main component are indicated to be less compatible than other compositions.     

Polyester-Polyether Block Copolymers II. Thermal and Mechanical Properties of Poly(hexamethylene terephthalate)/Poly(oxytetramethylene) Block Copolymers

The melting and crystallisation behaviour of crystalline phases in poly (hexamethylene terephthalate)/poly(oxytetramethylene) block copolymers have been investigated in relation to copolymer composition and polyether block molecular weight (m.w.). In contrast to that in corresponding homopolymer blends, the polyester crystallinity in the block polymers is greatly reduced by incorporation of polyether units, though some persists even at low polyester contents. Concomitant changes in the glass transition temperatures show part of the polyester component to form a homogeneous component of the amorphous phase. The mechanical properties change with composition in parallel with the changes in copolymer crystallinity and T_g. Copolymers with 20-60 w % of poly(oxytetramethylene) units of m.w. 2000 are highly extensible elastomers. Those with higher m. w. polyether blocks have higher modulus and strength but suffer a serious loss of properties at 60d?C. The observations are interpreted in terms of a model in which polyester crystallites (and polyether crystallites also, for the higher m. w. polyether blocks) are supported within an amorphous matrix by tie-molecules whose nature changes with the copolymer compositions. The results are compared with those for analogous polyester-polyethers having different structural components.     

Block and random copolyamides of poly(m‐xylylene adipamide) and poly(hexamethylene isophthalamide‐co‐terephthalamide): Methods of preparation and relationships between molecular structure and phase behavior

Copolymerization of poly(m‐xylylene adipamide) (MXD6) and poly(hexamethylene isophthalamide‐co‐terephthalamide) (PA6I‐6T) was used as an efficient strategy to prepare amorphous homogeneous systems with improved properties mainly for packaging applications. The preparation of block copolymers was first of all tried by co‐extrusion of the two polymers and then by thermal treatments at high temperatures in DSC or mixing in Brabender, also in the presence of a catalyst. The occurrence of transamidation reactions led to macromolecular structures with different randomness degrees. Further, random copolymers, with the full range of compositions, were synthetized from monomers, by a fast and simple two‐stage melt polycondensation. For all the copolymers, the sequence distribution was studied by using a ¹H NMR method developed by the Authors. The effects of preparation procedures, of mixing temperature and time, of the presence of a catalyst on the chemical structure, and, then, on final properties were studied. Interesting correlations among block length, monomer distribution and phase behavior were discussed. POLYM. ENG. SCI., SCI., 55:1475–1484, 2015. © 2014 Society of Plastics Engineers     

Membranes based on poly(styrene-N-phenylmaleimide)/poly(2,6-dimethyl-1,4-phenylene oxide) blends

Blend membranes were prepared by casting chloroform solutions of mixtures of styrene-N-phenylmaleimide copolymer containing ca. 10 mol % imide units with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), and their phase behavior was evaluated. At a content of 20% PPO, the membranes were homogeneous; those having 40 or more % PPO exhibited phase separation. Membranes made of the parent polymers and their blends were tested in the pervaporation of aqueous ethanol solutions; permeabilities to oxygen, nitrogen, and carbon dioxide were also determined. The pervaporation characteristics and gas transport properties are discussed considering the interactions of polymer chains and the phase structure of the membranes. © 1995 John Wiley & Sons, Inc.     

Miscibility of poly(2,6-dimethyl-1,4-phenylene oxide)/poly(vinyl pyrrolidone) blends

The miscibility of blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and poly(vinylpyrrolidone) (PVP) was studied by differential scanning calorimetry (DSC) through the analysis of the glass transition temperature Tg. The dependence of Tg with the annealing temperature was determined for PPO and PVP samples of different molecular weights. The phase diagrams for blends containing three different PVP samples were established. Blends of PPO and PVP were found to be miscible for composition lower than 30% and higher than 65% of PVP. A inmiscibility window between 30 and 65% of PVP is also described.