Rubber-toughening epoxy thermosets with epoxidized crambe oil

Epoxidized crambe oil and rapeseed oil were synthesized by reaction of the oils with m-chloroperoxybenzoic acid. Formulating the neat epoxidized oils with epoxy-amine systems gave two-phase thermosets with epoxidized crambe oil, but not with epoxidized rapeseed oil. Glass transition temperature, mechanical properties, and fracture toughness of the epoxidized crambe oil thermoset specimen were measured. Fracture toughness values of the epoxy thermosets were increased approximately 100% by both 5 and 10% epoxidized crambe oil. Glass transition temperature and mechanical properties were affected only modestly.     

Novel flame retardant thermosets from nitrogen‐containing and phosphorus‐containing epoxy resins cured with dicyandiamide

A novel phosphorus‐containing epoxy resin (EPN‐D) was prepared by addition reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and epoxy phenol‐ formaldehyde novolac resin (EPN). The reaction was monitored by epoxide equivalent weight (EEW) titration, and its structure was confirmed by FTIR and NMR spectra. Halogen‐free epoxy resins containing EPN‐D resin and a nitrogen‐containing epoxy resin (XT resin) were cured with dicyandiamide (DICY) to give new halogen‐free epoxy thermosets. Thermal properties of these thermosets were studied by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), thermal mechanical analyzer (TMA) and thermal‐gravimetric analysis (TGA). They exhibited very high glass transition temperatures (T_gs, 139–175°C from DSC, 138–155°C from TMA and 159–193°C from DMA), high thermal stability with T_{d,5 wt %} over 300°C when the weight ratio of XT/EPN‐D is ≥1. The flame‐retardancy of these thermosets was evaluated by limiting oxygen index (LOI) and UL‐94 vertical test. The thermosets containing isocyanurate and DOPO moieties showed high LOI (32.7–43.7) and could achieve UL‐94 V‐0/V‐1 grade. Isocyanurate and DOPO moieties had an obvious synergistic effect on the improvement of the flame retardancy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Polyurea/vinylester hybrid thermoset resins with in situ produced silicate filler: Preparation and static mechanical properties

Proprietary polyurea‐based thermosets were produced from polyisocyanate and water glass (WG) using a phosphate‐type phase transfer catalyst. WG was dispersed in the polyisocyanate resulting in water‐in‐oil (W/O) type emulsion. The polyurea matrix, formed after crosslinking, contained the WG derived silicate in coarse particles showing a broad particle size distribution. The mean particle size of the silicate was markedly reduced and its distribution narrowed when the polyisocyanate was hybridized with a peroxide crosslinkable vinylester resin (VE) when the amount of the latter was <75%. This resin hybridization strongly improved the mechanical (flexural) properties of the related thermosets, however, at cost of the fracture mechanical characteristics (fracture toughness and energy under mode I condition). This was mostly attributed to the formation of a conetwork or interpenetrated network between the polyurea and VE. The static flexural and fracture mechanical properties were determined as function of the resin hybridization ratio. It was found that the mechanical properties change according to the additivity rule as a function of the resin hybridization in the first approximation. The silicate dispersion and the failure behavior in the polyurea/VE hybrids were studied by scanning electron microscopy (SEM) and discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 853–859, 2007     

Ring-opening metathesis polymerization (ROMP) of norbornenyl-functionalized fatty alcohols

Novel biorenewable-based thermosets have been successfully synthesized by the ring-opening metathesis polymerization (ROMP) of norbornenyl-functionalized fatty alcohols derived from soybean oil (NMSA), Dilulin (NMDA), ML189 (NMMA) and castor oil (NMCA). The effects of the monomer structure on the polymerization process, and the thermal and mechanical properties of the resulting thermosets have been extensively investigated. The number of ROMP-reactive rings appended to the fatty acid chain and the viscosity play an important role in controlling the initiation and propagation processes of the polymerization and the final properties of the thermosets obtained. The thermosets have been characterized by Soxhlet extraction, DMA, TGA, and tensile tests. It has been found that polyNMDA and polyNMMA have best thermo-mechanical properties. Compared with polyNMSA, the polyNMDA and polyNMMA thermosets exhibit lower soluble fractions, and higher thermal stabilities and mechanical properties, because of more effective crosslinking; whereas, polyNMCA exhibits a higher soluble fraction, and lower thermal stability, resulting from incomplete polymerization of the more viscous NMCA monomer.     

Hybrid thermosets from polyisocyanate/water glass/emulsifier systems: Effects of melamine‐formaldehyde resin

Melamine‐formaldehyde resin (MF) was selected as potential reactive emulsifier for polyurea‐based thermoset resins produced from polyisocyanate/water glass (WG)/emulsifier systems. As emulsifier tricresylphosphate and/or MF served for the initial water‐in‐oil type (“water” = WG; “oil” = polyisocyanate + emulsifier) emulsions. The MF content of the systems has been varied (≤15 wt %) and its effect on the structure, mechanical, thermal and flammability properties of the final polyurea‐based thermosets studied. It was found that MF is a suitable emulsifier, which can fully replace the phosphate without negatively affecting the properties of the resulting hybrid thermosets. Moreover, hybridization with MF was often accompanied with pronounced improvements in fracture mechanical and static flexural properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. VI. Time–temperature–transformation cure diagram and the effect of curing conditions on the thermoset properties

A new class of thermosetting resins has been developed that is based on the cationic copolymerization of regular soybean oil (SOY), low saturation soybean oil (LSS), or conjugated LSS (CLS) with various alkene comonomers initiated by boron trifluoride diethyl etherate (BFE) or related modified initiators. The activation energy for the gelation process for these thermosets ranges from 95 to 122 kJ/mol. A time‐temperature‐transformation (TTT) isothermal cure diagram has been established for the model system LSS45–ST32–DVB15–(NFO5–BFE3) ie 45 wt% low saturation soybean oil, 32 wt% styrene, 15 wt% divinylbenzene, and 5 wt% Norway fish oil ethyl ester plus 3 wt% boron trifluoride diethyl etherate. The effect of curing conditions on the thermophysical and mechanical properties, including the mechanical damping and shape memory properties, has been subsequently investigated using this model thermoset. These findings allow the efficient optimization of desired properties for specific applications. © 2003 Society of Chemical Industry     

Morphologies and properties of cured epoxy/brominated‐phenoxy blends

Morphologies of cured epoxy/brominated‐phenoxy blends were observed by scanning transmission electron microscopy (STEM) and energy dispersive X‐ray fluorescence spectroscopy (EDX). When brominated‐phenoxy content was 30 wt %, cocontinuous phase structures between cured epoxy and brominated‐phenoxy were found. Since every loss tangent (tan δ) curve as a function of temperature on dynamic mechanical analysis (DMA) showed 2 peaks at 128°C and 155°C respectively, cured epoxy phases and brominated‐phenoxy phases were incompatible together and T_gs of cured epoxy phases were not decreased. Tensile strength and tensile elongation of the cured blends were increased together. T‐peel adhesion strength and the lap‐shear adhesion strength were also increased together. These phenomena could be due to the cocontinuous structures consisted by the rigid cured epoxy phases of thermosets and ductile the brominated‐phenoxy phases of thermoplastics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1702–1713, 2007     

Hybrid resins from polyisocyanate,vinyl ester,melamine formaldehyde and water glass: structure and properties

Abstract

Hybrid thermosets were produced from polymeric methylene diphenyl isocyanate (PMDI), styrene cross-linkable vinyl ester (VE) and water glass (WG) using melamine formaldehyde (MF) resin as additional reactive emulsifier. Vinyl ester (VE) was added to the PMDI/MF mixture in which the WG was dispersed next. The content of MF in the resin formulation was varied between 0·5 and 15 wt-%. The resulting water in oil type (W/O) emulsion (water=WG, oil=organic phase composed of PMDI+VE+MF) was cured at room temperature for 24 h followed by post-curing at T=100°C for 4 h. The chemorheology of the hybrid resins was assessed by plate/plate rheometry. Information on the morphology of the cured hybrid resins was received from scanning electron microscope (SEM), atomic force microscopic (AFM) and dynamic mechanical thermal analysis (DMTA) studies. The mechanical and fracture mechanical properties as well as the resistance to thermal degradation of the hybrid thermosets were determined and discussed.     

Renewable thermoset copolymers from tung oil and natural terpenes

The cationic copolymerization of tung oil, limonene, and myrcene as comonomers, initiated by boron trifluoride, is presented and discussed in this work. Dynamic mechanical analysis revealed that all copolymers behave as thermosets. FTIR spectra for both copolymers, after extraction with dichloromethane, suggested that the major component of the insoluble fraction was reacted tung oil (a cross‐linked triglyceride network). Likewise, unreacted tung oil was found to be the main component of the soluble phase. Also, all the copolymers showed only one tan δ peak, indicating no phase separation. Glass transition temperature (Tg) increased with the myrcene content and decreased almost linearly as the limonene content increased. Furthermore, the Fox and Loshaek model showed a relatively good prediction of the Tg values of the polymers. The Young's modulus ranged from 33.8 to 4.7 MPa for all tested thermosets. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41155.     

Carboxylated Lignin as an Effective Cohardener for Enhancing Strength and Toughness of Epoxy

It is demonstrated that pristine or functionalized lignin can be used in epoxy as a cohardener or comonomer; however either unsatisfactory mechanical properties or low lignin content remains a challenge in utilizing the sustainable biomass to replace petrochemical product. In this study, carboxylic acid‐modified kraft lignin (lignin–COOH) is synthesized and used as a cohardener for epoxy with loading content of up to 10.0 wt%. With incorporation of 10.0 wt% of lignin–COOH, the resulting composite exhibits increments of 16%, 13%, 20%, and 95% on tensile modulus, flexural modulus, tensile strength, and toughness respectively, in contrast to neat epoxy. The good dispersion of lignin–COOH in epoxy, rigid aromatic structure of lignin, and the reduced crosslink density in the composite can simultaneously contribute to the high mechanical performance, which is verified by the thermal and mechanical analysis results. It suggests that lignin can be converted to effective alternative curing agents for epoxy thermosets.     

Tung oil‐based thermosetting polymers for self‐healing applications

Several bio‐renewable thermosetting polymers were successfully prepared from tung oil through cationic polymerization for the use as the healing agent in self‐healing microencapsulated applications. The tung oil triglyceride was blended with its methyl ester, which was produced by saponification followed by esterification. The changes in storage modulus, loss modulus, and glass transition temperature as functions of the methyl ester content were measured using dynamic mechanical analysis. In addition, the fraction of cross‐linked material in the polymer was calculated by Soxhlet extraction, while proton nuclear magnetic resonance, Fourier transform infrared spectroscopy and TEM were used to investigate the structure of the copolymer networks. The thermal stability of the thermosets as a function of their methyl ester blend contents was determined by thermogravimetric analysis. Finally, the adhesive properties of the thermosets were studied using compressive lap shear and the fracture surfaces were analyzed using SEM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40406.     

Effect of stoichiometric concentration of hardener and percentage styrene oxide diluent on the crosslinking and mechanical properties of an epoxy resin cured with DEAPA

Epoxy resin was cured with diethylaminopropylamine (DEAPA) in amounts ranging from 10% to 50% of stoichiometric amount. The yield strength of resulting thermosets formed by heat curing at 75°C is found to increase with decreasing amount of hardener. This is attributed to a more densely crosslinked structure resulting from increased tertiary amine-initiated epoxide–epoxide chain reaction and decreased primary and secondary amine–epoxide reaction. Infrared analysis and swelling data are also presented. Styrene oxide diluent is found to have a moderate effect on mechanical properties in the range from 10 to 25 parts per hundred (phr).     

Preparation of polysiloxane oligomers bearing benzoxazine side groups and tunable properties of their thermosets

A new pathway for the preparation of polysiloxane oligomers bearing benzoxazine side groups were reported via the hydrolysis and co‐polycondensation of benzoxazinyl siloxane (SBZ) with dimethyldiethoxysilane (DEDMS). The structures of SBZ and oligomers were characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. The average molecular weights of the obtained oligomers were estimated from size exclusion chromatography and ¹H‐NMR to be in the range of 2000–4000. The oligomers gave transparent films by casting in THF solution. The films were further thermally treated to produce crosslinked films via the ring opening polymerization of benzoxazine side group. The effects of siloxane content on polymerization behavior, glass transition temperature, and mechanical properties of the polybenzoxazine thermosets were investigated. Tensile test of the films revealed that the elongation at break increased with increasing siloxane content. The elongation at break of poly(I‐50) was up to 12.1%. Dynamic mechanical analysis of the thermosets showed that the T_gs were in the range of 119–165°C. Thermogravimetic analysis also revealed a better thermal stability as evidenced by the 5% weight loss temperatures in the range of 363–390°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40960.     

Lanthanide triflates as curing initiators for solid DGEBA resin: Thermal and mechanical characterization

A new class of cationic initiators, lanthanide triflates, has been studied in the curing of diglycidyl ether of bisphenol‐A (DGEBA). Two metal salts (Erbium and Ytterbium (III) trifluoromethanesulfonate) in various proportions (0.5, 1, and 2 parts per hundred of resin) have been used and the thermal and mechanical properties of the thermosets compared to a common solid epoxy system (crosslinked with o‐tolylbiguanide). The kinetics of these processes has been evaluated by the isoconversional method that has been proved to be an excellent tool to predict the principal curing parameters (conversion/time/temperature). Their mechanical properties have been evaluated by dynamic mechanical thermal analysis (DMTA), stress‐strain curves, impact resistances and adhesion to metallic substrates, and the thermal characteristics were measured by calorimetry (DSC) and thermogravimetry (TGA). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and investigation of flame‐retardant epoxy resin modified with a novel halogen‐free flame retardant containing phosphaphenanthrene,triazine‐trione,and organoboron units

In this article, a novel flame retardant (coded as BNP) was successfully synthesized through the addition reaction between triglycidyl isocyanurate, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and phenylboronic acid. BNP was blended with diglycidyl ether of bisphenol‐A to prepare flame‐retardant epoxy resin (EP). Thermal properties, flame retardancy, and combustion behavior of the cured EP were studied by thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the flame retardancy and smoke suppressing properties of EP/BNP thermosets were significantly enhanced. The LOI value of EP/BNP‐3 thermoset was increased to 32.5% and the sample achieved UL94 V‐0 rating. Compared with the neat EP sample, the peak of heat release rate, average of heat release rate, total heat release, and total smoke production of EP/BNP thermosets were decreased by 58.2%–66.9%, 27.1%–37.9%, 25.8%–41.8%, and 21.3%–41.7%, respectively. The char yields of EP/BNP thermosets were increased by 46.8%–88.4%. The BNP decomposed to produce free radicals with quenching effect and enhanced the charring ability of EP matrix. The multifunctional groups of BNP with flame retardant effects in both gaseous and condensed phases were responsible for the excellent flame retardancy of the EP/BNP thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45291.     

Anhydride Cured Bio‐Based Epoxy Resin: Effect of Moisture on Thermal and Mechanical Properties

This paper describes the development of a novel thermoset based on epoxidized hemp seed oil. The optimization of the hardener (anhydride) and crosslinking accelerator (2‐ethylimidazol) concentration as well as the curing parameters are discussed in detail. The optimized material exhibits a bio‐based carbon portion of 57.5 wt% and represents an innovative and sustainable substitute for fully petrochemical‐based resins in terms of thermal and mechanical performance characteristics. However, also a major challenge with regard to practical applications of (bio‐based) thermosets with anhydride curing agent thermosets is identified and addressed: the sensitivity to moisture absorption both during curing and in the fully cured state.     

Cyclopentadiene‐functionalized polyketone as self‐cross‐linking thermo‐reversible thermoset with increased softening temperature

Self‐cross‐linkable thermo‐reversible thermosets were obtained by a two‐steps post‐functionalization of aliphatic alternating polyketones yielding two different cyclopentadiene functionalization degree of 9 and 22% (with the respect of initial 1,4‐dicarbonyl units). Thermo‐reversibility was verified by gelation experiments and differential scanning calorimetry (DSC) scans displayed a broad transition varying from 75–100°C till 160°C that can be related to retro‐Diels Alder de‐bonding of the dicyclopentadienyl moieties. The dynamic mechanical thermal (DMTA) analysis showed the complete thermo‐mechanical recovery of the material up to six thermal cycles with a softening temperature around 210°C, thereby ensuring a suitable application window for high‐temperature resistant thermosets. Independently of the exact mechanism at the molecular level and in addition to previous studies which used the same Diels‐Alder diene‐dienophile system, it must be noticed that all prepared materials retained their mechanical behavior during at least six consecutive thermal cycles, thus indicating the re‐workability of the system. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42924.     

Enhancement of dielectric constants of epoxy thermosets via a fine dispersion of barium titanate nanoparticles

In this study, we examined a facile approach for achieving a fine dispersion of barium titanate (BT) nanoparticles (NPs) in epoxy thermosets. First, the surfaces of BT NPs were modified with poly(ε‐caprolactone) (PCL) via a surface‐initiated ring‐opening polymerization approach. We found that the PCL‐grafted BT NPs were easily dispersed in epoxy thermosets. The fine dispersion of the PCL‐grafted BT NPs in the epoxy thermosets was evidenced by transmission electron microscopy and dynamic mechanical thermal analysis. We found that the organic–inorganic nanocomposites displayed significantly enhanced dielectric constants and low dielectric loss compared to the control epoxy. The nanocomposites containing 14.1 wt % BT NPs possessed dielectric constants as high as at a frequency of 10³ Hz. The dielectric loss was measured to be 0.002 at a frequency of 10³ Hz. The improved dielectric properties are accounted for the fine dispersion of the BT NPs in the epoxy thermosets. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43322.     

Curing of epoxidized linseed oil: Investigation of the curing reaction with different hardener types

The effect of the hardener type and amount on the curing reaction and the resulting thermal and mechanical performance characteristics of epoxidized linseed oil are studied in detail. The analysis of the curing mechanism reveals that due to steric hindrance, side reactions and/or fast gelation, the optimal mixing ratio of bio-based epoxy resins and hardeners has to be determined experimentally and cannot be calculated. The investigated thermosets exhibit a glass transition temperature of 12, 54, and 145°C after curing. The overall mechanical performance of the resulting resin ranges from soft and flexible to stiff and rigid, depending on the hardener type applied, which can be utilized in the formation of epoxy composites and coatings.     

Polymerization reactions of epoxidized soybean oil and maleate esters of oil‐soluble resoles

In this study, the polymerization reactions of epoxidized soybean oil (ESO) with the maleate half‐esters of oil‐soluble resoles and the properties of the final products were demonstrated. The maleate half‐esters of the dimeric oil‐soluble resoles were obtained by the esterification reaction of maleic anhydride with a p‐tertiary butyl phenol (p‐TBP) resole and p‐nonyl phenol resole resins in the first step. The monomers were characterized by IR and ¹H‐NMR techniques. Then, the oil‐soluble resole maleates were polymerized with ESO to obtain tough and load‐bearing thermoset materials. The thermal and mechanical properties of the materials were determined by dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, and tensile strength testing. The tensile strengths and storage moduli of the crosslinked polymers varied between 0.17 and 13 MPa and 10 and 1088 MPa, respectively. The elongation percentages of the materials were between 1 and 128%. The thermal resistance of the thermosets was measured as the 5% weight loss temperature. The reaction product of the ESO and maleate ester of p‐TBP showed the highest 5% weight loss at 247°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41457.