Epoxy-amine Reaction Research Articles

Designing a New Class of Mechanophoric Polymer Based on Epoxy-Functionalized Rhodamine Derivative.

Mechanophoric polymers are an interesting class of smart polymers which contains a special force-sensitive molecular motif that can lead to a chemical change within the polymer network in response to mechanical force. This investigation reports the design of a mechanophoric polymer based on epoxy-functionalized rhodamine via a monomeric approach. In this case, rhodamine (Rh) is modified with glycidyl methacrylate (GMA) through an epoxy-amine reaction to design a vinyl-functionalized multi-armed macromonomer (Rh-GMA), which is reacted with butyl acrylate (BA) to prepare the crosslinked polymeric film. The crosslinked polymeric film demonstrates mechanophoric properties under UV and stretching conditions.

Eugenol-based dual-cured materials with multiple dynamic exchangeable bonds

In the present work, the preparation of sustainable thermosets has been approached simultaneously from three different points of view: a) the use of bio-based monomers chemically modified through green methodologies, b) the adoption of dual curing through click-type reactions to implement more efficient manufacturing processes, and c) inclusion of interchangeable groups in the network, to enable the reuse and recycling of the material at the end of its useful life and avoid waste generation.The first goal has been approached by synthesizing in a greener way an acrylate-epoxy derivative of eugenol (AEEU) and a glycerol triacrylate (GTA), both biobased resources. Then, the second approach was addressed by using biobased cystamine as a crosslinker to obtain materials through a dual-curing procedure based on a first “click” aza-Michael reaction and a second “click” epoxy-amine reaction. Intermediate and final materials could be prepared with different tailorable properties by controlling the molar ratio of the AEEU and GTA. By using DSC and rheology, we could evaluate the sequentiality and the gelation of the curing process. Finally, the covalent adaptable networks (CANs) prepared contained three different types of dynamic bonds (disulfide, esters, and β-aminoesters) and their thermomechanical properties were tested by DMA revealing Tgs above room temperature from 47 to 70 °C. Bending tests at break were performed to evaluate the mechanical properties reaching values up to 90 MPa of stress at break and 7 % of deformation. Stress relaxation tests showed that all materials could relax the stress at relatively low temperatures (120 °C) in less than 21 min. The associative and dissociative behavior of these materials was investigated through rheology revealing a clear drop of the modulus at high temperatures and frequencies when cystamine was used as a crosslinker. Moreover, their reprocessability was tested obtaining homogeneous samples with no significant changes in their chemical and thermal properties highlighting the great potential and wide range of possibilities in many different fields of these CANs.

A rational strategy for directly synthesizing strongly yellow solid-state fluorescent-emitting carbon nanodots composite microparticles by structure regulation

Carbon nanodots (CDs) have received huge attention of researchers due to their good optical properties. However, CDs generally suffer from severely fluorescence self-quenching once they are aggregated or in solid state, limitating their applications in light-emitting devices. In this work, we report a rational strategy for synthesis of yellow fluorescent carbon nanodots (Y-CDs)-based microparticles with a high solid-state photoluminescence quantum yield (32.02%). It is the first report on designing a lamellar structured matrix to disperse CDs to realize long-wavelength solid fluorescence. The matrix is confirmed as p-phenylenediamine dihydrochloride by X-ray diffraction (XRD). 3-glycidyloxypropyltrimethoxysilane (KH-560) acts as a bridge to connect CDs to the matrix based on epoxy-amine reaction and silane hydrolysis condensation for uniform dispersion of CDs and high solid-state luminescence can be easily achieved. Meanwhile, through adjusting the amount of KH-560, the morphology of Y-CDs-based microparticles can be controlled from cube to layered structure and the fluorescence intensity can be significantly improved. Importantly, the optimal Y-CDs particles can be combined with blue chips (450 nm) to fabricate high-performance white light-emitting diodes (WLEDs) without using commercial phosphor, and the constructed WLEDs exhibit a high color rendering index (CRI) of 84.2.

Synthesis of Cyano-Containing Epoxy Precursor from Vanillin for Engineering Multifaceted Performance-Enhancing Resins

Interest in producing chemicals and thermosets from sustainable resources is growing, yet their moderate performance drastically undermines their potential applicability. Herein, an aryl dinitrile epoxy precursor (DVN-EP) was developed from vanillin. After curing with 4,4′-diaminodiphenyl sulfone (DDS), cyano-containing resin (DVN-EP/DDS) was produced with eminent comprehensive properties on account of the dual-cross-linked network formed by the epoxy-amine reaction and the further cyclotrimerization of cyano groups. In particular, the glass transition temperature, storage modulus, char yield (at 800 °C in N2), and Young’s modulus of the DVN-EP/DDS were 201 °C, 2795 MPa, 47.4%, and 5034 MPa, respectively, all much higher than those of the cyano-free counterpart (DMG-EP/DDS). Moreover, the cyano dipole–dipole pairings combined with the H-bonding interactions contributed to a tremendously increased lap shear strength of up to 7.18 MPa as well as good energy dissipation and damping capacity. The rationally designed dual-cross-linked network strengthening mechanism reported here offers an important and universal strategy for significantly enhancing the comprehensive properties of thermosets.

Nitrogen-Rich Porous Organic Polymers from an Irreversible Amine-Epoxy Reaction for Pd Nanocatalyst Carrier.

Nitrogen-rich porous organic polymers were fabricated through a nonreversible ring-opening reaction from polyamines and polyepoxides (PAEs). The epoxide groups reacted with both primary and secondary amines provided by the polyamines at different epoxide/amine ratios with polyethylene glycol as the solvent to form the porous materials. Fourier-transform infrared spectroscopy confirmed the occurrence of ring opening between the polyamines and polyepoxides. The porous structure of the materials was confirmed through N2 adsorption-desorption data and scanning electron microscopy images. The polymers were found to possess both crystalline and noncrystalline structures, as evidenced by X-ray diffraction and high-resolution transmission electron microscopy (HR-TEM) results. The HR-TEM images revealed a thin, sheet-like layered structure with ordered orientations, and the lattice fringe spacing measured from these images was consistent with the interlayer of the PAEs. Additionally, the selected area electron diffraction pattern indicated that the PAEs contained a hexagonal crystal structure. The Pd catalyst was fabricated in situ onto the PAEs support by the NaBH₄ reduction of the Au precursor, and the size of the nano-Pd was about 6.9 nm. The high nitrogen content of the polymer backbone combined with Pd noble nanometals resulted in excellent catalytic performance in the reduction of 4-nitrophenol to 4-aminophenol.

Pendant isocyanate and epoxide-containing copolymers: synthesis, sequential dual-functionalization with amines, and surface modifications

Polymers carrying different reactive groups that can be orthogonally functionalized are desirable for the design of multi-functionalizable materials. While several orthogonally functionalizable polymers have been reported, most of the work utilizes handles that are reactive toward different functional groups. However, examples of polymers that are orthogonally reactive toward molecules bearing the same functional group are rare. In this work, we report polymeric materials that can be sequentially functionalized using different amine-bearing molecules. Herein, we synthesized isocyanate and epoxide group containing copolymers, and investigated their sequential functionalization with amine-containing molecules. We show that such copolymers can be first functionalized with a particular amine-bearing molecule at room temperature, using conjugation through the isocyanate group. Thereafter, a different amine-containing molecule can be attached through the epoxy-amine reaction at 65 °C. Chemical characterizations of parent and subsequently functionalized copolymers were done by 1H NMR and FTIR spectroscopy techniques, to establish orthogonal functionalization. Additionally, the epoxide side chains were utilized as surface anchoring group after the functionalization of the polymer via isocyanate-amine reaction. This straightforward approach for obtaining orthogonally reactive amine-functionalizable copolymers, and surfaces derived thereof, would be attractive materials for various biomedical applications.

Cure Kinetics of Commercial Epoxy-Amine Products with Iso-Conversional Methods

The dependence of the apparent activation energy for the epoxy-amine reaction on the degree of conversion can be obtained by applying iso-conversional methods to the non-isothermal cure data obtained by using differential scanning calorimetry (DSC). The application of three iso-conversional methods has been utilized for the analysis of non-isothermal DSC cure data for three commercial high solids epoxy-amine coatings. The average apparent activation energy for cure of the fully formulated commercial product(s) is very similar to that previously reported for the epoxy-amine clear coats, indicating that the presence of additives does not influence the epoxy-amine apparent activation energy. Among the methods tested, Friedman’s method performed the best in fitting the experimental DSC data. In addition, all three methods underpredict the experimental isothermal cure data for three commercial products at two different cure conditions (i.e., 23 °C/50% RH and 40 °C/70% RH), showing that the non-isothermal DSC experiments cannot capture the catalytic effect of water on the curing reaction of epoxy-amine coatings. Furthermore, for high-solids epoxy-amine products, at least 60% conversion is required to achieve the time when the applied coating will not show any tackiness (i.e., the T2 time measured using the Beck Koller method).

Soft Elastomers Based on the Epoxy–Amine Chemistry and Their Use for the Design of Adsorbent Amphiphilic Magnetic Nanocomposites

Poly(ethylene glycol) (PEG)-based soft elastomers, bearing tertiary amine and hydroxyl groups, were synthesized in bulk from the epoxy–amine reaction between poly(ethylene glycol) diglycidyl ether (PEGDE) and a poly(etherdiamine), Jeffamine ED600. High gel fractions (≥0.95) and low glass transition temperatures (Tg ≈ −50 °C) were attained after complete curing of the systems in bulk. The amphiphilicity of the network allowed the swelling of the materials in both aqueous solutions and a variety of organic solvents. Magnetic nanocomposites were synthesized by in situ coprecipitation of magnetic nanoparticles (MNPs) in the elastomeric matrix. The obtained materials were processed by cryogenic milling to obtain powders that were tested as potential magnetic adsorbents and that showed a fast and strong response to the action of a permanent magnet. These materials showed removal rates of at least 50% in 10 min when used in the adsorption of Cu+2 ions from an aqueous solution, making them interesting candidates for the design of magnetically separable metal ion adsorbents.

Properties tailoring of biobased epoxy resins by regulating the degree of polymerization of oligomers

Epoxy oligomers are preferred in the industry, and biobased epoxy resins derived from renewable biomass particularly attract extra attention. Herein, a series of epoxy oligomers with different polymerization degrees, which originated from biomass magnolol, were synthesized by the “tatty” and “fusion” methods. As the degrees of polymerization increased, P-DBP-EP-n changed from a liquid with a viscosity of 11.7 Pa·s to a solid owing to its high molecular weight and poor chain mobility. Cured resins were prepared with a two-step curing process: an amine-epoxy reaction first, followed by an allyl polymerization. Due to the higher polymerization degree of P-DBP-3 and P-DBP-5, the corresponding cured resins had glass transition temperatures of 334 ℃(P-DBP-EP-3/DDM) and >350 ℃ (P-DBP-EP-5/DDM), indicating superior heat resistance in comparison with P-DP-EP-1/DDM (300 ℃). Additionally, the tensile strength and notched impact strength of P-DBP-EP-3/DDM (22.7 MPa, 2.9 kJ/m2) and P-DBP-EP-5/DDM (25.2 MPa, 2.6 kJ/m2) were better than those of P-DBP-EP-1/DDM (20.7 MPa, 2.5 kJ/m2). The initial degradation temperatures of the three P-DBP-EP-n/DDM samples exceeded 410 ℃, and the char yield maintained above 33% at 700 ℃. What’s more, P-DBP-EP-n/DDM exhibited surprising intrinsic flame retardancy, with LOI values higher than 39% and V-0 rating for the UL 94 tests almost without any after-flame time. The synergy effect of nonflammable gases in the gaseous phase and tough protective char layer in the condensed phase simultaneously contributed to the intrinsic flame retardancy. This work offered a practical and promising method for synthesizing biobased epoxy oligomers with varying degrees of polymerization, obtaining cured resins with comprehensive properties including high heat resistance, excellent thermal stability, and intrinsic flame retardancy.

Bonding of Flexible Membranes for Perfusable Vascularized Networks Patch

BACKGROUND:In vitro generation of three-dimensional vessel network is crucial to investigate and possibly improve vascularization after implantation in vivo. This work has the purpose of engineering complex tissue regeneration of a vascular network including multiple cell-type, an extracellular matrix, and perfusability for clinical application.METHODS:The two electrospun membranes bonded with the vascular network shape are cultured with endothelial cells and medium flow through the engineered vascular network. The flexible membranes are bonded by amine-epoxy reaction and examined the perfusability with fluorescent beads. Also, the perfusion culture for 7 days of the endothelial cells is compared with static culture on the engineered vascular network membrane.RESULTS:The engineered membranes are showed perfusability through the vascular network, and the perfused network resulted in more cell proliferation and variation of the shear stress-related genes expression compared to the static culture. Also, for the generation of the complex vascularized network, pericytes are co-cultured with the engineered vascular network, which results in the Collagen I is expressed on the outer surface of the engineered structure.CONCLUSION:This study is showing the perfusable in vitro engineered vascular network with electrospun membrane. In further, the 3D vascularized network module can be expected as a platform for drug screening and regenerative medicine.

Deep eutectic solvents based on L-Arginine and glutamic acid as green catalysts and conductive agents for epoxy resins

Many engineered epoxy products in the recent years require sustainable materials to be contributive in the coming decades. The efficiency of [DES]Arg/Eg and [DES]Glu/Eg deep eutectic solvents (DESs) on the curing reaction of bisphenol A diglicydyl ether (DGEBA) with the application of differential scanning calorimetry (DSC) at temperatures 313–333 K is assessed. The both DESs studied here can act as the catalyst of epoxy-amine reaction, hardener and conducting agents in a simultaneous manner. Moreover, it reveals different reaction kinetics which strongly depend on the type of hydrogen bonding acceptor of the mixture. It is observed that there exist many fundamental differences between the progress of isothermal curing reaction in the presence of [DES]Arg/Eg and [DES]Glu/Eg considering the conductive ionic liquids and non-conductive conventional hardeners. The [DES]Glu/Eg at lower concentrations exhibits different catalytic behavior in the initial stages of the reaction, in a sense that the reaction progresses at higher rates up to 5 min and hampered afterward. In contrast, [DES]Arg/Eg act as a high-efficient catalyst in a sense that it allows the curing reaction approaches the completion level within 30 min which is comparable to previously reported conducting dopants. From kinetic results it is deduced that the mechanism of curing reaction follows the first-order kinetic in the presence of [DES]Arg/Eg and [DES]Glu/Eg and reaction occurring in the presence of [DES]Glu/Eg is characterized by higher activation energy compared to [DES]Arg/Eg. To analyze the efficiency of DESs as a catalyst for the epoxy-amine reaction, a computational study is run on a simplified model reaction catalyzed by [DES]Glu/Eg revealing a significant decrease in activation energy of the catalyzed reaction.

Zeolitic imidazolate frameworks based porous liquids for promising fluid selective gas sorbents

A kind of zeolitic imidazolate frameworks based porous liquids (e.g., ZIF-8 PLs) with permanent porosity was successfully fabricated by using amine-functionalized ZIF-8 nanoparticles (i.e., ZIF8-A) as the porous fillers and monoglycidyl ether terminated poly(dimethylsiloxane) (i.e., PDMS) as the hindered solvent, respectively. Those ZIF-8 PLs were homogenous and stable at room temperature because of the liquid-particle interaction derived from the epoxy-amine reaction. In addition, those ZIF-8 PLs have larger gas adsorption abilities than their reference hindered solvent because the well-preserved permanent porosity in ZIF-8 PLs could act as void space for gas accommodation. More importantly, those ZIF-8 PLs also show much higher propane adsorption capacity than both of carbon dioxide and nitrogen gas adsorption capacities under the same condition, suggesting that they could function as a kind of promising candidates for fluid selective gas sorbents.

Epoxy-Rich Systems with Preference for Etherification over Amine-Epoxy Reactions for Tertiary Amine Accelerators

Epoxies are often cured using primary and secondary amines in an efficient reaction catalyzed by tertiary amines. Through coordination effects, tertiary amines lower the transition-state energy enough to allow the reaction to take place under ambient conditions. In this paper, we demonstrate how, under ambient conditions, tertiary amines bound in close intramolecular proximity to a primary amine are able to catalyze amine-epoxy reactions as well as promote etherifications in epoxy-rich systems. 13C nuclear magnetic resonance (NMR) was used to identify the sequence of curing reactions in a model reaction of benzyl glycidyl ether (BGE) with the amines 3-diethylaminopropylamine (DEAPA), 3-dimethylaminopropylamine (DMAPA), and hexylamine, respectively. The results clearly show that DMAPA favors etherification over amine-epoxy reactions, while DEAPA displays the expected trend toward amine-epoxy reactions. This experiment was repeated for a curing epoxy system based on bisphenol A diglycidylether (BADGE) with the same three amines, and differential scanning calorimetry (DSC) confirmed this preference of reactions via quantification of the curing exotherms. Finally, a novel DMA setup corroborated the observed rate of reaction for each catalyst by measuring gelation time and vitrification during isothermal curing.

Graphene oxide functionalization via epoxide ring opening in bioconjugation compatible conditions

Graphene oxide (GO) functionalization has great importance for its practical application in many fields, and is a key step for GO bioconjugation. Polydispersity, limited colloidal stability and changeable extinction of GO complicates functional group quantification and the modification study. To bypass the mentioned limitations, we have used GO immobilization on glass support to quantify its epoxy groups surface load, and to study sustainability of the functional groups introduced through epoxy-amine reaction during hydrazine reduction. It was found out that GO contains near 1 epoxy group per nm2, and the major part of the functional groups are remaining after reduction process allowing to use this modification to make functionalized reduced graphene oxide (rGO). Then we modified colloidal GO with azide groups by aminotetraethylene glycol azide (H2N–TEG–N3) in mild conditions to avoid aggregation, and characterized it by means of immobilization on glass surface. Functional group surface load of the functionalized GO was determined as 0,7 groups per nm2. Finally, we proved capability of azide-functionalized GO for conjugation by strain promoted [3 + 2] azide-alkyne cycloaddition (SPAAC) with BCN derivative of organic fluorescent dye JOE.

Dual-cured thermosets from glycydil methacrylate obtained by epoxy-amine reaction and methacrylate homopolymerization

Dual-curing is a processing technology based in the combination of two polymerization processes and the proper selection of the formulation. This methodology allows the preparation of intermediate materials with tailored characteristics, which can be viscous-liquids or rubbery solids according to their application. Once applied, the second stage is performed leading to a high crosslinked network. Usually, different monomers are involved, and unreacted monomer are still present in the intermediate material. This monomer experiments polymerization during the second step, but it can drip or be exuded during storage. In the present work, a commercial monomer, glycidyl methacrylate has been selected, because of the presence in the same molecule of an epoxide group, which can react with amines in the first stage of the dual-curing, and a methacrylate group that can be thermally or photochemically homopolymerized to complete the curing process. Diglycidylether of bisphenol A has been added to obtain a gelled intermediate material. The evolution of both curing steps has been studied by DSC and FTIR. The stability of the intermediate material has been confirmed and the characteristics of intermediate and final material have been evaluated by TGA and DMTA.

Relation between the corrosion resistance and the chemical structure of hybrid sol-gel coatings with interlinked inorganic-organic network

Organic-inorganic hybrid coatings have been prepared by a sol-gel route from 3-glycidoxypropyltrimethoxysilane (GPTMS) and tetraethoxysilane (TEOS) with triethylenetetramine (TETA) added in the sol formulation. The main goal of this research was to evaluate how the chemical structure of the GPTMS/TEOS/TETA hybrid coatings influences the corrosion of mild steel. The presence of TETA as an epoxy opening agent offers the possibility to form interconnected epoxy-amine and silica networks. It was found by means of 29Si HRMAS NMR spectroscopy that TETA acted as an efficient basic catalyst for the condensation of GPTMS and TEOS. This accelerates the gelation and gives limited shelf life to GPTMS/TEOS/TETA sols. Structural characterization of the cured hybrid coatings was performed using 13C and 29Si Solid State NMR spectroscopies. The results show that the epoxy amine reaction is the principal epoxide ring opening reaction. The slow formation of diol units with sols prepared with an excess of epoxy groups has also been observed. It was found that the polymerization of the organic network hindered the polymerization of the siloxane network. As a result, the film based on an epoxy rich off-stoichiometric formulation had a higher Persoz hardness value compared to the stoichiometric film.The corrosion behavior of the coatings in neutral chloride solution was studied through electrochemical impedance spectroscopy (EIS). The results revealed that barrier properties have been improved by the addition of TETA to sol-gel films. The films based on epoxy rich off-stoichiometric formulation and those base on stoichiometric formulation resulted in similar barrier properties but a higher resistance to interfacial delamination was observed for the epoxy rich off-stoichiometric films. The relationship between the film structure and its corrosion behavior was discussed.

Zeolitic imidazolate framework promoters in one-pot epoxy–amine reaction

Epoxy composites are widely used in commercial products. For industrial purposes, storage stability is one of their most important characteristics. To enable this feature, alternative promoters that are stable at a low-energy state, where they do not react, are needed. Zeolitic imidazolate frameworks (ZIFs) are organic–inorganic complexes, and they contain imidazolate linkers, which are one of the promoters in the epoxy–amine reaction. In this study, the stability of a one-pot epoxy–amine composite was improved by using ZIFs as promoters. ZIFs were synthesized using the solvothermal method, and their structure were confirmed using X-ray diffraction analysis and field-emission scanning electron microscopy. The activation energy of the ZIFs was measured using the non-isothermal method of differential scanning calorimetry, and it was calculated using the Kissinger equation. Furthermore, the storage stability of the one-pot epoxy–amine system was measured considering the viscosity change with time at constant temperature. The viscoelastic behavior of the cured sample was demonstrated using dynamic mechanical analysis.

Design, synthesis, and properties of novel amino-ester and amino-ester-alcohol polymer backbones

Simultaneous polymerization of polyacrylic, polyamine, and polyepoxy monomers offers the potential to generate a novel polymer backbone with new and beneficial properties. The Aza-Michael addition of amines to acrylates is fast and exothermic and can thus increase the rate of amine epoxy reactions producing poly amino-ester-alcohol polymer backbones. The polymerization is shown to be remarkably tolerant of organic and aqueous solvent interactions. The resultant polymers are transparent and possess good compressive and thermal properties that are amenable to polymer design. The polymers of this article are predicated on efficient polymerization of the acrylate and amine functionalized monomers, so preliminary rules for their polymerization are provided as a preamble to the hybrid polymers with polyepoxy monomers.

Curing and percolation for carbon black-epoxy-amine nanocomposites

Particle agglomeration in carbon black (CB) filled epoxy (CB-E) and carbon black filled epoxy-amine (CB-EA) nanocomposites with CB concentrations ranging from 0.25 to 1.25 vol% was investigated by performing conductivity measurements as a function of time at 20 °C. For the thermoplastic CB-E samples the change in conductivity was not pronounced, while for the thermosetting CB-EA samples a percolation transition was observed appearing at ≅ 0.2 vol%. The concentration 1.25 vol% was selected for both CB-E and CB-EA samples to perform in situ isothermal electrical conductivity measurements at 20, 50, 70, and 100 °C, respectively. At higher temperature, the agglomeration process was faster, resulting in an initially sharp increase of conductivity. Despite the conductivity development of CB-EA samples being faster than that of CB-E samples, they are reaching lower final conductivity values, indicating that cluster aggregation for the CB-EA samples is restricted by polymer gelation, as confirmed by scanning and isothermal differential scanning calorimetry (DSC). Furthermore, thermodynamic DSC studies showed that no particle-particle and particle-polymer chemical reactions occurred during the epoxy-amine curing. However, physical adsorption of the epoxy and amine components on the CB particles is the likely cause for the observed slightly higher amine-epoxy reaction rates in the presence of CB. Particle agglomeration is thereby attributed to be controlled by diffusion-limited cluster aggregation (DLCA). Finally, the microstructures of CB-EA samples after curing were investigated by using TEM. The fractal dimension df was determined and showed a smaller value as compared to the universal DLCA value, illustrating the influence of gelation on fractal formation in this system.

Polyethylenimine-Grafted HKUST-Type MOF/PolyHIPE Porous Composites (PEI@PGD-H) as Highly Efficient CO2 Adsorbents

Searching for highly efficient and robust CO2 adsorbents is very important for CO2 capture, utilization, and storage. In this study, new polyethylenimine-grafted metal–organic framework (MOF)–polymer composites, abbreviated as PEI@PGD-H, were synthesized via high internal phase emulsion (HIPE) template polymerization of divinylbenzene and glycidyl methacrylate, followed by in situ generation of HKUST-type MOF in the presence of hydrophobic-modified CuO nanoparticles via the reaction of CuO with 1,3,5-benzenetricarboxylic acid and then polyethylenimine (PEI) functionalization via epoxy–amine reaction and amine–metal sites interaction. The coexistence of the hierarchical interconnected porous skeleton of poly(glycidyl methacrylate–divinylbenzene) (PGD), high specific surface area of MOF, and chemical CO2 adsorption of PEI endows PEI@PGD-H with high CO2 adsorption capacity, rate, and selectivity. PEI70@PGD-H shows a CO2/N2 separation factor as high as 76 and CO2 adsorption capacities of 4.3, 3.0, and 1.8 mmo...