A novel process for the formation of poly(p-phenylene terephthalamide) film from liquid crystalline solutions

A novel process for the formation of biaxially balanced films of poly(p-phenylene terephthalamide) was developed. The liquid crystalline sulphuric acid solution is extruded through a slit die on a flat plate. The optically anisotropic to isotropic transition is generated by controlling the temperature and/or the water content in sulphuric acid before coagulation. The wet gel films are dried while holding their width and length constant. The films thus produced are transparent and biaxially oriented. Young's modulus of 12 GPa, tensile strength of 450 MPa, and elongation at break of 25% were obtained in the plane of the film. Such films which possess high dimensional and thermal stabilities are expected to be useful for new practical uses under severe conditions.     

Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.     

Structure and properties of N-octadecylated poly(p-phenylene terephthalamide)

N-octadecylated PPTA's with various molecular weights were synthesized from PPTA and n-octadecyl bromide via the metalation reaction. The polymer exhibited side-chain crystallization at 314 K due to the long alkyl side chains and both crystallinity and the perfection of the crystal increase with increasing in the molecular weight. The results of IR spectra and the wide angle X-ray indicate that the polymer crystallizes in hexagonal form. The mechanical and the dynamic mechanical properties of N-octadecylated PPTA's were measured. Two tan δ peaks were observed in a temperature range of 310–350 K and at 260 K, respectively, which can be designated α_c and α_a relaxation, respectively. The concentrated solutions of N-octadecylated PPTA's in tetrahydrofuran, dichloroethane, tetrachloroethane, and bromoform showed liquid crystalline behavior of lyotropic type.     

Poly(p-phenylene terephthalamide) films formed from extrusion and coagulation of liquid crystalline sulphuric acid solutions: Characterization of orientation and void structure,annealing, and upgrading of film mechanical properties

Poly(p-phenylene terephthalamide) (PPD-T) films have been prepared by continuous extrusion of liquid crystalline 17 percent PPD-T/sulphuric acid solutions through an annular die followed by coagulation, Films extruded without drawdown exhibit some polymer chain orientation in the machine direction. This is increased by uniaxially drawing down films. Films produced with a lubricated conical mandrel sitting between the die and the coagulation bath exhibit an equal biaxial orientation. The uniaxially oriented films exhibit highly anisotropic mechanical properties, while the mandrel-produced film exhibits balanced properties. Heat treatment at 350°C results in significant enhancement of the tensile strength of the mandrel film. Void structures in the films have been investigated by mass density, scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS). Density measurement indicate a void content decreasing with decreasing film thickness and heat treatment. SEM locates micron-size voids in the thickest films, apparently caused by rapid coagulation. SAXS indicates much smaller void sixes which are roughly prolate ellipsoids (long axis in machine direction) for uniaxial films and oblate ellipsoids (short axis in thickness direction) for the mandrel produced films. Various techniques are used to estimate mean void size.     

含氯聚对苯二甲酰对苯二胺纤维的结构与性能

以邻氯对苯二胺(Cl-PPD)与对苯二甲酰氯(TPC)为单体,在N-甲基吡咯烷酮(NMP)/氯化钙(Ca Cl2)或氯化锂(Li Cl)体系中进行低温溶液聚合,合成了含氯聚对苯二甲酰对苯二胺(Cl-PPTA)溶液,直接进行湿法纺丝,制备了Cl-PPTA纤维。采用旋转流变仪测试了Cl-PPTA溶液的流变性能,利用傅里叶变换红外光谱、扫描电子显微镜、热失重分析、纤维强伸度仪、声速取向测量仪、氧指数测定仪对Cl-PPTA纤维的结构及性能进行了表征。结果表明:相比于NMP/Ca Cl2体系,NMP/Li Cl体系的Cl-PPTA溶液黏度更低,所制得的纤维其表面更光滑、结构更致密,纤维力学性能也较好;热处理后两种纤维力学性能均得到进一步改善;两种Cl-PPTA纤维具有较好的热稳定性,其阻燃性能均远高于PPTA纤维。     

Characterization of the adhesion of single-walled carbon nanotubes in poly(p-phenylene terephthalamide) composite fibres

Poly(p-phenylene terephthalamide)/single-walled carbon (PPTA/SWNT) composite fibres with different draw ratios have been spun using a dry-jet wet spinning process and their structure and deformation behaviour analysed using Raman spectroscopy. The dispersion of nanotube has been examined by Raman scattering intensity mapping along the fibre. The nanotubes improved the polymer orientation in composite fibre with a draw ratio of 2 but degraded the orientation at higher draw ratios. The mechanical reinforcing effect by nanotubes is related to the change of polymer orientation, suggesting a dominant role of polymer orientation in mechanical performance of the composite fibre. High efficiency of stress transfer within the strain range of 0-0.35% and breakdown of the interface at higher strains has been found in the composite fibres through an in situ Raman spectroscopic study during fibre deformation. Cyclic loading applied on the fibre has indicated reversible deformation behaviour at low strain and gradual damage of the interface at high strains.     

Diffusion of moisture in poly(p-phenylene terephthalamide) film: Analysis by the adsorption-controlled diffusion equation

Diffusion of moisture in poly(p-phenylene terephthalamide) films was observed using a gravimetric method at various vapor pressures at 25°C. The equilibrium moisture regain was 4.9% (g/g) and 4.2% (g/g) at 65% relative humidity for the 16-μm and 50-μm thick film, respectively. These values are slightly larger than regular Kevlar or Kevlar 49 that have the same chemical structure of poly(p-phenylene terephthalamide) (PPTA). The sorption and desorption curves were satisfactorily analyzed by the adsorption-controlled diffusion equation assuming reversible bimolecular kinetics. These results strongly indicate that the interaction between the water molecules and amide groups of polymer plays an important role in the diffusion process and has much effect on the shape of sorption/desorption curves. The diffusion coefficients for the films were in the order from 10^−-11 to 10^−-10 cm²/s, which were also larger than those for Kevlar fibers of 10^−-12 cm²/s. The higher moisture diffusivity in the film reflects sparser molecular packing and existence of interstitial microvoids due to the lower molecular orientation in the noncrystalline region in the PPTA film than in the fiber (Kevlar).     

Uniplanar orientation of poly(p-phenylene terephthalamide) crystal in thin film and its effect on mechanical properties

The uniplanar orientation of poly(p-phenylene terephthalamide) (PPTA) crystal was investigated by x-ray and infrared measurements. Thin PPTA films 3–15 μm thick were prepared by coagulating a sulfuric acid solution of PPTA with various coagulants. Two types of uniplanar orientation were observed, depending on the coagulant used. Thin film coagulated with water exhibits (0k0) uniplanar orientation and film coagulated with other coagulants such as methanol, ethanol, and acetone exhibits (h00) uniplanar orientation. These (h00) and (0k0) uniplanar orientations are formed with crystal modifications I and II, respectively. The (0k0) uniplanar orientation transforms to (h00) upon annealing, accompanying crystal transformation from modification II to modifications I. These uniplanar orientations may result from anisotropic crystal growth due to polymer–coagulant interaction along the hydrogen bond direction. The effect of these uniplanar orientations on the mechanical properties was also examined. The thin film having the (0k0) uniplanar orientation shows ductile fracture, whereas the one having the (h00) uniplanar orientation shows brittle fracture upon tensile deformation. These results are explained on the basis of the direction of the uniplanar orientation of the hydrogen-bonded sheet.     

Process for the formation of biaxially oriented films of poly(p-phenylene terephthalamide) from liquid crystalline solutions

A new process for making equal biaxially oriented films from liquid crystalline solutions of poly(p-phenylene terephthalamide) (PPD-T) is described. The process involves extruding solutions of PPD-T/H₂SO₄ through an annular die and over an oil-coated mandrel into a coagulation bath. The films were studied using wide angle X-ray diffraction (WAXS) and scanning electron microscopy (SEM). Tensile stress–strain properties were obtained on samples cut at various directions in the plane of the film. Biaxially oriented films which possess equal properties in the various directions in the plane of the film were produced. Moduli of 2.3 × 10⁹ Pa and tensile strengths of 9.6 × 10⁷ Pa were obtained in the plane of the film. Films with unequal biaxial orientation were also produced. These tend to have higher modulus/tensile strength in the direction of major orientation, the machine direction (up to 8.3 × 10⁹ Pa/2.5 × 10⁸ Pa), but become brittle in the transverse direction.     

Mesomorphic polyblends of poly(p-phenylene terephthalamide) and poly(4,4′-terephthanilide adipamide)

A simultaneous dissolution of two lyotropic polyamides, poly(p-phenylene terephthalamide) (PPTA) and poly(4,4′-terephthanilidc adipamide) (PTAd), in a concentrated H₂SO₄ (1 to 1.5% wt) produced an isotropic single phase solution. The crystallinity of PPTA/PTAd blends confirmed formation of a mesomorphic polyblend to the molecular level. With increasing concentration, solutions of these PPTA/PTAd blends in 100% H₂SO₄ showed a sequential phase change typical of a single lyotropic polymer. Further, the ternary solution exhibited a wider biphase range than both binary solutions of PPTA/100% H₂SO₄ and PTAd/100% H₂SO₄. Dry-jet wet spinning of anisetropic solution of this ternary composition with a PTAd weight fraction less than 0.5 enabled us to obtain PPTA/PTAd blend fibers. Including a PTAd weight fraction of 0.1-0.15 reduced both the orientation angle and fibrillation. The particular blend fiber with a PTAd weight fraction of 0.15 exhibited a synergistic effect on the mechanical properties.     

Tensile deformation of poly(p-phenylene terephthalamide) fibres,an experimental and theoretical analysis

The tensile deformation of poly(p-phenylene terephthalamide) fibres has been investigated. Functional relationships observed between stress, crystallite orientation distribution, dynamic modulus and strain are derived from an analysis of the deformational behaviour of a series model consisting of a linear arrangement of crystallites. It is shown that the deformation of these fibres is largely brought about by the elastic strain and irreversible rotation of the crystallites. A formula is derived for the stress—strain relationship of a crystalline polymeric fibre with a narrow crystallite orientation distribution.     

Preparation and properties of graft and block copolymers of poly(p-phenylene terephthalamide) with polybutadiene

Graft copolymers of polybutadiene (PBD) onto poly(p-phenylene terephthalamide) (PPTA) were prepared by the nucleophilic substitution of N-metalated PPTA with telechelic PBD having bromide end groups. Block copolymers were synthesized by the condensation reaction of telechelic PBD having acid chloride end groups with amino-group-terminated PPTA. The structure of these copolymers was identified by IR spectra. Graft and block copolymers contained PBD segments up to 85 wt % and 45 wt %, respectively. Thermomechanical analyses (TMA) proved the existence of distinctive primary absorption peak corresponding with T_g of PBD for both graft and block copolymers. The T_g's of both types of the copolymers were further ascertained by the DSC curves. TMA curves suggested that the microphase separation occurred between PPTA and PBD. The incorporation of PPTA segments into PBD increased the decomposition temperature compared with the blend polymer composed of PPTA and PBD with the same composition.     

Processing and properties of poly(p-phenylene benzobisthiazole)/nylon fibers

Composite fibers of poly(p-phenylene benzobisthiazole) (PBT) with nylons were spun from dilute acid solutions. The effects of wet-stretching, heat treatment time, tension, and temperature on the tensile properties are reported. Nylon 6,6 and nylon 6 at several molecular weights were studied. Moduli of 40 GPa and tensile strengths of 375 MPa were achieved for 30/70 PBT/nylon composites. Heat treatment of the nylon/PBT fibers at 160–225°C for 12–19 h increased the tensile modulus by 20–50% and the tensile strength by a smaller amount. At the same time, the intrinsic viscosity of the nylons increased as much as 100%, indicating the solid-state polymerization of the nylon. The largest tensile modulus attained is less than half the theoretical value predicted by a linear “rule of mixtures” as might be expected for an oriented molecular composite. Although differential scanning calorimetry shows a melting transition at temperatures 5–10°C higher than the pure nylons, the composite does not flow at temperatures above this transition. Sulfuric acid dissolves most of the nylon, but does not destroy the mechanical integrity of the fibers; differential scanning calorimetry indicates that the remaining fiber contains little or no nylon. The results are consistent with a microstructure consisting of a microfibrillar network of PBT, surrounded by a separate nylon phase.     

Compatibility improvement of poly(lactic acid)/thermoplastic starch blown films using acetylated starch

The present research aims to improve the compatibility between relatively hydrophobic poly(lactic acid) (PLA) and hydrophilic thermoplastic starch (TPS) and the properties of the PLA/TPS blends by replacing TPS from native cassava starch (TPSN) with TPS from acetylated starch (TPSA). The effects of the degree of acetylation (DA) of acetylated starch, that is, 0.021, 0.031, and 0.074, on the morphological characteristics and properties of PLA/TPS blend are investigated. The melt blends of PLA and TPS with a weight proportion of PLA:TPS of 50:50 are fabricated and then blown into films. Scanning electron microscopy confirms the dispersion of TPS phase in the PLA matrix. Better dispersion and smaller size of the TPS phase are observed for the PLA/TPSA blend films with low DA of acetylated starch, resulting in improved tensile and barrier properties and increased storage modulus, thermal stability, and T_g, T_cc, and T_m of PLA. Elongation at break of the PLA/TPSA blend increases up to 57%, whereas its water vapor permeability and oxygen permeability decrease about 15%. The obtained PLA/TPSA blend films have the potential to be applied as biodegradable flexible packaging.     

Rheological properties of liquid-crystalline solutions of poly(p-phenylene terephthalamide) and behavior of the jet in spinning through an air space

LC solutions of PPTA behave like liquids with a power law of flow and n =0.65–0.78 for flow through the channels of standard spinnerets with small diameters and q =0.88–0.95 for longitudinal flow in jets. Spinneret expansion of a freely falling jet in channels with small diameters is equal to 1.70–1.75 and is not a function of the shear rate on the wall. Spinneret expansion is preserved in conditions of repeated drawing of the jets in the air space until very small air spaces at 1.5–2.5 mm are used. In spinning PPTA fibres through an air space with a high jet draw ratio, only a small fraction of this drawing in the spinning bath is possible. Translated from Khimicheskie Volokna, No. 2, pp. 3–7, March–April, 1997.     

Electrochemical synthesis of poly(p-phenylene) and poly(p-phenylene)/TiO2 nanowires in an ionic liquid

This study shows for the first time that poly(p-phenylene) (PPP) nanowires can be easily obtained by electrochemical synthesis at room temperature. The method involves the template assisted electropolymerization of benzene in the air and water stable ionic liquid 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIm]FAP). Track-etched polycarbonate membranes (PC) with an average pore diameter of 90 nm were used as templates. Dense and highly flexible bundles of PPP nanowires with a high aspect ratio (>160) were easily obtained by this method. In addition, we present here our first results to obtain PPP/TiO₂ nanowires by the combination of a sol–gel technique with electropolymerization. HR-SEM, TEM and EDX were used for the structural characterization of the nanowires.     

The Preparation and property of poly(lactic acid)/tourmaline blends and melt‐blown nonwoven

Poly(lactic acid) melt‐blown (MB) webs were melt‐spun by MB processing of poly(lactic acid) and poly(lactic acid)/filler blends. The effect of tourmaline particles on the structure, morphology, mechanical and filtration properties of poly(lactic acid) blends, and MB webs were reported. The blends and MB webs were characterized using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WXRD), scanning electron microscopy (SEM), and pore size meter (PSM). The degree of crystallinity of blends with tourmaline particles was more than that of poly(lactic acid) alone. SEM micrographs revealed a good dispersion of the additive in the blends and fiber webs. The tourmaline particles offered some benefits to the mechanical properties of the MB web. MB web samples with tourmaline had larger pore size, high surface charge density, and higher filtration efficiency. POLYM. COMPOS., 36:264–271, 2015. © 2014 Society of Plastics Engineers     

Improved properties of molecular composite of nitrile rubber and poly (p-phenylene terephthalamide) by blending with poly (vinyl chloride)

Summary Nitrile rubber (NBR) was reinforced by poly(p-phenylene terephthalamide) (PPTA) with a coprecipitation method from a common solvent of them. PPTA was converted to N-sodium PPTA with sodium hydride in DMSO, forming homogeneous solution. DMF dissolves NBR. Both solutions were blended to form an isotropic solution. The precipitant was NBR reinforced by PPTA which was regenerated from N-sodium PPTA at coagulation as reported previously. The molecular composite thus obtained was mill-blended with poly(vinyl chloride) (PVC) in order to enhance solvent resistant property. The vulcanized composite of NBR/PVC reinforced by PPTA showed higher modulus, higher strength and more improved solvent resistance than the gum stock and the black stock of NBR/PVC. The properties of the molecular composite containing 5phr PPTA found approximately comparable to those of the black stock of NBR/PVC with 30–40phr ISAF carbon black.On Leave from Japan synthetic Rubber Co., Ltd., Higashi-yurigaoka, Assao-ku, Kawasaki 215, Japan