Modification of aromatic diamine-cured epoxy resins by poly(oxymethylene) or hybrid modifiers containing poly(oxymethylene)

A copolymer comprising poly(oxymethylene) (POM, polyacetal) was used to improve the fracture toughness of a resin based on diglycidyl ether of bisphenol A (DGEBA) cured with 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenyl methane. POM was a less effective modifier for epoxies and a third component was used as a toughener or a compatibilizer for POM. The third component includes polypropylene glycol-type urethane prepolymer (PU) and aromatic polyesters. The hybrid modifiers composed of POM and PU were more effective as modifiers for toughening epoxies than POM alone. In the ternary DGEBA/POM/PU (90/10/10wt ratio) blend, the fracture toughness, K_IC, for the modified resin increased 50% with retention of flexural properties and a slight decrease in glass transition temperature (T_g) compared with those of the unmodified epoxy resin. The aromatic polyesters include poly(ethylene phthalate) (PEP), the related copolyesters and poly(butylene phthalate). PEP was most effective of them as a third component in the hybrid modifier. In the ternary DGEBA/POM/PEP (85/15/10) blend, K_IC for the modified resin increased 70% with medium loss of flexural strength and retention of T_g. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviour of the modified epoxy resin systems. ©1997 SCI     

The preparation and thermomechanical properties of high-temperature foams based on thermoplastic poly(phthalazinone ether ketone)

Poly(phthalazinone ether ketone) (PPEK) is an amorphous thermoplastic polymer with a high glass transition temperature (T_g) exceeding 250°C. We describe the preparation of foams from PPEK and characterize their properties. PPEK foams were prepared using dichloromethane as a foaming agent. The foaming agent was swollen into discs of the PPEK, which were then foamed by heating. Foams could be prepared at temperatures far below the T_g of the PPEK due to plasticization of the polymer by the foaming agent. Foams with densities ranging from 0.1 to 0.65 g/cm³ were prepared. Their thermal conductivity and modulus (measured approximately by indentation tests) were found to decrease with density, and the trends were similar to those expected from existing models. The foams could be annealed at 200°C without collapse suggesting that they may be useful in structural or insulation applications where stability at high temperature is essential.     

Partially miscible blends based on a polyarylate and poly(trimethylene terephthalate)

The miscibility of blends of a polyarylate (PAr) with poly(trimethylene terephthalate) (PTT) was investigated in the whole composition range by DSC measurements. With the exception of the 90/10 composition, which was fully miscible, the blends showed partial miscibility, and contained a nearly pure PTT phase and a PAr‐rich phase with 18% PTT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1559–1561, 2004     

Glass transition of poly(oxymethylene)

Heat capacity data of semicrystalline poly(oxymethylene) samples. Delrin and Celcon, are analysed in order to discuss the glass transition behaviour of this polymer. There are two types of non-crystalline poly(oxymetheylene). the mobile and rigid amorphous parts. The glass transition of the former occurs in a rather wider range of temperature: it starts at 180 K and could end at 265 K. The latter, under restraint due to the crystallites, remains frozen up to the melting temperature.     

PE100管及其热熔接头的蠕变裂纹扩展行为

聚乙烯(PE)管性能优异,广泛应用于城市水及燃气供应系统。PE管的主要破坏形式是长期静压载荷下的慢速裂纹扩展失效。在蠕变条件下,采用光滑试样和裂纹圆棒试样对PE100管及其热熔接头进行了测试,得到了基于蠕变断裂参数C*的蠕变裂纹扩展动力学关系式。利用扫描电子显微镜(SEM)分析了裂纹圆棒试样的断面形貌,对比分析结果发现,蠕变裂纹扩展失效模式对应的最大应力为15.05 MPa,热熔接头熔合面分布有约11个/mm^2、直径范围为1~5μm的微气孔,热熔接头断裂微纤平均长度比母材约小20%~45%。当热熔对接时,熔合面存在的微气孔以及系带分子的浅渗透是导致PE100热熔接头蠕变裂纹扩展抗力降低的主要原因。     

Plasticization of poly(vinyl butyral) by water: Glass transition temperature and mechanical properties

The effect of plasticization by water on the mechanical properties of additive-free poly(vinyl butyral) (PVB) was investigated. PVB is hygroscopic and the amount of absorbed water was measured in various environmental conditions. Two kinds of interactions with hydrophilic sites was demonstrated. The thermal and thermomechanical studies (differential scanning calorimetry and dynamic mechanical thermal analysis) showed that water decreases the glass transition temperature thus acting as a plasticizer. This gives the material larger deformation capability and increased toughness. Surprisingly, the modulus remains high and this was explained by a structure consisting in two phases with different levels of plasticization, reflected by a double peak of relaxation associated to multiple phases with different glass transition temperature. Atomic force microscopy measurements on samples with high level of hydration shows evidence of nanometric hydrated domains acting as an elastomeric phase and thus inducing toughening of the material. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47230.     

Morphology,drug release behavior,thermal, and mechanical properties of poly(ethylene oxide) (PEO)/poly(vinyl pyrrolidone) (PVP) blends

Poly(ethylene oxide) (PEO)/poly(vinyl pyrrolidone) (PVP) blends containing different amounts of PVP (0, 10, 25, 50, and 100 wt %) prepared by a solution casting method were characterized in terms of microstructure, thermal, and mechanical properties along with their drug release behavior. Fourier‐transform infrared spectroscopy results confirmed formation of hydrogen bonds between PEO and PVP. Although scanning electron microscopy micrographs showed no phase separation in the blends, the elemental analysis data obtained by energy dispersive X‐ray technique revealed partial miscibility between the blend components. The miscibility of the blend and degree of crystallinity of PEO component of the blend were decreased with increasing PVP content of the blend. The nucleating role of PVP in crystallization of PEO was confirmed by differential scanning calorimetry analysis. A synergistic effect on mechanical properties was obtained as a result of blending PVP with PEO. The results of curcumin release studies from the films indicated that, the blends have lower diffusion coefficients and slower drug release rate as compared to the neat PEO. Theoretical analysis of the drug release data using Peppas's model revealed that the kinetic of drug release from all the films is governed by a non‐Fickian diffusion mechanism. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46403.     

Structure and properties of thermoplastic poly(glycerol sebacate) elastomers originating from prepolymers with different molecular weights

Thermoplastic poly(glycerol sebacate) (TMPGS) elastomers originating from three prepolymers with different molecular weights were prepared first, and then the structure and properties were studied. Specifically, by swelling tests, gel permeation chromatography, X‐ray diffraction, and differential scanning calorimetry, the crosslinking densities, sol contents and compositions, crystallization, and thermal performances of three TMPGSs were examined. Finally, the degradability in a 37°C phosphate‐buffered saline solution (pH = 7.4) was also illuminated. The three TMPGSs had similar chemical structures, but the different molecular weights of the prepolymers influenced their final compositions and properties to a great extent. Furthermore, both hydrogen bonding and plasticization action in the elastomers played important roles in balancing the overall properties of the TMPGS elastomers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1131–1137, 2007     

Optimizing mechanical and morphological properties of biodegradable thermoplastic elastomer based on epoxidized natural rubber and poly(butylene succinate) blends

Biodegradable thermoplastic elastomer (BTPE) blends of epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) were prepared by the melt mixing process. Influences of the processing parameters mixing temperature, rotor speed, and mixing time on mechanical and morphological properties of BTPE were investigated. Taguchi method was applied to improve the mechanical and morphological properties by optimizing the processing parameters. That is, the experimental design adopted the L9 Taguchi orthogonal array with three manipulated factors (i.e., mixing temperature, rotor speed, and mixing time). Analysis of mean and analysis of variance were also exploited and the mixing temperature was found to be the most significant processing parameter regarding mechanical properties. The mixing temperature showed large contributions to Young's modulus, 100% modulus, tensile strength, and elongation at break, namely 45.33, 40.38, 49.31, and 36.04%, respectively. Furthermore, the optimum conditions found for mixing temperature, rotor speed, and mixing time were 140 °C, 100 rpm and 10 min, respectively. The result was confirmed by atomic force microscopy and scanning electron microscopy micrographs showing fine‐grained co‐continuous phase morphology of the ENR/PBS blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46541.     

Effect of chain extrender on the compatibility,mechanical and gas barrier properties of poly(butylene adipate-co-terephthalate)/poly(propylene carbonate) bio-composites

Bio-composites consisting of poly(butylene adipate-co-terephthalate) (PBAT), poly(propylene carbonate) (PPC) and epoxy chain extender ADR 4468 were fabricated via melt blending using a torque rheometer. The relationship of the torque, melt viscosity, and molecular weight of the bio-composites was established via polymeric liquid theory to estimate the real-time chain extension reaction rate under different ADR contents. At the meantime, rheological behavior, thermal and mechanical properties, morphologies, gas barrier properties of the PBAT/PPC/ADR bio-composites were systematically characterized. The corresponding results revealed that the water vapor transmission rate (WVTR) reduced by 50% under 30 phr (parts per hundreds of resin) PPC content. The addition of ADR is beneficial to improve the mechanical properties, thermal stability and phase dispersion of PBAT/PPC without affecting the water barrier property. With 3 phr ADR, the tensile stress and elongation at break were increased from 19.5 MPa and 1184% to 26.9 MPa and 1443%, respectively. In addition, the data of the torque rheometer revealed that the chain extension reaction rate and the melt viscosity was increased with the increasing ADR content, but the reaction rate was reduced with the excessive viscosity.     

Copolymers of poly(arylene sulfide sulfone)/poly(ether sulfone): Synthesis,structure, and rheology properties

In order to overcome the poor flowability of poly(arylene sulfide sulfone) (PASS), we introduced ether bonds into the polymer main chain. A series poly(arylene ether sulfide sulfone) copolymers (PAESS) containing different proportion of ether bonds were synthesized with 4,4′‐dichlorodiphenyl sulfone (DCDPS), sodium sulfide (Na₂S·xH₂O), and 4,4′‐dihydroxydiphenyl ether (DHDPE). The copolymers were characterized by Fourier transform infrared (FTIR), ¹H‐nuclear magnetic resonance (NMR), differential scanning calorimetry, dynamic mechanical analysis (DMA), and rheometer. The results of FTIR and ¹H‐NMR indicate the copolymers are synthesized successfully. PAESS were found to have excellent thermal properties with glass transition temperature (T_g) of 175.7–219.1 °C and 5% weight lost temperature were all above 420 °C. The tensile and DMA test indicates that these resultant copolymers have good mechanical properties with tensile strength of 60 MPa and storage modulus of 1.5 GPa. From the results of rheology properties testing, we found that the melt stability and melt flowability of PASS were improved distinctly from 25,470 Pa s down to 355 Pa s with the incorporation of ether bonds. That will be quite beneficial to the processing of PASS, especially for the thermoforming of precision products. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46534.     

Structure and properties development in poly(phenylene sulfide) fibers,part I: Effect of material and melt spinning process variables

The detailed research study of manufacturing PPS fibers using melt spinning and further enhancement of tensile properties by drawing and annealing experiments, a study lacking as of today in open scientific literature, was the focus of this research. This article discusses the effect of polymer molecular weight (MW) and melt spinning process variables on the structure and properties development in melt spun fibers manufactured from proprietary Fortron® linear PPS resins. Structure‐properties relationship was studied using several characterization tools like tensile testing, differential scanning calorimetry, polarized light optical microscopy, and wide‐angle x‐ray scattering. Changes in dynamic mechanical behavior of as‐spun fibers manufactured from resins of varying MW and different melt spinning take‐up speeds were also studied. The study showed that by a combination of higher MW of the polymer and spinning at higher take‐up speeds, tensile properties of as‐spun PPS fibers can be improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compositional trend analysis on poly(phenylene ether) based thermoplastic elastomers

Detailed statistical trend analysis of thermoplastic elastomers based on poly (phenylene ether) (PPE), polystyrene (PS), ethylene vinyl acetate (EVA) and styrene‐ethylene‐butylene‐styrene (SEBS) was done through Design Expert software by Stat‐Ease. D optimal crossed design was followed to capture the interaction with the parameters. Effect of blend ratio, vinyl acetate (VA) content of EVA, molecular weight (MW) of SEBS and intrinsic viscosity (IV) of PPE on the blend performance (response) was studied in detail. Design of Experiment (DOE) analysis showed the “optimized formulation” of the blend. Increase in PPE‐polystyrene (PS) content increased tensile strength and modulus of the blend, followed by a decrease in strain at break. However, EVA had a reverse effect on tensile strength and modulus. Strain at break increased significantly with increasing SEBS content in the blend. Graphical and numerical optimization showed that superior mechanical properties (tensile strength, strain at break and modulus) could be achieved at VA content ～ 50% at a particular loading of EVA. Low MW SEBS was found to be more compatible with the other components of the blend. Mechanical properties of the quaternary blend were marginally affected with change in IV of PPE in the range of 0.33 to 0.46. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Structure and thermodynamics in polymer blends. Neutron scattering measurements on blends of poly(methyl methacrylate) and poly(styrene-co-acrylonitrile)

Neutron scattering on polymer blends of deutero-poly(methyl methacrylate) (D-PMMA) and poly(styrene-co-acrylonitrile) with 19 wt% acrylonitrile (PSAN-19) exhibits excess scattering for scattering vectors Q0.2 nm⁻¹ if the volume fraction of D-PMMA is less than 0.5 and greater than 0.05. The range of occurrence and the amount of excess scattering depends to a certain degree on the procedure of sample preparation. If the excess scattering is eliminated by linear extrapolation from large to small Q in the Zimm representation, the residual scattering intensity in the small and intermediate Q-range can be interpreted by the mean field approach of de Gennes with a concentration-dependent effective interaction parameter. The scattering intensity in the intermediate Q-range can be described with the coil scattering function of Debye using effective radii of gyration and interaction parameters obtained from Q → 0 extrapolated scattering data. In the intermediate Q-range the scattering curves of D-PMMA in the bulk and in the investigated blends show small differences outside the limits of experimental error. These differences are interpreted as an environmental influence of the conformation of the PMMA chain.     

聚酯酰亚胺聚醚嵌段共聚物的合成与性能研究

采用均苯四酸酐与氨基乙酸合成了酰亚胺二元酸单体,此单体与乙二醇、聚乙二醇熔融缩聚合成3 种不同软／硬段比例分别为7／3,6／4,5／5的耐高温聚酯酰亚胺聚醚嵌段共聚物。通过红外光谱与氢谱确定 了酰亚胺二元酸单体的化学结构,DSC测定其熔点为358℃;利用显微熔点仪、乌式粘度计测定了共聚物的 熔点和特性粘数,3种共聚物熔点分别为232,248,260℃,软／硬段比例为7／3的共聚物的特性粘数为1.12 dL／g。将共聚物熔融纺丝,可纺性较好,纤维在120℃较160℃热定型效果好。     

Synthesis and properties of bio-based thermoplastic polyurethane based on poly (L-lactic acid) copolymer polydiol

The goal of this work is the synthesis of a new kind of bio-based thermoplastic polyurethane (BTPU) based on poly(L -lactic acid) (PLA) and poly(tetramethylene) glycol (PTMEG) segments via chain-extension reaction of dihydroxyl terminated (HO-PLA-PTMEG-PLA-OH) copolymer using hexamethylene diisocyanate (HDI) as a chain extender. Polydiols were synthesized through polycondensation of lactic acid and PTMEG in bulk. The chemical structures and molecular weights of polydiols and BTPUs containing different segment lengths and weight fractions of PLA, were characterized by ¹H-NMR and FTIR. The effects of the structures on the physical properties of BTPUs were studied by means of DSC, SEM, and tensile test; crystallization behavior was characterized by POM. The DSC and SEM results indicate that PLA segment is perfectly compatible with PTMEG segment and the crystallization of BTPU is predominantly caused by PLA segment. Polydiol with lower PLA content shows lower T_g and lower crystallinity. Tensile test shows that the elongation at break of BTPU is above 340% at the composition of PLA/PTMEG = 80/20 (w/w). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and properties of crosslinked poly(arylene ether nitriles) containing pendant phthalonitrile

In this study, poly(arylene ether nitriles) containing pendant carboxyl groups (PEN‐COOH) was first synthesized via nucleophilic aromatic substitution reaction from phenolphthalein, hydroquinone and 2,6‐dicholorobenzonitrile. Then, poly(arylene ether nitriles) with pendant phthalonitrile groups (PEN‐CN) was obtained via the Yamazaki–Higashi phosphorylation route from 4‐(4‐aminophenoxy)phthalonitrile (APN) with PEN‐COOH in the presence of CaCl₂, thus the phthalonitrile as pendant groups in PEN‐CN were easily crosslinked by further thermal treatment. The effect of crosslinking density on the thermal stabilities, dielectric properties and water absorption of the PEN‐CNs was investigated. These results showed that the T_g of PEN‐CN was improved from 182 to 213°C, dielectric constant (ε) was increased from 3.1 to 3.9, and dielectric loss (tan δ) was decreased from 0.090 to 0.013 at 1 kHz. The water absorption of PEN‐CNs after thermal crosslinking was <1.01 wt %, which showed excellent water resisting property. Therefore, this kind of poly(arylene ether nitriles) containing pendant phthalonitrile could be a good candidate as matrix resins for high‐performance polymeric materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of blending conditions on mechanical,thermal, and rheological properties of plasticized poly(lactic acid)/maleated thermoplastic starch blends

This research work has concerned a study on relationship between structure and properties of maleated thermoplastic starch (MTPS)/plasticized poly(lactic acid) (PLA) blend. The aim of this work is to investigate the effects of blending time, temperature, and blend ratio on mechanical, rheological, and thermal properties of the blend. The MTPS was prepared by mixing the cassava starch with glycerol and maleic anhydride (MA). Chemical structure of the modified starch was characterized by using a FTIR technique, whereas the degree of substitution was determined by using a titration technique. After that, the MTPS prepared by 2.5 pph of MA was further used for blending with triacetin‐plasticized PLA under various conditions. Mechanical, thermal, and rheological properties of the blends were evaluated by using a tensile test, dynamic mechanical thermal analysis, and melt flow index (MFI) test, respectively. It was found that tensile strength and modulus of the MTPS/PLA blend increased with the starch content, blending temperature, and time, at the expense of their toughness and elongation values. The MFI values also increased with the above factors, suggesting some chain scission of the polymers during blending. SEM images of the various blends, however, revealed that the blend became more homogeneous if the temperature was increased. The above effect was discussed in the light of trans‐esterification. Last, it was found that mechanical properties of the PLA/MTPS blend were more superior to those of the normal PLA/TPS blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of poly(dimer acid-sebacic acid) copolymer

Summary Poly (dimer acid-sebacic acid) P(DA-SA) copolymers have been prepared by melt polycondensation of the corresponding mixed anhydride prepolymers. The copolymers were characterized by FT-IR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). In vitro studies showed that all the copolymers are degradable in phosphate buffer at 37°C, and leaving an oily dimer acid residue after hydrolysis for the copolymer with high content of dimer acid. The release profiles of hydrophilic model drug, ciprofloxcin hydrochloride, from the copolymers, follows first order release kinetics. The in vivo biocompatibility of the copolymer in rabbit brain was also evaluated, macroscopic observation and microscopic analysis demonstrated that the copolymer is biocompatible and well tolerated in vivo. All the preliminary results suggested that the copolymer might be potentially used as drug delivery devices for brain implantation. Received: 4 April 2001/Revised version: 10 May 2001/Accepted: 22 May 2001