Developing toughened aromatic polybenzoxazines using thermoplastic oligomers and telechelics,part 1: Preparation and characterization of the functionalized oligomers

The preparation and characterization of three families of thermoplastic oligomers (M_n = 2918–13263 g mol^?1) based on polyarylsulfone (PSU) differing in both molecular weight and terminal functionality and one series of polyarylethersulfone (PES) of different molecular weights is reported. Infrared and nuclear magnetic resonance spectroscopy data support the formation of both the hydroxyl terminated oligomers and conversion (67–89% depending on molecular weight) to the telechelic PSU oligomer bearing reactive benzoxazine groups. Differential scanning calorimetry reveals that the onset of homopolymerization in the telechelic PSU oligomer occurs at around 100°C (peak maximum 125°C at 10 K/min) and rescans show values of the glass transition (for the homopolymers) ranging from 124 to 167°C depending on molecular weight. The influence on the oligomer backbone and terminal functionality is examined using thermal analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40875.     

Poly(ethyleneterephthalate) glycolysates as effective toughening agents for epoxy resin

The potential of poly(ethyleneterephthalate) glycolysates toward improving the energy absorption characteristics of cycloaliphatic epoxy resins has been explored. Microwave‐assisted glycolytic depolymerization of PET was performed in the presence of polyether diols of different molecular weights. The obtained glycolysates were blended with epoxy, and their mechanical properties were studied under both quasi‐static and dynamic conditions. Significant improvements were observed, which were found to depend both on the amount as well as nature of glycolysate. Amine functionalities were introduced at the terminal positions of glycolysates to improve the compatibility between the two phases. The amine derivatives exhibited superior performance and the Mode I fracture toughness (K_IC) of epoxy increased by ～18% in optimized compositions, which is indicative of its improved notch sensitivity. Neat epoxy specimens fractured in a brittle fashion, but all the blends exhibited ductile failure, as evidenced by surface morphological investigations. The mechanical properties of epoxy blends prepared with analogous aliphatic polyols, both before and after amine functionalization, were also studied which clearly reveal the beneficial role of aromatic groups toward improving the toughness of the base cycloaliphatic epoxy resin without compromising on the material stiffness. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39941.     

Investigation of cure kinetics in epoxy/multiwalled carbon nanotube nanocomposites

With the increased interest in thermoset resin nanocomposites, it is important to understand the effects of the material on nanoscale characteristics. In this study, a curing reaction of an epoxy resin, which contained 0.25, 0.50, or 1.00 wt % of multiwalled carbon nanotubes (MWCNTs), at different heating rates was monitored by differential scanning calorimetry; cure kinetics were also evaluated to establish a relationship between crosslinking (network formation) and mechanical properties. MWCNT concentrations above 0.25 wt % favored crosslinking formation and decreased the activation energy (E_a) in the curing reaction. Examination of the kinetic mechanism suggests that the MWCNT locally restricted the spatial volume and favored the formation of nodular morphology in the resin, especially for high MWCNT concentrations. The MWCNT exhibited some entanglement in the matrix, which hindered a more pronounced effect on the mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39857.     

Cell morphology,bubbles migration,and flexural properties of non‐uniform epoxy foams using chemical foaming agent

Epoxy foams with different densities and microstructures were prepared by changing the process parameters including the foaming temperature, chemical foaming agent (CFA) content and precuring extent. The microstructure of foams reveals a smaller cell size, higher cell density, and more homogeneous distribution of cells at higher precuring extent. However, the cell size and distribution are not affected by the foaming temperature and CFA content without precuring process. In addition, the bubbles migration, which resulted in non‐uniform cell density distribution, was promoted by increasing the foaming temperature and depressed by increasing the CFA content and precuring extent. The flexural properties of the non‐uniform epoxy foams were also studied. Results showed that the flexural modulus was related to the cell morphology, while the flexural strength was affected by both the cell morphology and the position of the specimens during test. It was also found that the relative flexural modulus and strength exhibited a power‐law dependence with respect to the relative density. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41175.     

Photocuring of cycloaliphatic epoxy formulations using polyesters with multiarm star topology as additives

Multiam star polyesters were synthesized by growing poly(ε‐caprolactone) (PCL) arms from hyperbranched polyesters cores of different molecular weight and used as polymeric modifiers in UV‐curable cationic formulations based on a biscycloaliphatic epoxy resin. The effect of the multiarm stars on the curing kinetics has been investigated by real‐time FTIR. The thermal‐mechanical properties of the photocured thermosets have been studied with calorimetry and dynamomechanical and thermogravimetric analysis. Impact strength tests have been performed to assess their effect on the toughness of the cured materials. An accelerative effect of these modifiers has been observed as a consequence of the participation of the hydroxyl groups of the modifiers in the cationic curing of the epoxy resin. A modest increase in toughness accompanied by a decrease in the glass transition are observed, as a consequence of the incorporation of the modifiers into the network structure, leading to homogeneous, in situ reinforced materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40005.     

Bio‐oil from whole‐tree feedstock in resol‐type phenolic resins

Renewable chemicals are of growing importance in terms of opportunities for environmental concerns over fossil‐based chemicals. Lignocellulosic biomass can be converted into energy and chemicals via thermal and biological processes. Among all the transformation processes available, fast pyrolysis is the only one to produce a high yield of a liquid‐phase product called bio‐oil or pyrolysis oil. Bio‐oil is considered to be a promising substitute for phenol in phenol formaldehyde (PF) resin synthesis. In this work, bio‐based phenolic resins have been formulated, partially substituting phenol by bio‐oils from two Canadian whole‐tree species. The new resins are produced by replacing 25, 50, and 75% of phenol with bio‐oil for each species (three bioresins per species). The aim of this study is to synthesize renewable resins with competitive price and satisfactory quality. The results obtained have shown that substitution degree up to 50% provided reactivity and performance equal or superior to the pure PF resin. They also present a good storage stability, improved shear strength, and thermal stability comparable to the pure PF. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40014.     

Shape memory CTBN/epoxy resin/cyanate ester ternary resin and their carbon fiber reinforced composites

Carboxylated-terminated liquid acrylonitrile rubber (CTBN) and epoxy resin (JEF-0211) were coreacted with cyanate ester (CE) to form CTBN/EP/CE ternary resin systems. Further, the ternary resin system was applied as prepreg for carbon fiber composites with vacuum bag degassing molding process. CTBN/EP/CE ternary shape memory polymer (SMP) exhibited relatively high tensile strength, Young's modulus, impact strength, and excellent shape memory properties. Compared with CTBN/EP/CE ternary SMP, CTBN/EP/CE carbon fiber composites showed much higher mechanical properties, such as their tensile strength and Young's modulus were high to 570 MPa and 36.7 GPa, respectively. Furthermore, CTBN/EP/CE carbon fiber composites exhibited good shape memory properties, their shape fixity ratio and shape recovery ratio were more than 95% after 30 times repeating shape memory tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48756.     

Biphenyl liquid crystal epoxy containing flexible chain: Synthesis and thermal properties

A biphenyl type liquid crystal epoxy (LCE) monomer 4,4′-di(2,3-epoxyhexyloxy)biphenyl (LCBP4) containing flexible chain was synthesized and the curing behavior was investigated using 4,4′-diaminodiphenylmethane (DDM) as the curing agent. The effect of curing condition on the formation of the liquid crystalline phase was examined. The cured samples show good mechanical properties and thermal stabilities. Moreover, the relationship between thermal conductivity and structure of liquid crystalline domain was also discussed. The samples show high thermal conductivity up to 0.28–0.31 W/(m*K), which is 1.5 times as high as that of conventional epoxy systems. In addition, thermal conductive filler, Al₂O₃, was introduced into LCBP4/DDM to obtain higher thermal conductive composites. When the content of Al₂O₃ was 80 wt%, the thermal conductivity of the composite reached to 1.86 W/(m*K), while that of diglycidyl ether of bisphenol A (Bis-A) epoxy resin/DDM/Al₂O₃ was 1.15 W/(m*K). Compared with Bis-A epoxy resin, the formation of liquid crystal domains in the cured LCE resin enhanced the thermal conductivity synergistically with the presence of Al₂O₃. Furthermore, the introduction of Al₂O₃ also slightly increased the thermal stabilities of the cured LCE.     

Subtle variations in the structure of crosslinked epoxy networks and the impact upon mechanical and thermal properties

Presented here is an investigation of the structure–property relationships of crosslinked networks using three bi-functional glycidyl ether aromatic epoxy resins, two bi-aryl and one tri-aryl, cured with bi- and tri-aryl amines. Subtle changes to the monomer chemistry including changing aromatic substitution patterns from meta to para, methylene to isopropyl and isopropyl to ether were explored. Changing an epoxy resin backbone from methylene to isopropyl enhances backbone rigidity thus increasing glass transition temperature (T_g), yield strength, and strain despite reducing modulus. Changing meta-substitution to para increases T_g and yield strain while leaving strength unaffected and reducing modulus. Changing isopropyl linkages to ether reduces modulus, strength, T_g, and yield strain reflecting increased molecular flexibility. Using three instead of two aromatic rings increases the molecular weight between crosslinks thereby decreasing T_g and yield strain while increasing modulus and strength. Despite the complexities of multiple systems for varying epoxy resins and amine hardeners, the effect upon network properties is explained in terms of short- and long-range molecular and segmental mobility, crosslink density, and equilibrium packing density. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48874.