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     

Rheological and mechanical properties of poly(vinyl chloride)/chlorinated poly(vinyl chloride) miscible blends

The properties of poly(vinyl chlorlde)/ehlorinated poly(vinyl chloride) (61.6 percent C1) blends, prepared by melt and solution blending, were measured by various tests. Based on the chlorinated poly(vinyl chloride) (CPVC) composition, percent chlorine, and mole percent CC1₂ groups, these blends were expected to show intermediate properties between miscible and immiscible systems. Indicative of miscible behavior were the single glass transition temperatures over the entire composition range for both melt and solution blended mixtures. A single phase was also indicated by transmission electron microscopy. However, the yield stress showed a minimum value less than either of the pure components in the 50 to 75 percent CPVC range, which is characteristic of two-phased systems. Specific volume, glass transition temperature, and heat distortion temperature were linear with binary composition. The storage modulus showed a small maximum, suggesting a weak interaction between the two miscible polymers. Heats of melting for the residual PVC crystallinity were also less than expected from linear additivity. At 160°C and 210°C, the logarithm of the complex viscosity was essentially linear with volume fraction of CPVC, except for a very slight decrease in the 50 to 75 percent CPVC range, which may have been a result of lower crystallinity. At 140°C, the complex viscosity of the CPVC was less than that of PVC owing to the higher crystallinity of the latter. The viscosities were similar at 160°C, but at 210°C, where most of the crystallites had melted, the complex viscosity of the CPVC was higher because of its higher glass transition temperature.     

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.     

Photostability,thermal and mechanical properties of poly(vinyl chloride)/novel acrylate terpolymer blend

Methyl methacrylate/2‐hydroxyethyl methacrylate/maleic anhydride terpolymer with various compositions was synthesized, characterized and investigated as a photostabilizer for rigid polyvinyl chloride (PVC). The chemical structure of the terpolymer MMA/HEMA/MA, was confirmed by ultraviolet–visible and FTIR, spectroscopy. The molecular weights of the terpolymer were determined by applying gel permeation chromatography. The stabilizing efficiency of the terpolymer was evaluated by the determination of the weight loss of PVC/terpolymer blends after various irradiation times. The content of the formed gel as well as the intrinsic viscosity of the soluble fraction of the photodegraded polymer were also determined. The efficiency was also evaluated by measuring the extent of the discoloration of the photodegraded polymer. Thermal gravimetric analysis of the terpolymer and PVC/terpolymer blend were measured. Moreover, physicomechanical properties of photodegraded stabilized PVC samples were as well measured. The results revealed that the photostabilizing efficiency as well as thermal stability increased in the presence of the terpolymer as blended with PVC and by the increase of maleic anhydride ratio in the terpolymer. The photostabilizing efficiencies were compared with the industrially known UV absorber 2‐hydroxy‐4‐(octyloxy) phenylbenzophenone. J. VINYL ADDIT. TECHNOL., 25:E55–E62, 2019. © 2018 Society of Plastics Engineers     

PVC/G-POSS共混物的力学性能与热性能

考察了2,3-环氧丙氧乙基笼型倍半硅氧烷(G-POSS)对聚氯乙烯(PVC)共混物力学和热性能的影响。结果表明:加入G-POSS可缩短PVC的塑化时间;100 g PVC中G-POSS用量不超过7 g时共混物的拉伸强度得到提高;加入G-POSS可改善PVC的耐热性能,G-POSS用量为13 g时,共混物的维卡软化温度和初始分解温度分别提高12,27℃。     

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。     

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.     

Effect of poly(epichlorohydrin) on the thermal and mechanical properties of poly(vinyl chloride)

Five kinds of polyepichlorohydrin (PECH) of different molecular weights were synthesized and characterized by gel permeation chromatography (GPC). Mechanical blending was used to mix PECH and poly(vinyl chloride) (PVC) together. The blends of different PVC/PECH ratios were characterized by thermogravimetric analysis (TGA), tensile tests, differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). TGA results show the thermal stability of PVC/PECH blends is desirable. Tensile tests indicate elongation at break is raised by increasing both the amount and the molecular weight of PECH. DSC is used to determine the glass transition temperature of PECH, and a quite low T_g is obtained. DMA results indicate that PECH has a perfect compatibility with PVC, when PECH concentration is below 20 wt %. There is only one peak in each tan δ curve, and the corresponding T_g decreases as PECH amount increases. However, above 20 wt %, phase separation takes place. The molecular weight of PECH also has a great influence on the glass transition temperature of the blends. This study shows that PECH is an excellent plasticizer for PVC, and one can tailor the glass transition temperature and tensile properties by changing the amount and the molecular weight of PECH. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of composite resin by vinyl chloride grafted onto poly(BA-EHA)/poly(MMA-St)

Crosslinked poly(butyl acrylate-co-2-ethylhexyl acrylate)/poly(methyl methacrylate-co-styrene) (ACR I) latex was synthesized by multi-stage emulsion polymerization. A series of grafting vinyl chloride (VC) composite latices were prepared by emulsion copolymerization in the presence of core-shell ACR I latex. The effects of ACR I amount and its core/shell ratio on particle diameters of the composite latices and mechanical properties of the prepared materials were investigated. The grafting efficiency (GE) of VC grafted onto ACR I increases with an increasing ACR I content. Transmission electron microscope (TEM) study indicates that ACR I latex particles have a regular core-shell structure obviously. However, when styrene content in the shell of ACR I is more than 70 percent of the shell by weight, ACR I latex particles have an irregular core-shell morphology like sandwich. The composite latex particles synthesized by core-shell ACR I latex grafting VC have a clear three-layered core-shell structure. Dynamic mechanical analysis (DMA) study reveals that the compatibility between ACR I and PVC is well improved. With increasing ACR I content, the loss peak in low temperature range for every composite sample becomes stronger and stronger and gradually shifts to a higher temperature. Scanning electron microscope (SEM) graphs showed that the fractured surface of the composite sample exhibited better toughness of the material. TEM graphs showed that ACR I was uniformly dispersed in the PVC matrix.     

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.     

Study on thermal,mechanical and morphological properties of recycled poly(vinyl chloride)/fly ash composites

The present study deals with the development of composite materials utilizing recycled poly(vinyl chloride) (r‐PVC) recovered from waste electrical and electronic materials and waste fly ash obtained from thermal power plants. The effect of the incorporation of fly ash on the mechanical, thermal and morphological properties of the r‐PVC matrix was studied. The primary characterization of r‐PVC and fly ash was done employing FTIR, EDX, particle size analysis and XRD analysis. Subsequently, fly ash with a particle size of approximately 9.29 μm was incorporated within the r‐PVC matrix. Composite sheets were prepared using a melt blending process followed by compression moulding. The mechanical test revealed an increase in the tensile strength and elongation at break of the r‐PVC/fly ash composite up to 30 wt% loading of fly ash beyond which there was a decrease in the tensile strength. The impact strength, however, decreased with increasing fly ash content in the r‐PVC matrix. The morphological properties of the composites showed a good distribution of the filler within the recycled matrix. The thermal properties of r‐PVC also improved with the incorporation of fly ash which was revealed from DSC and TGA studies. The water absorption test showed an increase in water uptake with the addition of fly ash in the r‐PVC matrix. © 2020 Society of Chemical Industry     

The effect of layered double hydroxides dispersion on thermal and mechanical properties of poly(vinyl chloride)/poly(methyl methacrylate) blends

Poly(vinyl chloride) (PVC)/layered double hydroxide (LDH) composites and PVC/poly(methyl methacrylate) (PMMA)/LDH composites were prepared via solution intercalation into PVC using both unmodified and organo‐modified LDHs and variable‐molecular‐weight PMMA as additional components. The LDH dispersion was investigated using X‐ray diffraction analysis and electron microscopy in scanning and transmission modes. Spotlight fourier transform infrared (FTIR) chemical imaging analysis was also used to obtain a deeper insight into the dispersion of polymer phases and LDH segregation. Thermal properties were determined using thermogravimetric analysis and differential scanning calorimetry; moreover, a preliminary investigation of mechanical properties in tensile mode and evaluation of the Vicat softening temperature were carried out. The morphological analysis of PVC/LDH and PVC/PMMA/LDH composites evidenced in both cases the presence of disordered micro‐aggregates with loss of the LDH crystallographic symmetry depending on the amount and molecular weight of PMMA. In particular, in the case of PVC/PMMA/LDH composites, the FTIR imaging analysis showed that PMMA mostly segregated in the LDH phase. However, even if the degree of LDH dispersion was not elevated (micro‐aggregates with disordered structures and size ranging from 0.5 up to 11 µm were evidenced), thermal stability and mechanical properties of the composites were improved with a synergic effect of PMMA and LDH. © 2013 Society of Chemical Industry     

Correlation between some solution and mechanical properties of poly(vinyl chloride) and chlorinated poly(vinyl chloride)

Correlations have been found between solubility parameters and some mechanical properties of a series of vinyl polymers containing 56.6–69.9% chlorine when tested below their glass transition temperature. It is shown that stress at yield increases similarly with chlorine content and with the volume occupied by a monomer unit in the polymer. Using the Reiner-Weissenberg theory of the dynamic strength of materials as a criterion and a rheological model based on a pair of Maxwell bodies in parallel with a Hooke spring, the amount of dissipated and conserved work to yield point was calculated. A parameter, defined as the ratio of work to cohesive energy density, describes the efficiency of the system. The overall efficiency of the system, based on work to break, and proportional efficiency, based on work to yield point, are affected by chlorine content and strain rate. In addition, a potential energy parameter is defined which describes the cohesive energy per volume occupied by monomer unit of the polymer. This parameter is proportional to the total work to break as well as to the ratio of the residual work after yield to total work at all strain rates tested. The major portion of work is conserved up to yield; only a small portion is dissipated. From the yield point to break, after the onset of viscous flow, the major part of this work is dissipated.     

The surface modification of diatomite,thermal, and mechanical properties of poly(vinyl chloride)/diatomite composites

Pristine diatomite was first purified by acid treatment and then modified with γ‐methacryloxy propyl trimethoxysilane molecule (KH570) to introduce hydrophobic chains on the surface of acid‐treated diatomite. Fourier‐transform infrared spectroscopy and thermogravimetric analysis (TGA) indicated that the silane coupling agent (KH570) was successfully grafted on the diatomite through covalent bonding. The digital photos showed that the silanization process changed the surface property of the diatomite. The poly(vinyl chloride) (PVC)/pristine diatomite and PVC/modified diatomite composites were prepared via two‐roll mill. The thermal stability and mechanical properties of PVC composites were investigated by TGA, mechanical properties tests, and dynamic mechanical analysis. The results showed that the thermal stability of the composites improved and maximum weight loss temperature (T_max) of the PVC composite with 1 phr modified diatomite was about 20°C higher than that of PVC composite without diatomite. The PVC/modified diatomite composites exhibited better mechanical properties owing to the stronger interfacial interaction between PVC matrix and modified diatomite. But the impact strength reduced sharply when the addition of diatomite was more than 1 phr. The reason of the phenomenon is that the diatomite plays the role of defects in PVC and it works against the absorption of impact strength energy. It was proved by the results of scanning electron microscopy. J. VINYL ADDIT. TECHNOL., 25:E39–E47, 2019. © 2018 Society of Plastics Engineers     

Investigation of the thermal,mechanical and morphological properties of poly(vinyl chloride)/polyhedral oligomeric silsesquioxane nanocomposites

Research into organic–inorganic nanocomposites has recently become popular, particularly the development of new polymer nanocomposites. Compared to pristine polymers or conventional composites, these nanocomposites exhibit improved properties. The storage modulus of a poly(vinyl chloride) (PVC)/polyhedral oligomeric silsesquioxane (POSS) nanocomposite slightly decreased with POSS content, but had a higher modulus from 50 to 100 °C. Some of the material appeared to be aggregated with 1 wt% POSS in the polymeric matrix. Conversely, with a POSS content of 5 wt%, a better dispersion of the nanoparticles was observed. The presence of POSS in the plasticised PVC compound had little influence on the final properties of the nanocomposites, showing weaker interactions between the POSS and the plasticised PVC compound. Copyright © 2010 Society of Chemical Industry     

Rheological and mechanical properties of plasticized poly(vinyl chloride)

The dependence of rheological properties of a plasticized, filled poly(vinyl chloride) compound on three different methods of thermomechanical treatments has been studied. These three different states of the compound are the dry blend mixed at a maximum temperature of 93°C, the two-roll milled sample prepared at 150°C from the dry blend and the molded sample pressed at 170°C from the previously milled material. At 150°C the viscosity and elasticity of the molded sample are considerably higher than those of the dry blend and the milled sample. At higher temperatures, although their flow curves more or less merge, extrudate swell, extrudate appearance and extrudate tensile properties of the three samples vary. The mechanical and Theological properties of the quenched and annealed molded samples and those of the same compound without filler have also been investigated.     

Investigation of thermal,mechanical and electrochemical properties of nanocomposites based on CuO modified poly(vinyl chloride)/poly(methyl methacrylate) blend

The preparation of binary polymer blend nanocomposites with different nanomaterials is a relatively new approach to achieve desired physical, thermal, mechanical, and electrochemical properties because it has the collective effects of both polymer blending and fillers. Transition metal oxides constitute a large class among those fillers because the precursors for metal oxides are abundantly available. However, very few studies have been accomplished on incorporating transition metal oxides into binary polymer blends. In this project, cuprous oxide (CuO) nanoparticles (NPs) with a crystallite size of 24.95 nm were incorporated into poly(vinyl chloride)/poly(methyl methacrylate) (PVC/PMMA) blend, and thin films of the nanocomposites were obtained through a solution casting technique. Scanning electron microscopy, X‐ray diffraction, universal testing machine testing, thermogravimetric analysis, and cyclic voltammetry were used to study morphological, crystalline, mechanical, thermal, and electrochemical properties of the nanocomposites. Scanning electron micrographs showed that the blend was completely miscible and CuO NPs were well dispersed within the matrix. Mechanical properties greatly improved with each wt% addition of CuO NPs. Thermogravimetric analysis thermograms revealed a two‐stage degradation for neat PVC/PMMA blend and CuO/PVC/PMMA. Cyclic voltammetry results indicated a free electron transfer in neat blend that further improved with the incorporation of increasing percentage of CuO NPs. J. VINYL ADDIT. TECHNOL., 23:80–85, 2017. © 2015 Society of Plastics Engineers     

Dynamic mechanical properties of poly(vinyl chloride)–xonotlite composite system

The filler effect of xonotlite (6CaO.6SiO₂.H₂O; needle-shaped) on dynamic mechanical properties, such as storage modulus (E′), loss modulus (E″), and tan δ was studied for the PVC—xonotlite composite system. And the properties of the system containing mechanically or chemically disaggregated particle of xonotlite were compared with those of the system-filled aggregates. The dynamic mechanical properties obviously depends on the dispersion condition of xonotlite particle. The aggregates of xonotlite produces a remarkably high modulus, an increase in T_g, and a decrease in mechanical damping near T_g in the system. On the other hand, the disaggregates, especially the chemical disaggregate one, bring softer or more rubbery properties in these systems. The interaction between matrix and filler was the strongest in the aggregates system and decreases in the order, mechanical disaggregates system, chemical disaggregates system.