Nanostructured Thermosets Research Articles

Nanocomposites of epoxy with one-dimensional fibrous poly(ε-caprolactam) nanocrystals via crystallization-driven self-assembly

In this contribution, we reported the preparation of nanocomposites of epoxy with one-dimensional (1D) poly(ε-caprolactam) (PA6) nanocrystals via crystallization-driven self-assembly. First, a novel diblock copolymer composed of poly(ethylene oxide) and poly(ε-caprolactam) subchains (PEO-b-PA6) was synthesized via the anionic ring-opening polymerization (ROP) of ε-caprolactam. It was found that the PEO-b-PA6 diblocks displayed crystallization-driven self-assembly (CDSA) behavior in the selective solvents (e.g., water); the 1D fibrous nanocrystals of PA6 were obtained via CDSA approach. Such a CDSA behavior was utilized to generate 1D fibrous PA6 nanocrystals into epoxy thermosets. In this case, the epoxy precursors were used as the solvent selective for PEO subchain of the diblock. Notably, the 1D fibrous PA6 nanocrystals were generated in the epoxy precursors via the CDSA approach. Upon curing, the nanocomposites (i.e., the nanostructured thermosets containing PA6 nanocrystals) were successfully obtained. It was found that epoxy thermoset was significantly nanoreinforced by the PA6 nanocrystals. In the meantime, the fracture toughness of the materials was significantly improved with the incorporation of 1D fibrous PA6 nanocrystals.

Generation of One-Dimensional Fibrous Polyethylene Nanocrystals in Epoxy Thermosets.

The one-dimensional (1D) polyethylene (PE) nanocrystals were generated in epoxy thermosets via crystallization-driven self-assembly. Toward this end, an ABA triblock copolymer composed of PE midblock and poly(ε-caprolactone) (PCL) endblocks was synthesized via the ring opening metathesis polymerization followed by hydrogenation approach. The nanostructured thermosets were obtained via a two-step curing approach, i.e., the samples were cured first at 80 °C and then at 150 °C. Under this condition, the one-dimensional (1D) fibrous PE microdomains with the lengths up to a couple of micrometers were created in epoxy thermosets. In contrast, only the spherical PE microdomains were generated while the thermosets were cured via a one-step curing at 150 °C. By the use of the triblock copolymer, the generation of 1D fibrous PE nanocrystals is attributable to crystallization-driven self-assembly mechanism whereas that of the spherical PE microdomains follows traditional self-assembly mechanism. Compared to the thermosets containing the spherical PE microdomains, the thermosets containing the 1D fibrous PE nanocrystals displayed quite different thermal and mechanical properties. More importantly, the nanostructured thermosets containing the 1D fibrous PE nanocrystals displayed the fracture toughness much higher than those only containing the spherical PE nanocrystals; the KIC value was even three times as that of control epoxy.

Incorporation of crosslinked polydicyclopentadiene nanoparticles into epoxy thermosets via ring opening metathesis polymerization-induced self-assembly

In this contribution, we reported the generation of crosslinked polydicyclopentadiene nanoparticles in epoxy thermosets via polymerization-driven self-assembly approach. First, poly(ε-caprolactone)s (PCLs) with single cis -2-butene moieties in the main chains were synthesized, which were then employed as the macromolecular chain transfer agents (Macro-CTAs) for the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD). The ROMPs were carried out with the precursors of epoxy ( i.e., trimethylolpropane triglycidyl ether + 4,4′-methylenebis(2-chloroaniline)) as the medium of dispersion. At a lower temperature ( e.g. , 60 °C), the ROMPs were undergone completion and then the systems were heated to elevated temperature to start the curing reaction. It was found that the nanostructures were created in the cured thermosets, in which the crosslinked PDCPD nanoparticles were well dispersed in the thermosetting matrix. The crosslinked PDCPD nanoparticles displayed spherical, cylindrical and lamellar morphologies, influenced by the contents of modifier ( viz. DCPD + Macro-CTA) and the molecular weights of Macro-CTAs. Both dynamic light scattering and transmission electron microscopy showed that the generation of nanostructures followed a typical polymerization-induced self-assembly mechanism. Compared to plain epoxy, the nanostructured thermosets significantly displayed improved fracture toughness. The fracture toughness was readily modulated by controlling the contents of DCPD and the molecular weights of Macro-CTAs. • ROMP-induced self-assembly was performed with epoxy precursors as dispersion medium. • Crosslinked polydicyclopentadiene nanoparticles were generated in epoxy thermosets. • The nanostructured epoxy thermosets displayed improved fracture toughness.

Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture

AbstractNanostructured polymeric materials play important roles in many advanced applications, however, controlling the morphologies of polymeric thermosets remains a challenge. This work uses multi‐arm macroCTAs to mediate polymerization‐induced microphase separation (PIMS) and prepare nanostructured materials via photoinduced 3D printing. The characteristic length scale of microphase‐separated domains is determined by the macroCTA arm length, while nanoscale morphologies are controlled by the macroCTA architecture. Specifically, using 2‐ and 4‐ arm macroCTAs provides materials with different morphologies compared to analogous monofunctional linear macroCTAs at similar compositions. The mechanical properties of these nanostructured thermosets can also be tuned while maintaining the desired morphologies. Using multi‐arm macroCTAs can thus broaden the scope of accessible nanostructures for extended applications, including the fabrication of actuators and potential drug delivery devices.

Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture.

Nanostructured polymeric materials play important roles in many advanced applications, however, controlling the morphologies of polymeric thermosets remains a challenge. This work uses multi‐arm macroCTAs to mediate polymerization‐induced microphase separation (PIMS) and prepare nanostructured materials via photoinduced 3D printing. The characteristic length scale of microphase‐separated domains is determined by the macroCTA arm length, while nanoscale morphologies are controlled by the macroCTA architecture. Specifically, using 2‐ and 4‐ arm macroCTAs provides materials with different morphologies compared to analogous monofunctional linear macroCTAs at similar compositions. The mechanical properties of these nanostructured thermosets can also be tuned while maintaining the desired morphologies. Using multi‐arm macroCTAs can thus broaden the scope of accessible nanostructures for extended applications, including the fabrication of actuators and potential drug delivery devices.

Polyhydroxyurethane thermosets from novolac epoxide: Synthesis and its nanostructured blends with poly(trifluoroethylacrylate)-block-poly(N-vinylpyrrolidone) diblock copolymer

A novel five-membered cyclic carbonate compound was synthesized via the reaction of novolac epoxide with carbon dioxide. The cyclic carbonate was then used as the precursor to prepare polyhydroxyurethane (PHU) thermosets with a trifunctional polyetheramine (i.e., Jeffamine T 403) as the crosslinking agent. To improve the thermomechanical properties as well as hydrophobicity, the PHU thermosets were further nanostructured by the use of a poly(trifluoroethyl acrylate)-block-poly(N-vinylpyrrolidinone) (PTFEA-b-PVPy) diblock copolymer. Compared to plain PHU thermoset, the nanostructured thermosets displayed enhanced glass transition temperatures (Tg's) and mechanical properties. Meanwhile, the surface hydrophobicity was significantly improved; the water surface contact angles of the thermosets have been increased up to 94.6°. With the introduction of PTFEA-b-PVPy, the nanostructured PHU thermosets still preserved the excellent shape memory and reprocessability at elevated temperature.

Nanostructured thermosets involving epoxy and poly(ionic liquid)-Containing diblock copolymer

A novel poly(ionic liquid) (PIL)-containing diblock copolymer was synthesized via a sequential living/controlled polymerization approach. First, the ring-opening polymerization of ε-caprolactone (CL) was carried out to obtain a monohydroxyl-terminated PCL. The terminal hydroxyl group of the PCL chain was then exploited to react with carboxyl group of 2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid to obtain a trithiocarbonate-terminated PCL. Thereafter, such trithiocarbonate-terminated PCL was used to mediate the radical polymerization of tri-n-butyl-(4-vinylbenzyl) phosphoniumbis(trifluoromethane)sulfonamide (TBP+-TFSI-) to afford PIL diblock copolymers. Notably, the PIL diblock copolymers are capable of displaying self-assembly behavior in selective solvent (e.g., ethyl acetate). In the suspensions of ethyl acetate, the self-assembly generated the spherical micelles with the aggregates of P(TBP+-TFSI-) as the cores and with PCL blocks as the coronas. Such a self-assembly behavior was further employed to obtain epoxy thermoset with nanostructures. Owing to the introduction of fluorine-containing PIL diblock copolymer, the surface dewettability of the thermosets was significantly improved owing to the enrichment of P(TBP+-TFSI-) at the surface. The introduction of PIL microdomains in epoxy resulted that the dielectric constants of the materials were significantly enhanced. More importantly, the dielectric constants were temperature-dependent and can be further enhanced while the nanostructured thermosets were heated above the glass transition temperature of PIL blocks.

Investigation of Azobenzene Photoisomerization Effect on Morphologies and Properties of Nanostructured Thermosets Involving Epoxy and a Diblock Copolymer.

This work highlights the effect of azobenzene photoisomerization on the morphologies and properties of the nanostructured thermosets involving epoxy and a diblock copolymer. First, a diblock copolymer composed of poly(ethylene oxide) (PEO) and poly(6-(4-(4-cyanophenylazo)phenoxy)hexyl methacrylate) (PCPHM) was synthesized, and this diblock copolymer was composed of an epoxy-philic block (i.e., PEO) and an azobenzene moiety-beating block (viz., PCPHM). This diblock copolymer was introduced into epoxy to obtain the nanostructured thermosets via reaction-induced microphase separation approach. To control the configuration of azobenzene moieties of the PCPHM block, the curing reactions were performed in the absence and/or presence of ultraviolet (UV) irradiation, respectively. It was found that, without UV irradiation, the PCPHM microdomains were generated with the trans isomers of azobenzene. Under UV irradiation, however, the PCPHM microdomains were formed with the cis configuration of azobenzene moieties. The ultraviolet-visible light (UV-vis) spectroscopy showed that the trans and cis configurations of azobenzene moieties were significantly fixed with the occurrence of curing reactions. The photoluminescent measurements showed that the nanostructured thermosets with trans-azobenzene moieties can emit fluorescence, which was in sharp contrast to those with cis-azobenzene moieties. The results of small-angle X-ray and atomic force microscopy showed that the nanostructured thermosets with trans and cis isomers of azobenzene moieties had quite different morphologies. It was found that the sizes of the PCPHM microdomains with cis configuration of azobenzene moieties were significantly larger than those with trans configuration. The difference in configuration of azobenzene moieties also resulted in the difference in glass-transition temperatures and dielectric properties of the materials. The results suggest a new approach to modulate the morphologies and physical properties of the nanostructured thermosets by means of photoisomerization of azobenzene moieties.

Toughening of epoxy thermosets with polystyrene‐block‐polybutadiene‐block‐ polystyrene triblock copolymer via formation of nanostructures

In this contribution, we reported to utilize polystyrene‐block‐polybutadiene‐block‐polystyrene (PS‐b‐PB‐b‐PS), a commercial triblock copolymer to toughen epoxy thermosets. First, a PS‐b‐PB‐b‐PS triblock copolymer was chemically modified with hydroboration‐oxidation reaction, with which the midblock was hydroxylated whereas the endblocks remained unaffected. It was found that the degree of hydroxylation was well controlled. One of the hydroxylated PS‐b‐PB‐b‐PS samples was then used as the macromolecular initiator to synthesize a poly(ε‐caprolactone)‐grafted PS‐b‐PB‐b‐PS via the ring‐opening polymerization. It was found that the PS‐b‐PB‐b‐PS with poly(ε‐caprolactone) grafts can be successfully employed to nanostructure epoxy thermosets; the “core‐shell” microdomains composed of PB and PS were generated in the nanostructured thermosets. The nanostructured thermosets displayed improved fracture toughness. POLYM. ENG. SCI., 59:2387–2396, 2019. © 2019 Society of Plastics Engineers

Fluorescence Enhancement Induced by Curing Reaction in Nanostructured Epoxy Thermosets Containing a Diblock Copolymer.

In this work, a novel curing-induced fluorescence (FL) enhancement phenomenon in the nanostructuring process of epoxy thermosets was investigated. Toward this end, a diblock copolymer composed of poly(ethylene oxide) and poly(((4-vinylphenyl)ethene-1,1,2-triyl)tribenzene) (PTPEE) blocks was introduced into epoxy thermosets. Before curing reaction, the mixtures of epoxy precursors with the diblock copolymer only emitted feeble FL under ultra-visible (UV) irradiation. However, photoluminescence was significantly enhanced after the curing reaction was carried out. It was found that the novel FL enhancement phenomenon resulted from the aggregation-induced emission behavior of PTPEE blocks, which was triggered by curing reaction. In the nanostructured thermosets, the fluorophore blocks (viz. PTPEE) of this diblock copolymer were segregated into aggregates, that is, a reaction-induced microphase separation occurred. Owing to the generation of PTPEE microdomains, the epoxy nanocomposites significantly displayed the enhanced dielectric constants due to the promoted contribution from electron polarizations via π-π conjugation in the materials.

The effect of reaction-induced micro-phase separation of block copolymer on curing kinetics of epoxy thermosets

The curing kinetics of epoxy system modified with Poly(e-caprolactone)-block-Polystyrene (PCL-b-PS) diblock copolymer was investigated by differential scanning calorimetry(DSC). PCL-b-PS was synthesized Via the combination of ROP and ATRP, then incorporated into epoxy to access the nanostructured thermosets. The results of TEM, SAXS and DSC demonstrated the occurrence of Reaction-induced Micro-phase Separation. Kinetic studies showed that the PCL-b-PS block copolymer delayed the curing reactions of epoxy system. The occurrence of Reaction-induced Micro-phase Separation had no significant effect on the total heat of reaction ∆H and the total activation energy, but resulted in a higher activation energy at the beginning of curing. The increase in activation energy at the initial stage of curing was related to the size and distribution of the dispersed phase. It is expected that the investigation of cure kinetics of EP/PCL-b-PS could provide more theoretical basis for the preparation of block copolymer modified epoxy resin.

Morphologies and dielectric properties of epoxy thermosets containing poly(N-vinylcarbazole), fullerene-C60 and their charge transfer complex nanophases

Both poly(ethylene oxide)-block-poly(N-vinylcarbazole) (PEO-b-PVK) diblock copolymer and fullerene-capped poly(ethylene oxide) (PEO-C60) were synthesized in this work. The former was obtained via reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate process whereas the latter via click reaction of azido-capped poly(ethylene oxide) with fullerene-C60. Both of the amphiphiles were incorporated into epoxy to obtain the nanostructured thermosets. It was found that the PVK-C60 charge transfer complexes were formed in the ternary thermosetting blends of epoxy, PEO-b-PVK and PEO-C60. The nanostructured epoxy thermosets containing PVK or/and fullerene displayed the enhanced dielectric constants whereas the dielectric loss remained almost unchanged. Nonetheless, the dielectric constants were significantly decreased while both PEO-b-PVK and PEO-C60 were simultaneously incorporated into the thermosets. The depression in dielectric constant is attributable to the formation of the charge transfer complexes of PVK with fullerene-C60. It was found that the dielectric constants can be modulated with the contents of the PVK-C60 charge transfer complexes.

Epoxy toughening via formation of polyisoprene nanophases with amphiphilic diblock copolymer

In this contribution, we reported the investigation of epoxy toughening via the formation of nanostructures by the use of poly(ε-caprolactone)-block-polyisoprene (PCL-b-PI) diblock copolymer. The novel diblock copolymer was synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerizations. This diblock copolymer can be used to access the nanostructures of epoxy thermosets. Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) showed that the nanostructured thermosets were successfully obtained. In the nanostructured thermosets, the spherical or vesicular polyisoprene microdomains were dispersed in continuous epoxy matrix. It is the formation of the PI nanophases that endowed the thermosets with significantly improved fracture toughness.

Tuning Mesoporosity in Cross-Linked Nanostructured Thermosets via Polymerization-Induced Microphase Separation

Using the synthetic approach of polymerization-induced microphase separation (PIMS), we prepared cocontinuous and cross-linked nanostructured monoliths from bulk polymerizations of styrene and divinylbenzene (DVB) in the presence of polylactide macro-chain-transfer agents (PLA-CTAs). The resulting monolithic precursors were converted to cross-linked mesoporous materials following hydrolytic degradation of the PLA domain, the morphology and porosity of which were characterized through a combination of small-angle X-ray scattering, scanning electron microscopy, and nitrogen sorption experiments. This report highlights the concept, functionality, and limitations of PIMS for the generation of mesoporous materials through variation of reaction parameters found to strongly influence the porous properties of the matrix: the cross-linker-to-monomer ratio, reaction temperature, molar mass and mass fraction of PLA-CTA, and the reactivity of the DVB isomer. Increases in the cross-linker-to-monomer ratio (≥40 mol % D...

Mesoporous Carbons from Nanostructured Phenolic Thermosets Containing Poly(styrene-alt-maleic anhydride)-block-polystyrene Diblock Copolymer

The nanostructured phenolic thermosets were prepared from the ternary mixtures composed of novolac resin, poly(styrene-alt-maleic anhydride)-block-polystyrene [P(S-alt-MAH)-b-PS] diblock copolymer, and hexamethylenetetramine, which were cured at elevated temperature. The P(S-alt-MAH)-b-PS diblock copolymer was synthesized via a one-pot RAFT polymerization approach. The morphologies of the nanostructured thermosets were modulated by changing the content of the diblock copolymer. The as-obtained nanostructured phenolic thermosets were further used as the precursors to obtain the mesoporous carbons via pyrolysis under highly pure nitrogen atmosphere. The mesoporous carbons were successfully obtained with adjustable porosity. The mesoporous carbons had specific surface areas of 398.9–491.4 m2 g–1 and pore volumes of 0.22–0.31 cm3 g–1.

Photophysical and dielectric properties of nanostructured epoxy thermosets containing poly(N-vinylcarbazole) nanophases

In this contribution, we reported the preparation of the nanostructured epoxy thermosets containing poly(N-vinylcarbazole) (PVK) microdomains. Toward this end, we first synthesized poly(N-vinylpyrrolidone)-block-poly(N-vinylcarbazole)-block-poly(N-vinyl pyrrolidone) (PVPy-b-PVK-b-PVPy) triblock copolymer via sequential reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; then this triblock copolymer was incorporated into epoxy to obtain the nanostructured thermosets. It was found that reaction-induced microphase separation occurred in the mixtures of this triblock copolymer with epoxy. The formation of the PVK microdomains in epoxy thermosets were investigated by means of transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). Owing to the creation of PVK nanophases, the nanostructured epoxy thermosets became light-emissive under ultraviolet irradiation. The photoluminescent behavior is attributable to the formation of the excimers within the PVK microdomains. Compared to control epoxy, the nanostructured thermosets significantly displayed the enhanced dielectric constants due to the formation of PVK nanophases. The enhanced dielectric constants resulted from the dominant contribution of electron polarization and interfacial polarization with the formation of PVK nanophases.

Micron and nanostructured rubber toughened epoxy: A direct comparison of mechanical, thermomechanical and fracture properties

Phase separating rubbers are a well-documented toughening additive to epoxies. However, their effectiveness begins to plateau as the loading approaches 10 phr. To better understand this phenomenon, we directly compared the mechanical, thermomechanical, fracture properties and toughening mechanisms of the diglycidyl ether of bisphenol-A (DGEBA)/m-phenylenediamine (mPDA) system (Tg = 154 °C) toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN) and the triblock copolymer poly(styrene)-block-poly(butadiene)-block-poly(methylmethacrylate) (SBM), respectively. The SBM formed a nanostructured thermoset and thus was a more efficient toughening agent than CTBN, which forms micron scale, rubbery inclusions in the epoxy. At 10 phr SBM, the fracture toughness (MPa*m1/2) was increased by 220%, while the 10 phr CTBN modified epoxy containing 18 and 26% acrylonitrile showed 60 and 80% increases, respectively. Unlike the CTBN modified epoxy, SBM increased the fracture toughness with increasing concentration. Fracture surface analysis of the SBM modified epoxy via scanning electron microscopy identified the toughening mechanism as cavitation of ∼100 nm spherical micelles, void growth of the epoxy and concomitant matrix shear yielding. While both the CTBN and SBM modified epoxy exhibit similar toughening mechanisms, the nanoscopic SBM particles had an interparticle distance one order of magnitude smaller than that of the CTBN modified epoxy. Thus, a finer dispersion of nanoscopic, spherical micelles resulted in massive plastic deformation of the epoxy upon activation of cavitation, void growth and matrix shear yielding toughening mechanisms. Finally, dynamic mechanical analysis indicated that SBM did not decrease epoxy Tg, while the Tg of CTBN modified epoxy decreased with both increasing concentration and acrylonitrile content.

Nanostructured Epoxy Thermosets Containing Poly(vinylidene fluoride): Preparation, Morphologies, and Dielectric Properties

The nanostructured thermosets involving epoxy and poly(methyl methacrylate)-grafted poly(vinylidene fluoride-co-trifluoroethylene) copolymer (P(VDF-TrFE)-g-PMMA) were successfully prepared in this work. The P(VDF-TrFE)-g-PMMA graft copolymer was synthesized via the atom transfer radical polymerization of methyl methacrylate (MMA) with poly(vinylidene fluoride-co-chlorotrifluoroethylene) copolymer as the macromolecular initiator. It was characterized by means of proton nuclear magnetic resonance spectroscopy, gel permeation chromatography, differential scanning calorimetry, and dynamic laser scattering. Owing to the amphiphilicity, this graft copolymer can be readily incorporated into epoxy to obtain the nanostructured thermosets. Transmission electron microscopy showed that the spherical nanophases with a size of 10–100 nm in diameter were dispersed into the continuous epoxy matrix, depending on the content of P(VDF-TrFE)-g-PMMA. The measurement of dielectric properties showed that the modified epoxy thermosets displayed enhanced dielectric constants and quite low dielectric loss. The surface contact angle measurements showed that the surface hydrophobicity of the nanostructured thermosets was higher than the plain epoxy thermoset.

Novel Approach to Trigger Nanostructures in Thermosets Using Competitive Hydrogen-Bonding-Induced Phase Separation (CHIPS)

A new route to prepare nanostructured thermosets by the utilization of intermolecular hydrogen-bonding interactions is demonstrated here. In this study, competitive hydrogen-bonding-induced microphase separation (CHIPS) in epoxy resin (ER) containing an amphiphilic block copolymer poly(e-caprolactone)-block-poly(2-vinylpyridine) (PCL-b-P2VP) is investigated for the first time. The phase separation takes place due to the disparity in the hydrogen-bonding interactions in ER/P2VP and ER/PCL pairs leading to the formation of ordered nanostructures in the ER/block copolymer blends. SAXS and TEM results indicate that the hexagonally packed cylindrical morphology of neat PCL-b-P2VP block copolymer remains but becomes a core–shell structure at 10 wt % addition of ER, and changes to regular lamellae structures at 20–50 wt % then to disordered lamellae with 60 wt % ER. Wormlike structures are obtained in the blends with 70 wt % ER, followed by a completely homogeneous phase of ER/P2VP and ER/PCL. The formation of n...

Hyperbranched block copolymer from AB2 macromonomer: Synthesis and its reaction‐induced microphase separation in epoxy thermosets

ABSTRACTIn this contribution, we reported the synthesis of a hyperbranched block copolymer composed of poly(ε‐caprolactone) (PCL) and polystyrene (PS) subchains. Toward this end, we first synthesized an α‐alkynyl‐ and ω,ω′‐diazido‐terminated PCL‐b‐(PS)2 macromonomer via the combination of ring‐opening polymerization and atom transfer radical polymerization. By the use of this AB2 macromonomer, the hyperbranched block copolymer (h‐[PCL‐b‐(PS)2]) was synthesized via a copper‐catalyzed Huisgen 1,3‐dipolar cycloaddition (i.e., click reaction) polymerization. The hyperbranched block copolymer was characterized by means of 1H nuclear magnetic resonance spectroscopy and gel permeation chromatography. Both differential scanning calorimetry and atomic force microscopy showed that the hyperbranched block copolymer was microphase‐separated in bulk. While this hyperbranched block copolymer was incorporated into epoxy, the nanostructured thermosets were successfully obtained; the formation of the nanophases in epoxy followed reaction‐induced microphase separation mechanism as evidenced by atomic force microscopy, small angle X‐ray scattering, and dynamic mechanical thermal analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 368–380