Cure behavior,morphology, and mechanical properties of the melt blends of epoxy with polyphenylene oxide

Cure behavior, miscibility, and phase separation have been studied in blends of polyphenylene oxide (PPO) with diglycidyl ether of bisphenol A (DGEBA) resin and cyanate ester hardener. An autocatalytic mechanism was observed for the epoxy/PPO blends and the neat epoxy. It was also found that the epoxy/PPO blends react faster than the neat epoxy. During cure, the epoxy resin is polymerized, and the reaction‐induced phase separation is accompanied by phase inversion upon the concentration of PPO greater than 50 phr. The dynamic mechanical measurements indicate that the two‐phase character and partial mixing existed in all the mixtures. However, the two‐phase particulate morphology was not uniform especially at a low PPO content. In order to improve the uniformity and miscibility, triallylisocyanurate (TAIC) was evaluated as an in situ compatibilizer for epoxy/PPO blends. TAIC is miscible in epoxy, and the PPO chains are bound to TAIC network. SEM observations show that adding TAIC improves the miscibility and solvent resistance of the epoxy/PPO blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 26–34, 2000     

Blends of epoxy resins and polyphenylene oxide as processing aids and toughening agents 2: Curing kinetics,rheology, structure and properties

The curing behaviour, chemorheology, morphology and dynamic mechanical properties of epoxy ? polyphenylene oxide (PPO) blends were investigated over a wide range of compositions. Two bisphenol A based di‐epoxides ? pure and oligomeric DGEBA ? were used and their cure with primary, tertiary and quaternary amines was studied. 4,4′‐methylenebis(3‐chloro‐2,6‐diethylaniline) (MCDEA) showed high levels of cure and gave the highest exotherm peak temperature, and so was chosen for blending studies. Similarly pure DGEBA was selected for blending due to its slower reaction rate because of the absence of accelerating hydroxyl groups. For the PPO:DGEBA340/MCDEA system, the reaction rate was reduced with increasing PPO content due to a dilution effect but the heat of reaction were not significantly affected. The rheological behaviour during cure indicated that phase separation occurred prior to gelation, followed by vitrification. The times for phase separation, gelation and vitrification increased with higher PPO levels due to a reduction in the rate of polymerization. Dynamic mechanical thermal analysis of PPO:DGEBA340/MCDEA clearly showed two glass transitions due to the presence of phase separated regions where the lower T_g corresponded to an epoxy‐rich phase and the higher T_g represented the PPO‐rich phase. SEM observations of the cured PPO:DGEBA340/MCDEA blends revealed PPO particles in an epoxy matrix for blends with 10 wt% PPO, co‐continuous morphology for the blend with 30 wt% PPO and epoxy‐rich particles dispersed in a PPO‐rich matrix for 40wt% and more PPO. © 2014 Society of Chemical Industry     

An Intumescent-Like Flame-Retardant Effect of Hollow Carbon Precursor on Acrylonitrile–Butadiene–Styrene/Oligomeric Aryl Phosphate/Novolac Epoxy Composites

An intumescent-like char layer was formed by introducing hollow phenolic microspheres into acrylonitrile–butadiene–styrene/oligomeric aryl phosphate/novolac epoxy resin. Acrylonitrile–butadiene–styrene-grafted maleic anhydride was used to improve their compatibility. Combustion and thermal degradation behaviors were studied. The results showed that the ABS composites containing 25 wt% oligomeric aryl phosphate/novolac epoxy (3/2) obtains a limiting oxygen index as high as 50; however, it cannot be classified in the UL-94 test. Combination of oligomeric aryl phosphate/novolac epoxy, acrylonitrile–butadiene–styrene-grafted maleic anhydride, and hollow phenolic microspheres (23/10/2) improves the UL-94 grade of acrylonitrile–butadiene–styrene composites to V-1. A continuous and compact porous intumescent-like char layer is generated during combustion; thus, better flame retardancy is obtained.     

A Probe on the Failure Mechanism in Rubber-Modified Epoxy Blends: Morphological and Acoustic Emission Analysis

In this work, diglycidyl ether of bisphenol A based epoxy resin (DGEBA) was modified with varying amounts of two liquid rubbers: carboxyl terminated copolymer of butadiene and acrylonitrile (CTBN); and a hydroxyl terminated polybutadiene (HTPB), using an anhydride hardener. The ultimate aim of this study was to investigate the failure mechanism operating in the rubber-modified epoxies and to evaluate this by correlating these results with the miscibility and interfacial adhesion between the components and the morphology of the cured network. Some of the mechanical and fracture properties, which are associated with the two-phase particulate morphology, were investigated. The visoelastic behavior of modified epoxies was also analyzed and variations in the shift of T _g values in toughened epoxies were explained. The samples were carefully analyzed by an acoustic emission technique to investigate the failure mechanism operating in them. From the response of force and number of acoustic events as well as from the amplitude of acoustic events, we were able to explain the failure mechanisms in the elastomer incorporated epoxy resins supplemented by morphological evidence.     

Effects of extensional flow on properties of polyamide‐66/poly(2,6‐dimethyl‐1,4‐phenylene oxide) blends: A study of morphology,mechanical properties,and rheology

In this study, polyamide‐66/poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PA66/PPO) blends with high viscosity ratio were processed by a self‐designed triangle‐arrayed triple‐screw extruder (TTSE, which simulates extensional flow) and a commercial twin‐screw extruder (TSE), respectively. Furthermore, in order to improve the mechanical properties of the immiscible PA66/PPO blends, PPO‐grafted maleic anhydride (PPO‐g‐MA) and styrene–ethylene–butylene–styrene (SEBS) block copolymer were used. The mechanical properties, phase morphology, and rheological properties of both binary PA66/PPO blends and toughened PA66/PPO/PPO‐g‐MA blends were comprehensively investigated to compare the above mentioned two processing method. Samples processed with TTSE exhibited better mechanical properties than the TSE‐processed blends. The morphologies of the blends were examined by scanning electron microscopy, exhibiting smaller particles sizes and narrower particle size distributions, which were attributed to the significant effects of extensional flow in TTSE. The toughening mechanism of compatibilized blends was investigated through morphology analysis, dynamic mechanical, and rhelogical analysis. Thus, TTSE with an extensional effect was proved to be efficient in the blending of high viscosity ratio polymers. POLYM. ENG. SCI., 57:1090–1098, 2017. © 2016 Society of Plastics Engineers     

Relationship between structure and properties in high‐performance PA6/SEBS‐g‐MA/(PPO/PS) blends: The role of PPO and PS

This work aimed at studying the role of poly(phenylene oxide) (PPO) and polystyrene (PS) in toughening polyamide‐6 (PA6)/styrene‐ethylene‐butadiene‐styrene block copolymer grafted with maleic anhydride (SEBS‐g‐MA) blends. The effects of weight ratio and content of PPO/PS on the morphology and mechanical behaviors of PA6/SEBS‐g‐MA/(PPO/PS) blends were studied by scanning electron microscope and mechanical tests. Driving by the interfacial tension and the spreading coefficient, the “core–shell” particles formed by PPO/PS (core) and SEBS‐g‐MA (shell) played the key role in toughening the PA6 blends. As PS improved the distribution of the “core–shell” particles due to its low viscosity, and PPO guaranteed the entanglement density of the PPO/PS phase, the 3/1 weight ratio of PPO/PS supplied the blends optimal mechanical properties. Within certain range, the increased content of PPO/PS could supply more efficient toughening particles and bring better mechanical properties. Thus, by adjusting the weight ratio and content of PPO and PS, the PA6/SEBS‐g‐MA/(PPO/PS) blends with excellent impact strength, high tensile strength, and good heat deflection temperature were obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45281.     

PP–elastomer–filler hybrids. I. Processing,microstructure, and mechanical properties

Three-component systems with a polypropylene (PP) matrix consisting of polar elastomer (ethylene–propylene rubber and styrene–ethylene–butylene–styrene grafted with maleic anhydride) or of polar PP (PP grafted with maleic anhydride) and filler were investigated. Three microstructures of PP–elastomer–filler hybrids were obtained by processing control and elastomer or PP modification with the maleic anhydride: fillers and rubber particles were separated in the PP matrix, rubber particles with filler core were distributed in the PP matrix, and mixed microstructures of the first and second. A study of mechanical properties showed that the elastic modulus increased in the first microstructure and impact strength increased in the second microstructure. Mechanisms for the relationships between microstructure, processing, and mechanical properties are discussed. © 1996 John Wiley & Sons, Inc.     

Thermal and mechanical properties of PPO filled epoxy resins compatibilized by triallylisocyanurate

A series of blends has been prepared by adding a poly(phenylene oxide) (PPO), in varying proportions, to an epoxy resin cured with dicyandiamide. All the materials show two‐phase morphology when characterized by SEM and DMA. SEM and DMA indicate that partial mixing exists in all the blends especially with high PPO content. This implies that the epoxy oligomer or low crosslinking density epoxy exists in the PPO phase after curing. The tensile strength and modulus of these blends are nearly independent of the PPO content, while the fracture toughness (G_IC) is improved by PPO. However, the two‐phase particulate morphology is not uniform. In order to improve the uniformity and miscibility, triallylisocyanurate (TAIC) has been used as an in situ compatibilizer for the polymer blends of epoxy and PPO. SEM and DMA reveal improvement of miscibility and solvent resistance for this system. The fracture toughness of these TAIC‐modified systems are also improved by adding TAIC (0–20 phr). © 2000 Society of Chemical Industry     

Rubber-modified epoxies: III. Influence of the rubber molecular weight on the phase separation process

The effect of varying the rubber molecular weight on the reaction induced phase separation taking place in rubber-modified epoxies is reported. Three butadiene–acrylonitrile copolymers with number-average molecular weights of 2030, 3600 and 6050 g mol^?1 were used. The thermosetting polymer was an epoxy based on diglycidylether of bisphenol-A cured with a cycloaliphatic diamine. Increasing the rubber molecular weight showed the following effects: (i) a decrease in the conversion at the cloud point; (ii) a corresponding decrease in the viscosity at the cloud point; (iii) a primary morphology of a low concentration of particles with a large size; (iv) a more complete segregation of the rubber from the matrix leading to a smaller decrease of the glass transition temperature of the system; (v) a decrease in the toughening. The Flory–Huggins lattice model may be used as a simple approximation to describe the phase separation process when varying the rubber molecular weight.     

Properties of impregnation resin added to multifunctional epoxy at cryogenic temperature

A multifunctional epoxy tetraglycidyl dibenzmethyldiamine and triglycidyl benzylamine were blended, respectively, into impregnation resin, which mainly consists of diglycidyl ether of bisphenol A (DGEBA) and acid anhydride hardener. This resin is expected to impregnate HT‐7U superconducting Tokamak toroidal field coils and improve the fracture toughness of DGEBA–acid anhydride resin at cryogenic temperature. However, the experimental results reveal that resin lap shear strengths decrease remarkably both at ambient and liquid nitrogen temperatures. After blending multifunctional epoxy for several hours, its viscosity increased quickly at room temperature. The usable potting life is too short to impregnate large coils such as those used in fusion reaction. By FTIR the possible reason was investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1385–1389, 2003     

Toughening epoxy resins with solid acrylonitrile–butadiene rubber

The feasibility of using solid acrylonitrile–butadiene rubbers (NBR) with 19 and 33% w/w acrylonitrile to toughen diglycidyl ether of bisphenol A (DGEBA) epoxy resins has been investigated. Thermal analysis experiments revealed a two‐phase morphology of these rubber‐modified epoxies. However, the higher content of acrylonitrile in the rubber caused better compatibility between NBR and the epoxy resin. The rubber with 33% acrylonitrile was found to be an effective toughening agent for DGEBA epoxy resins. Fracture surface studies and also the high tensile strength of crosslinked high molecular weight NBR suggest that the toughening effect should arise from rubber bridging and tearing mechanisms. © 2000 Society of Chemical Industry     

纳米粒子／环氧树脂复合材料的固化动力学研究

为了改善纳米SiO2粒子在环氧树脂基体中的分散性,提高无机粒子与基体的界面结合力,文章选择马来酸酐和苯乙烯单体在粒予表面进行接枝改性。改性粒予与环氧树脂在固化条件下基本不发生反应,而固化剂2-乙基-4-甲基咪唑使得改性粒子上的酸酐开环生成羧酸;固化动力学分析表明：纳米粒子表面的羟基对环氧树脂的固化起促进作用;与未改性的粒子相比,填充SiO2-SMA粒子的固化体系的粘度较低,所以固化起始温度降低,但反应活化能较高。     

Poly(phenylene ether)/epoxy thermoset blends based on anionic polymerization of epoxy monomer

Low molar mass poly (phenylene ether) (LMW‐PPE) with phenol‐reactive chain ends was used as modifier of epoxy thermoset. The epoxy monomer was diglycidylether of bisphenol A (DGEBA), and several imidazoles were used as initiators of anionic polymerization. The curing and phase separation processes were investigated by different techniques: Differential Scanning Calorimetry, Size Exclusion Chromatography, and Light Transmission measurements. The final morphology of blends was observed by Environmental Scanning Electron Microscopy and Transmission Electron Microscopy. The epoxy network is obtained by imidazole initiated DGEBA homopolymerization. Initial LMW‐PPE/DGEBA mixtures show an UCST behavior with cloud point temperatures between 40 and 90°C. PPE phenol end‐groups can react with epoxy, leading to a better interaction between phases. The curing mechanism and phase separation process are not influenced by the chemical structure of initiators, except when reactive amine groups are present. The phase inversion is observed at 30 wt % of PPE. The mixtures with amine‐substituted imidazole present important differences in the initial miscibility and curing process interpreted in terms of fast room temperature amine‐epoxy reaction during blending. Final domain size is affected by this prereaction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2678–2687, 2004     

Poly(sulfobetaine)s and corresponding cationic polymers. IX. Synthesis and aqueous solution properties of zwitterionic poly(sulfobetaine) derived from a styrene–N,N‐dimethylaminopropyl maleamidic acid copolymer

A styrene–N,N‐dimethyl(maleamidic acid)propyl ammonium propane sulfonate (SDMMAAPS) copolymer was synthesized through an amidoacidation reaction of a styrene–maleic anhydride alternating copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction) and then reacted with propane sultone. The cloud point and minimum salt concentration (msc) of this ampholytic SDMMAAPS copolymer were determined in aqueous salt solutions. The effects of counterions on the cloud point and msc of SDMMAAPS were not entirely the same as those of other zwitterionic poly(sulfobetaine)s. The greatest difference from other poly(sulfobetaine)s, such as styrene–N,N‐dimethyl(maleimido propyl)ammonium propane sulfonate copolymers, was the carboxylic group on the polymer chain unit of SDMMAAPS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1884–1889, 2003     

Matrix–particle interactions in catalyzed and uncatalyzed copper-filled epoxy matrix composites

Epoxy composites filled with copper particles with sizes of the order of 100 μm are studied with the aim of analyzing the particle–matrix interphase. Two matrixes are used: diglycidyl ether of bisphenol A resin (DGEBA)–anhydride catalyzed using a tertiary amine, and uncatalyzed DGEBA–anhydride. The surface of both types of composites was analyzed using scanning electron microscopy, X-ray photoelectron spectroscopy, and instrumented nanoindentation. The formation of Cu(I) and Cu(II) complexes is revealed using X-ray photoelectron spectroscopy, while instrumented nanoindentation measurements allow us to determine regions with different mechanical properties in the uncatalyzed composite. The influence of anhydride and the type of curing reaction on the formation of copper complexes is analyzed. The main results point out that copper particles can interact strongly with the epoxy, depending on the chemistry and kinetics of the curing reaction, to modify the composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47511.     

Blends of epoxy–amine resins with poly(phenylene oxide) as processing aids and toughening agents: I. Uncured systems

The effect of two different bisphenol‐A‐based diepoxides—nearly pure DGEBA340 and a DGEBA381 oligomer—and an aromatic diamine curative (MCDEA) on the solubility and processability of poly(phenylene oxide) (PPO) was studied. The solubility parameters of the diepoxies and the curative calculated from Fedors's method suggest miscibility of PPO with the components, and this was observed at the processing temperature; however, some of the blends were not transparent at room temperature, indicating phase immiscibility and/or partial PPO crystallization. The steady shear and dynamic viscosities of the systems agreed well with the Cox–Merz relationship and the logarithmic viscosities decreased approximately linearly with increasing amounts of DGEBA381, DGEBA340 or MCDEA, thus causing a processability enhancement of the PPO. The dynamic rheology of intermediate PPO:DGEBA compositions at 200 °C showed gel‐like behaviour. Dynamic mechanical analysis of blends with varying PPO:DGEBA ratios showed that the main glass transition temperature (T_g) of the blends decreased continuously with increasing epoxy content, with a slightly higher plasticizing efficiency being exhibited by DGEBA340 compared to DGEBA381. However, blends with 50 and 60 wt% PPO had almost identical T_g due to the phase separation of the former blends. The blends of MCDEA and PPO were miscible over the concentration range investigated and T_g of the blends decreased with increasing MCDEA concentration. © 2013 Society of Chemical Industry     

颜料分散用马来酸酐-乙醇胺-苯乙烯水性高分子助剂的合成

以乙酸乙酯为溶剂,马来酸酐、乙醇胺、苯乙烯为单体,过氧化苯甲酰为引发剂,采用溶液聚合法合成了聚羧酸型马来酸酐–乙醇胺–苯乙烯(MA–EA–St)高分子分散剂,研究了聚合反应温度和时间、引发剂用量及酰化马来酸酐与苯乙烯的摩尔比对TiO2颗粒悬浮率的影响,获得了较佳的聚合反应条件为:n(酰化马来酸酐)∶n(苯乙烯)=1.25,聚合反应温度75°C、时间5 h,引发剂用量占单体总质量的2%。当此条件下合成的MA–EA–St分散剂用量为2.5 g/L时,TiO2颗粒的悬浮率为97.42%,达到较佳的分散效果。     

Modification of the grafting character to prepare PA6/ABS-g-MA blends with higher toughness and stiffness

Tert-dodecyl mercaptan (TDDM) was used to modify the grafting character of maleic anhydride–functionalized acrylonitrile–butadiene–styrene core–shell particles (ABS-g-MA). With the increase of TDDM content, the grafting degree and grafting efficiency of ABS-g-MA particles decrease, which induce the decrease of grafted acrylonitrile–styrene–maleic anhydride copolymer (g-SAM) and the increase of free acrylonitrile–styrene–maleic anhydride copolymer (f-SAM). The change of the g-SAM and f-SAM content modifies the chemical reactions degree at the interface and in the matrix. The interface reaction can decrease the interfacial tension and prohibit the agglomeration of ABS-g-MA particles, which have been testified by Molau test and SEM observation. The interface reaction is beneficial to the toughness improvement and the reaction in the matrix leads to higher stiffness. In the present paper, when TDDM content is 0.28 %, PA6/ABS-g-MA blend shows superior toughness and higher stiffness.     

Chemical modification of unsaturated polyesters influence of polyester's structure on thermal and viscoelastic properties of low styrene content copolymers

In this study, the chemical modification of unsaturated polyesters and the influence of polyester's structure on thermal and viscoelastic properties have been presented. The structure of unsaturated polyesters obtained in polycondensation of cyclohex‐4‐ene‐1,2‐dicarboxylic anhydride (THPA), maleic anhydride and only one suitable symmetrical glycol: ethylene glycol or 1,4‐butanediol (BDO) or 1,6‐hexanediol has been modified by peracetic acid. The selective oxidation of unsaturated polyesters conducted in mild time and temperature conditions was a successful and effective method to prepare new materials/unsaturated epoxy polyesters/containing epoxy groups in cycloaliphatic rings and carbon–carbon double bonds in polyester chain. The unsaturated epoxy polyesters were capable of both copolymerization with vinyl monomer and polyaddition reactions with suitable curing agent. Therefore, they were successfully used as a component of low styrene content copolymers. As was confirmed by DSC, DMA, and TGA analyses, polyester's structure had significant influence on thermal and viscoelastic properties of styrene copolymers. The properties of styrene copolymers prepared from unsaturated epoxy polyesters were considerably better compared with those obtained for styrene copolymers from unsaturated polyesters.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Epoxy‐amine networks with varying epoxy polydispersity

Solid, high molecular weight DGEBA‐based epoxies were blended with high purity liquid DGEBA to create several resins with equivalent epoxy equivalent weights, but with polydispersity indices (PDIs) ranging from 3 to over 10. The resins were cured with a stoichiometric amount of polyetheramine and compared to a nonblended epoxy with PDI of 1.8. Modulus, glass transition temperatures, and molecular weight between cross‐links were measured using dynamic mechanical analysis. Coefficients of thermal expansion (CTE) were measured and used to extend room temperature density measurements as a function of temperature. Fracture properties were also measured. Overall, the increased polydispersity has almost negligible effect, with the main difference occurring in the slope of the glassy CTE, with more polydisperse epoxies having a slower increase in CTE. In comparison to previous work where bimodal amines were blended with DGEBA, we conclude that epoxy resins are far more sensitive to distributions in the flexible portion, rather than the more rigid one. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41503.