Nanocomposites of Rigid Polyurethane Foam and Graphene Nanoplates Obtained by Exfoliation of Natural Graphite in Polymeric 4,4'-Diphenylmethane Diisocyanate.

The influence of graphene nanoplates (GNPs) obtained by the ecofriendly exfoliation of natural graphite has been addressed on the mechanical and thermal insulating properties of rigid polyurethane foams (RPUFs). Few-layer GNPs with few defects were prepared in polymeric 4,4'-diphenylmethane diisocyanate (pMDI) under ultrasonication to obtain a GNP/pMDI dispersion. GNP/pMDI dispersions with different GNP concentrations were used to prepare RPUF nanocomposites via in situ polymerization. An important finding is that the GNP/pMDI dispersion exhibits lyotropic liquid crystalline behavior. It was found that the unique orientation of GNPs above the concentration of 0.1 wt% in the dispersion affected the mechanical and thermal insulation properties of the RPUF nanocomposites. GNP/RPUF nanocomposites with GNP concentrations at 0.2 wt% or more showed better thermal insulating properties than neat RPUF. The lyotropic liquid crystalline ordering of GNPs provides stable nucleation for bubble formation during foaming and prevents bubble coalescence. This decreases the average cell size and increases the closed cell content, producing GNP/RPUF nanocomposites with low thermal conductivity. Furthermore, GNPs incorporated into RPUF act as a barrier to radiant heat transfer through the cells, which effectively reduces the thermal conductivity of the resulting nanocomposites. It is expected that the nanocomposite of RPUF investigated in this study can be applied practically to improve the performance of thermal insulation foams.

Rationally Designed Eugenol-Based Chain Extender for Self-Healing Polyurethane Elastomers.

Bio-based polyurethane (PU) has recently drawn our attention due to the increasing interest in sustainability and the risks involved with petroleum depletion. Herein, bio-based self-healing PU with a novel polyol, i.e., eugenol glycol dimer (EGD), was synthesized and characterized for the first time. EGD was designed to have pairs of primary, secondary, and aromatic alcohols, which all are able to be involved in urethane bond formation and to show self-healing and antioxidant effects. EGD was incorporated into a mixture of the prepolymer of polyol (tetramethylene ether glycol) and 4,4'-methylene diphenyl diisocyanate to synthesize PU. EGD-PU showed excellent self-healing properties (99.84%), and it maintained its high self-healing property (84.71%) even after three repeated tests. This dramatic self-healing was induced through transcarbamoylation by the pendant hydroxyl groups of EGD-PU. The excellent antioxidant effect of EGD-PU was confirmed by 2,2-diphenyl-1-picrylhydrazyl analysis. Eugenol-based EGD is a promising polyol chain extender that is required in the production of bio-based, self-healing, and recyclable polyurethane; therefore, EGD-PU can be applied to bio-based self-healable films or coating materials as a substitute for petroleum-based PU.

Self-Healing and Mechanical Properties of Thermoplastic Polyurethane/Eugenol-Based Phenoxy Resin Blends via Exchange Reactions.

The possibility of exchange reactions and thermal self-healing in blends of thermoplastic polyurethane (TPU) and phenoxy resin was investigated herein. The analyses were based on characterization obtained via differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), and tensile test. A new phenoxy resin was synthesized from eugenol, and blends with different types of TPU were prepared to investigate the exchange reaction, thermal self-healing, and mechanical properties. The influence of phenoxy resin content on the mechanical behavior and healing efficiency was studied. Improvement of storage modulus owing to the increase of phenoxy resin content was observed. Results suggest that the exchange reaction between phenoxy- and ester-type TPU occurred during thermal treatment. However, little exchange occurred between phenoxy resin and ether-type TPU. Specifically, only ester-type TPU exhibited a significant exchange reaction in the phenoxy resin blend. Furthermore, in the presence of a catalyst (e.g., zinc acetate), the exchange reaction readily occurred, and the healing efficiency improved by the addition of the catalyst and increase in the phenoxy content.

Characteristics of Self-Healable Copolymers of Styrene and Eugenol Terminated Polyurethane Prepolymer.

With limited biomass that can be currently utilized as a renewable resource, it is important to develop a method to convert biomass into materials that can replace fossil fuel product. In this paper, eugenol, a bio-based allyl chain-substituted guaiacol, was used to synthesize self-healable copolymers. Eugenol terminated polyurethane prepolymer (ETPU) was synthesized from eugenol and polyurethane prepolymers terminated with isocyanate groups. ETPU contained two allyl groups. Self-healing copolymer networks were obtained by copolymerization of ETPU and styrene monomer via free radical polymerization. Effects of ETPU content on the properties of copolymers were then studied. These copolymers containing ETPU exhibited good thermal stability and mechanical properties. These copolymers showed higher tensile strength and elongation at break than PS. Their maximum tensile strength reached 19 MPa. In addition, these copolymers showed self-healing property at elevated temperature due to the reversible nature of urethane units in ETPU.

Thermally Healable and Recyclable Graphene-Nanoplate/Epoxy Composites Via an In-Situ Diels-Alder Reaction on the Graphene-Nanoplate Surface.

In this work, thermally healable graphene-nanoplate/epoxy (GNP/EP) nanocomposites were investigated. GNPs were used as reinforcement and crosslinking platforms for the diglycidyl ether of bisphenol A-based epoxy resin (DGEBA) through the Diels-Alder (DA) reaction with furfurylamine (FA). The GNPs and FA could then be used as a derivative of diene and dienophile in the DA reaction. It was expected that the combination of GNPs and FA in DGEBA would produce composites based on the interfacial properties of the components. We confirmed the DA reaction of GNPs and FA at the interface during curing of the GNP/EP nanocomposites. This procedure is simple and solvent-free. DA and retro DA reactions of the obtained composites were demonstrated, and the thermal healing properties were evaluated. The behavior of the GNP/EP nanocomposites in the DA reaction is similar to that of thermosetting polymers at low temperatures due to crosslinking by the DA reaction, and the nanocomposites can be recycled by a retro DA reaction at high temperatures.

Introduction of Reversible Urethane Bonds Based on Vanillyl Alcohol for Efficient Self-Healing of Polyurethane Elastomers.

Urethane groups formed by reacting phenolic hydroxyl groups with isocyanates are known to be reversible at high temperatures. To investigate the intrinsic self-healing of polyurethane via a reversible urethane group, we synthesized vanillyl alcohol (VA)-based polyurethanes. The phenolic hydroxyl group of vanillyl alcohol allows the introduction of a reversible urethane group into the polyurethane backbone. Particularly, we investigated the effects of varying the concentration of reversible urethane groups on the self-healing of the polyurethane, and we proposed a method that improved the mobility of the molecules contributing to the self-healing process. The concentration of reversible urethane groups in the polyurethanes was controlled by varying the vanillyl alcohol content. Increasing the concentration of the reversible urethane group worsened the self-healing property by increasing hydrogen bonding and microphase separation, which consequently decreased the molecular mobility. On the other hand, after formulating a modified chain extender (m-CE), hydrogen bonding and microphase separation decreased, and the mobility (and hence the self-healing efficiency) of the molecules improved. In VA40-10 (40% VA; 10% m-CE) heated to 140 °C, the self-healing efficiency reached 96.5% after 30 min, a 139% improvement over the control polyurethane elastomer (PU). We conclude that the self-healing and mechanical properties of polyurethanes might be tailored for applications by adjusting the vanillyl alcohol content and modifying the chain extender.

Effects of Isosorbide Incorporation into Flexible Polyurethane Foams: Reversible Urethane Linkages and Antioxidant Activity.

Isosorbide (ISB), a nontoxic bio-based bicyclic diol composed from two fuzed furans, was incorporated into the preparation of flexible polyurethane foams (FPUFs) for use as a cell opener and to impart antioxidant properties to the resulting foam. A novel method for cell opening was designed based on the anticipated reversibility of the urethane linkages formed by ISB with isocyanate. FPUFs containing various amounts of ISB (up to 5 wt%) were successfully prepared without any noticeable deterioration in the appearance and physical properties of the resulting foams. The air permeability of these resulting FPUFs was increased and this could be further improved by thermal treatment at 160 °C. The urethane units based on ISB enabled cell window opening, as anticipated, through the reversible urethane linkage. The ISB-containing FPUFs also demonstrated better antioxidant activity by impeding discoloration. Thus, ISB, a nontoxic, bio-based diol, can be a valuable raw material (or additive) for eco-friendly FPUFs without seriously compromising the physical properties of these FPUFs.

Thermal Healing, Reshaping and Ecofriendly Recycling of Epoxy Resin Crosslinked with Schiff Base of Vanillin and Hexane-1,6-Diamine.

A bio-derived dihydroxylimine hardener, Van2HMDA, for the curing of epoxy resin was prepared from vanillin (Van) and hexamethylene-1,6-diamine (HMDA) by Schiff base formation. The epoxy resin of diglycidyl ether of bisphenol A was cured with Van2HMDA in the presence of the catalyst, 2-ethyl-4-methylimidazole (EMI). The crosslinked epoxy resin showed thermal-healing properties at elevated temperatures. Moreover, the crosslinked epoxy resin can be reshaped by heating via imine metathesis of the hardener units. The imine metathesis of Van2HMDA was confirmed experimentally. Stress-relaxation properties of the epoxy resin crosslinked with Van2HMDA were investigated, and the activation energy obtained from Arrhenius plots of the relaxation times was 44 kJ/mol. The imine bonds in the epoxy polymer matrix did not undergo hydrolysis after immersing in water at room temperature for one week. However, in the presence of acid, the crosslinked polymer was easily decomposed due to the hydrolysis of imine bonds. The hydrolysis of imine bonds was used for the ecofriendly recycling of crosslinked polymer. It is inferred that thermal-healing, reshaping, and reprocessing properties can be implemented in the various crosslinked epoxy resins with the bio-derived dihydroxylimine hardener, albeit the recycled epoxy resin is of inevitably lower quality than the original material.

Synthesis of Self-Healing Waterborne Polyurethane Systems Chain Extended with Chitosan.

In this study, the self-healing properties of waterborne polyurethane (WPU) were implemented by chitosan as a chain extender of polyurethane prepolymers. The physical properties and self-healing efficiency of WPU were studied by changing the molar fractions of chitosan from 0.1 to 0.3. After thermal treatment for 24 h at 110 °C, the self-healing efficiency for the tensile strength of the highest chitosan content (WPU-C3) was found to be 47%. The surface scratch was also completely restored. The efficiency of the sample with the lowest chitosan content (WPU-C1) was found to be 35%, while that of the control sample without chitosan (WPU-C0) was 4%. The self-healing properties of the as-prepared films were attributed to the exchange reactions between the hydroxyl groups of chitosan and the urethane groups in the films at elevated temperature. It is inferred that self-healing WPU can be synthesized by chain extension with chitosan.

Rheological Properties and Thermal Conductivity of Epoxy Resins Filled with a Mixture of Alumina and Boron Nitride.

Electronic packaging materials with high thermal conductivity and suitable viscosity are necessary in the manufacturing of highly integrated electronic devices for efficient heat dissipation during operation. This study looked at the effect of boron nitride (BN) platelets on the rheology and thermal conductivity of composites based on alumina (Al2O3) and epoxy resin (EP) for the potential application as electronic packaging. The viscosity and thermal conductivity of the composite were increased upon increasing filler content. Furthermore, thermal conductivity of the BN/Al2O3/EP was much higher than that of Al2O3/EP at almost the same filler loadings. These unique properties resulted from the high thermal conductivity of the BN and the synergistic effect of the spherical and plate shapes of these two fillers. The orientation of BN platelets can be controlled by adjusting their loading to facilitate the formation of higher thermally conductive pathways. The optimal content of the BN in the Al2O3/EP composites was confirmed to be 5.3 vol %, along with the maximum thermal conductivity of 4.4 W/(m·K).

Synthesis and Characterization of Healable Waterborne Polyurethanes with Cystamine Chain Extenders.

In this study, environmentally friendly, self-healing waterborne polyurethanes (WPUs) were prepared based on the disulfide metathesis reaction in cystamine. The cystamine acted as a chain extender in the WPU film, which showed a high mechanical strength of 19.1 MPa. The possibility of self-healing reaction was simultaneously modeled via liquid chromatography-mass spectrometry (LC-MS). WPU was confirmed to self-heal a surface crack thermally after a scratch test, and the efficiency was measured by comparing the mechanical properties before and after a cut-and-healing test. In addition, the disulfide-thiol exchange reaction was confirmed to occur in WPU with cystamine as a chain extender and 2-mercaptoethanol. Hot press tests confirmed the possibility of reprocessing the WPU. The WPU incorporating disulfide groups showed great potential as a smart self-healing material.

Thermally Self-Healing Graphene-Nanoplate/Polyurethane Nanocomposites via Diels⁻Alder Reaction through a One-Shot Process.

Thermally self-healing graphene-nanoplate/polyurethane (GNP/PU) nanocomposites were prepared via a bulk in-situ Diels⁻Alder (DA) reaction. Graphene-nanoplate (GNP) was used as a reinforcement and crosslinking platform by a DA reaction with a furfuryl-based chain extender of polyurethane (PU). Results showed that a DA reaction occurred in GNP during the PU forming cure process. This procedure is simple and solvent free because of the absence of any independent surface modification process. Through the calculation of the interfacial tensions, the conditions of the bulk in-situ DA reaction were determined to ensure that GNP and the furfuryl group can react with each other at the interface during the curing process without a solvent. The prepared composites were characterized in terms of thermal, mechanical, and thermally self-healing properties via the DA reaction. In the PU capable of a DA reaction (DPU), characteristic peaks of DA and retro DA reactions were observed in the Fourier transform infrared (FT-IR) spectroscopy and endothermic peaks of retro DA reactions appeared in differential scanning calorimetry (DSC) thermograms. The DPU showed significantly enhanced physical properties and chemical resistance. The thermally self-healing capability was confirmed at 110 °C via the retro DA reactions. It is inferred that thermally self-healable crosslinked GNP/PU nanocomposites via DA reactions could be prepared in a simple bulk process through the molecular design of a chain extender for the in-situ reaction at the interface.

Preparation and Characterization of Isosorbide-Based Self-Healable Polyurethane Elastomers with Thermally Reversible Bonds.

Polyurethane (PU) is a versatile polymer used in a wide range of applications. Recently, imparting PU with self-healing properties has attracted much interest to improve the product durability. The self-healing mechanism conceivably occurs through the existence of dynamic reversible bonds over a specific temperature range. The present study investigates the self-healing properties of 1,4:3,6-dianhydrohexitol-based PUs prepared from a prepolymer of poly(tetra-methylene ether glycol) and 4,4'-methylenebis(phenyl isocyanate) with different chain extenders (isosorbide or isomannide). PU with the conventional chain extender 1,4-butanediol was prepared for comparison. The urethane bonds in 1,4:3,6-dianhydrohexitol-based PUs were thermally reversible (as confirmed by the generation of isocyanate peaks observed by Fourier transform infrared spectroscopy) at mildly elevated temperatures and the PUs showed good mechanical properties. Especially the isosorbide-based polyurethane showed potential self-healing ability under mild heat treatment, as observed in reprocessing tests. It is inferred that isosorbide, bio-based bicyclic diol, can be employed as an efficient chain extender of polyurethane prepolymers to improve self-healing properties of polyurethane elastomers via reversible features of the urethane bonds.

Large Improvement in the Mechanical Properties of Polyurethane Nanocomposites Based on a Highly Concentrated Graphite Nanoplate/Polyol Masterbatch.

In this study, a highly concentrated graphite nanoplate (GNP)/polyol masterbatch was prepared by the exfoliation of natural graphite in an aqueous system using cetyltrimethylammonium bromide and the replacement of aqueous solution with a polyol, viz. poly(tetramethylene ether glycol), and it was subsequently used to prepare polyurethane (PU) nanocomposites by simple dilution. The polyol in the masterbatch efficiently prevented the aggregation of GNPs during the preparation of PU nanocomposite. In addition, the dispersed GNPs in the masterbatch exhibited rheological behavior of lyotropic liquid crystalline materials. In this study, the manufacture and application methods of the GNP/polyol masterbatch were discussed, enabling the facile manufacture of the PU/GNP nanocomposites with excellent mechanical properties. In addition, the manner in which the GNP alignment affected the microphase separation of PU in the nanocomposites was investigated, which determined the improvement in the mechanical properties of the nanocomposites. High-performance PU/GNP nanocomposites are thought to be manufactured from the GNP/polyol masterbatch by the simple dilution to 0.1 wt% GNP in the nanocomposite.

Design of Azomethine Diols for Efficient Self-Healing of Strong Polyurethane Elastomers.

Azomethine diols (AMDs) were synthesized by condensation between a terephthalic aldehyde, polyether diamine, and ethanol amine. The synthesized AMDs were employed to introduce azomethine groups into the backbones of polyurethane elastomers (PUEs). Different AMDs were designed to control the concentration and distribution of azomethine groups in PUEs. In this study, we explored the intrinsic self-healing of AMD-based PUEs by azomethine metathesis. Particularly, the effects of the concentration and distribution of the azomethine groups on the AMD-based PUEs were considered. Consequently, as the azomethine group concentration increased and the distribution became denser, the self-healing properties improved. With AMD3-40, the self-healing efficiency reached 86% at 130 °C after 30 min. This represents a 150% improvement over the control PUE. Additionally, as the AMD content increased, the mechanical properties improved. With AMD3-40, the tensile strength reached 50 MPa. Therefore, we concluded that the self-healing and mechanical properties of PUEs can potentially be tailored for applications by adjusting the concentration and design of AMD structure for PUEs.

Sorbitol as a Chain Extender of Polyurethane Prepolymers to Prepare Self-Healable and Robust Polyhydroxyurethane Elastomers.

A self-healable polyhydroxyurethane (S-PU) was synthesized from sorbitol, a biomass of polyhydric alcohol, by a simple process that is suitable for practical applications. In the synthesis, only two primary hydroxyl groups of sorbitol were considered for the chain extension of the polyurethane (PU) prepolymers to introduce free hydroxyl groups in PU. As a control, conventional PU was synthesized by hexane diol mediated chain extension. Relative to the control, S-PU showed excellent intrinsic self-healing property via exchange reaction, which was facilitated by the nucleophilic addition of the secondary hydroxyl groups without any catalytic assistance and improved tensile strength due to the enhanced hydrogen bonding. We also investigated the effect of the exchange reaction on the topological, mechanical, and rheological properties of S-PU. The suggested synthetic framework for S-PU is a promising alternative to the conventional poly hydroxyurethane, in which cyclic carbonates are frequently reacted with amines. As such, it is a facile and environmentally friendly material for use in coatings, adhesives, and elastomers.

Controllable Surface and Optical Properties of Methacrylic Copolymer Films Using Various Monomer Combinations.

Various fluorinated methacrylic copolymers (PFPMA- X) were prepared from 2,2,3,3,3-pentafluoropropyl methacrylate (PFPMA), methyl methacrylate (MMA), and three other nonfluorinated monomers. The surface and the optical properties of these copolymers were controlled by changing the ratio of PFPMA to MMA while keeping the sum of the concentration of the two monomers fixed at 60 wt %. The parameter X represents the nominal concentration of PFPMA in various feed ratios of all five monomers. Depending on the increase in PFPMA content in PFPMA- X, the surface energy varied proportionately between 26.7 (PFPMA content: 20 wt %) and 17.4 mN/m (PFPMA content: 60 wt %), which is well-correlated with the fluorine content on the surface. Interestingly, we found that all PFPMA- X-coated glasses showed different transmittance curves in the wavelength range of 300-700 nm, and the wavelength at which maximum transmittance was recorded shifted as a function of the copolymer composition. In addition, the surface coatings of PFPMA- X with higher fluorine contents increased the transmittance of bare glass by approximately 1-2%. Quite lower and tunable refractive indices were obtained depending on the fluorine content, and all PFPMA- X showed extremely lower birefringences. Freestanding films of PFPMA- X were also well-formed, indicating that they can be used in a wide range of applications.

The Effects of in Situ-Formed Silver Nanoparticles on the Electrical Properties of Epoxy Resin Filled with Silver Nanowires.

A novel method for preparing epoxy/silver nanocomposites was developed via the in situ formation of silver nanoparticles (AgNPs) within the epoxy resin matrix while using silver nanowires (AgNWs) as a conductive filler. The silver⁻imidazole complex was synthesized from silver acetate (AgAc) and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole (imidazole). AgNPs were generated in situ during the curing of the epoxy resin through the thermal decomposition of the AgAc⁻imidazole complex, which was capable of reducing Ag⁺ to Ag by itself. The released imidazole acted as a catalyst to cure the epoxy. Additionally, after the curing process, the in situ-generated AgNPs were stabilized by the formed epoxy network. Therefore, by using the thermal decomposition method, uniformly dispersed AgNPs of approximately 100 nm were formed in situ in the epoxy matrix filled with AgNWs. It was observed that the nanocomposites containing in situ-formed AgNPs exhibited isotropic electrical properties in the epoxy resins in the presence of AgNWs.

Thermal, Mechanical, and Electrical Properties of Graphene Nanoplatelet/Graphene Oxide/ Polyurethane Hybrid Nanocomposite.

Hybrid nanocomposites of polyurethane (PU) were prepared by in-situ polymerization of 4,4'- diphenyl methane diisocyanate (MDI) with mixture of graphene oxide (GO) and graphene nanoplatelet (GNP) dispersed in a poly(tetramethylene ether glycol) (PTMEG). Effects of the fillers, GO and GNP, on the thermal, mechanical, and electrical properties of the nanocomposites of PU were investigated. Sonication of the hybrid of GNP and GO with PTMEG enabled effective dispersion of the fillers in the solution than the sonication of GNP alone. The addition of PTMEG in the solution prevented the GNPs from the restacking during the drying process. It was observed that the electrical conductivity and mechanical property of the nanocomposites based on the hybrid of GO and GNP were superior to the nanocomposite based on GNP alone at the same loading of the filler. At the loading of the 3 wt% hybrid filler in PU, we observed the improvement of Young's modulus -200% and the surface resistivity of 10(9.5) ohm/sq without sacrificing the elongation at break.

Thermal and mechanical properties of reduced graphene oxide/polyurethane nanocomposite.

Reduced graphene oxide (RGO) based polyurethane (PU) nanocomposites have been successfully prepared without using solvent by in-situ polymerization. RGO was derived from microwave (MW) irradiation of graphite oxide (GO) powder prepared by a modified Hummer's method. A minimum amount of poly(tetramethylene glycol) (PTMEG) was added during the dispersion of RGO in a solvent to stabilize the graphene sheets and to prevent RGO from the restacking after the removal of the solvent. After the reaction of RGO with 4,4'-diphenylmethane diisocyanate (MDI), we obtained the concentrate of RGO in MDI with a minimum amount of PTMEG. Our method facilitated the fine dispersion of RGO in PU elastomers and improved the interfacial strength between RGO and PU. With the incorporation of 2.0 wt% of RGO, the tensile strength and Young's modulus of the PU nanocomposites increased by 30% and 50%, respectively without sacrificing the elongation at break. It was found that the crystalline portion of hard segments of the PU was lowered by the RGO in the nanocomposites.