Polymerization Strategy Research Articles

3D covalent organic framework membrane with fast and selective ion transport

3D ionic covalent organic framework (COF) membranes, which are envisioned to be able to break the trade-off between ion conductivity and ion selectivity, are waiting for exploitation. Herein, we report the fabrication of a 3D sulfonic acid-functionalized COF membrane (3D SCOF) for efficient and selective ion transport, using dual acid-mediated interfacial polymerization strategy. The 3D SCOF membranes possess highly interconnected ion transport channels, ultramicroporous pore sizes (0.97 nm), and abundant sulfonate groups (with a high ion exchange capacity of 4.1 mmol g−1), leading to high proton conductivity of 843 mS cm−1 at 90 °C. When utilized in osmotic energy conversion, a high power density of 21.2 W m−2, and a remarkable selectivity of 0.976 and thus an exceptional energy conversion efficiency of 45.3% are simultaneously achieved. This work provides an alternative approach to 3D ionic COF membranes and promotes the applications of 3D COFs in ion transport and separation.

Functionalizing Cu nanoparticles with fluoric polymer to enhance C2+ product selectivity in membraned CO2 reduction

Copper-based nanomaterials are attractive in CO2 electroreduction into valuable chemicals but still suffer from limited selectivity of C2+ products due to the parasitic hydrogen evolution reaction and inefficient dimerization of absorbed CO intermediate (*CO). Herein, we report an in situ polymerization strategy to coat hydrophobic polymer containing methoxyl silane ((CH3O)3Si–) and trifluoromethyl (–CF3) functional groups on Cu nanoparticles. The optimized Cu-poly exhibits a high Faradaic efficiency of 71.08 % and a remarkable partial current density of 355.4 mA cm−2 for C2+ products in a membrane electrode assembly electrolyzer using a bicarbonate electrolyte. A combined study of density functional theory calculations and in situ infrared characterizations indicates that the enhanced performances could be ascribed to the decreased formation energy of *COCOH, induced by the withdraw-electron effect of –CF3 and enhanced coverage of *CO. This work offers a new insight in tuning the electrocatalytic microenvironment through the surface polymerization process.

Wheat straw fibre based semi-IPN composite: Preparation and evaluation as a matrix for water and fertilizer release and in slope reinforcement

To improve the utilization rate of fertilizer and reduce environmental pollution, the effective management of water and fertilizer is extremely significant for the development of modern agriculture. Herein, using agricultural wastes (wheat straw fibre, WS) and phosphoric acid-based geopolymers (PGs) as eco-friendly materials, a novel wheat straw fibre composited polymer/PGs (WS-Po/PGs), was prepared by in-situ graft polymerization strategy, and a kind of nutrient-water carrier with semi-IPN was formed. Its structure and morphology were revealed by XRD, FT-IR, BET and SEM. Its water-retaining and controlled release behavior, and the nutrient release model were studied, while the effects on plant growth and loess slope of WS-Po/PGs were further investigated. The results illustrated that the obtained nutrient-water carrier had excellent water absorption (270.27 g/g) and salt tolerance (131.58 g/g) as straw fibres were mixed into polymer networks and formed semi-interpenetrating structures (semi-IPN). Comparing with controls, the WS-Po/PGs significantly improved the water retention capacity and N release longevity (30 d, 66.2%). Its nutrient release fitted the Fickian diffusion model (n < 0.5). Furthermore, the WS-Po/PGs could remarkably enhance the erosion resistance and stability of the loess slope, regulate the pH of the soil, and promote the germination rate of slope vegetation. In summary, by using agricultural wastes straw and loess as resources, the obtained WS-Po/PGs presented excellent slow-release behavior, salt tolerance and slope reinforcement function, and this kind of semi-IPN nutrient-water carrier could provide an insight for agriculture and slope protection.

Präzise Graphen‐Nanostreifen Heteroübergänge durch Kettenwachstumspolymerisation

AbstractGraphene‐Nanostreifen (GNS, engl. GNR) werden als vielversprechende Kandidaten für Nanoelektroniken der nächsten Generation gehandelt. Besonders Heteroübergänge in diesen Materialien erhalten durch ihre exotischen topologischen elektronischen Phasen am Heteroübergang in letzter Zeit viel Aufmerksamkeit. Allerdings sind Synthesestrategien für die atompräzise Synthese noch am Beginn ihrer Entwicklung. Hier berichten wir von einer neuartigen Strategie zur Kettenwachstumspolymerisation für die Konstruktion von Heteroübergängen zwischen N=9 Sessel‐GNR (engl. armchair, 9‐AGNR) und chevron GNRs (cGNR). Die Synthese beinhaltet eine kontrollierte Suzuki–Miyaura Katalysatortransferpolymerisation (engl. SCTP) zwischen 2‐(6′‐bromo‐4,4′′‐ditetradecyl‐[1,1′:2′,1′′‐terphenyl]‐3′‐yl)boronsäureester (M1) und 2‐(7‐bromo‐9,12‐diphenyl‐10,11‐bis(4‐tetradecylphenyl)‐triphenylen‐2‐yl)boronsäureester (M2) um das Blockcopolymer poly‐M1/M2 mit einem kontrollierten Mn (18 kDa) und einem schmalen Polydispersitätsindex Đ (1.45) zu erhalten. Darauf folgt eine Schollreaktion des Blockcopolymers zur Heterostruktur 9‐AGNR/cGNR. NMR und SEC von poly‐M1/M2 bestätigen die erfolgreiche Blockcopolymerisation. Die lösungsvermittelte Zyklodehydrierung von poly‐M1/M2 zu 9‐AGNR/cGNR wurde eindeutig über FT‐IR, Raman und UV/Vis Spektroskopie nachgewiesen. Weiter konnten wir die Ausbildung von 9‐AGNR/cGNR durch Oberflächenchemie des unsubstituierten Blockcopolymers mit Hilfe von Rastertunnelmikroskopie (RTM) direkt visualisieren.

Precision Graphene Nanoribbon Heterojunctions by Chain-Growth Polymerization.

Graphene nanoribbons (GNRs) are considered promising candidates for next-generation nanoelectronics. In particular, GNR heterojunctions have received considerable attention due to their exotic topological electronic phases at the heterointerface. However, strategies for their precision synthesis remain at a nascent stage. Here, we report a novel chain-growth polymerization strategy that allows for constructing GNR heterojunction with N=9 armchair and chevron GNRs segments (9-AGNR/cGNR). The synthesis involves a controlled Suzuki-Miyaura catalyst-transfer polymerization (SCTP) between 2-(6'-bromo-4,4''-ditetradecyl-[1,1':2',1''-terphenyl]-3'-yl) boronic ester (M1) and 2-(7-bromo-9,12-diphenyl-10,11-bis(4-tetradecylphenyl)-triphenylene-2-yl) boronic ester (M2), followed by the Scholl reaction of the obtained block copolymer (poly-M1/M2) with controlled Mn (18k) and narrow Đ (1.45). NMR and SEC analysis of poly-M1/M2 confirm the successful block copolymerization. The solution-mediated cyclodehydrogenation of poly-M1/M2 toward 9-AGNR/cGNR is unambiguously validated by FT-IR, Raman, and UV-vis spectroscopies. Moreover, we also demonstrate the on-surface formation of pristine 9-AGNR/cGNR from the unsubstituted copolymer precursor, which is unambiguously characterized by scanning tunneling microscopy (STM).

Polymeric Nanoparticles: Prospective on the Synthesis, Characterization and Applications in Nose-to-Brain Drug Delivery

Abstract: For the treatment of brain illnesses, there is growing interest in nose-to-brain drug administration. Other, more traditional methods of crossing the blood–brain barrier (BBB) are ineffective. As a result, the therapeutic concentration in the brain cannot be achieved, and the reaction is inadequate. Intranasal medication delivery is one intriguing technique for avoiding first-pass metabolism and bypassing the blood-brain barrier. It lowers medicine doses while reducing systemic side effects. Compared to conventional drug delivery platforms, a nanoparticulate drug delivery method allows for greater penetration via the nasal route. It is better to make the nanoparticles for nose-to-brain administration when a good carrier (polymers) is used. This review focuses on the many processes for creating polymeric nanoparticles, strategies and tactics for improving nose-tobrain drug delivery efficiency, and nanoparticle characterization. The use of the nose-to-brain drug delivery platform is being explored using a variety of nanoparticles created by researchers for the treatment of brain illnesses.

Contributing to the Revolution of Electrolyte Systems via In Situ Polymerization at Different Scales: A Review.

Solid-state batteries have become the most anticipated option for compatibility with high-energy density and safety. In situ polymerization, a novel strategy for the construction of solid-state systems, has extended its application from solid polymer electrolyte systems to other solid-state systems. This review summarizes the application of in situ polymerization strategies in solid-state batteries, which covers the construction of polymer, the formation of the electrolyte system, and the design of the full cell. For the polymer skeleton, multiple components and structures are being chosen. In the construction of solid polymer electrolyte systems, the choice of initiator for in situ polymerization is the focus of this review. New initiators, represented by lithium salts and additives, are the preferred choice because of their ability to play more diverse roles, while the coordination with other components can also improve the electrical properties of the system and introduce functionalities. In the construction of entire solid-state battery systems, the application of in situ polymerization to structure construction, interface construction, and the use of separators with multiplex functions has brought more possibilities for the development of various solid-state systems and even the perpetuation of liquid electrolytes.

Surface-Initiated Zerovalent Metal-Mediated Controlled Radical Polymerization (SI-Mt0CRP) for Brush Engineering.

ConspectusThe surface-tethered polymer brush has become a powerful approach to tailoring the chemical and physical properties of surfaces and interfaces and revealed broad application prospects in widespread fields such as self-cleaning, surface lubrication, and antibiofouling. Access to these diverse functional polymer brushes is highly dependent on versatile and powerful surface-initiated controlled radical polymerization (SI-CRP) strategies. However, conventional SI-CRP typically requires oxygen exclusion, large amounts of catalysts and monomer solution, and a long reaction time, making it time-consuming and sophisticated. When using a two-plate system consisting of an initiator-bearing substrate and a metal plate, we and our collaborators introduced surface-initiated zerovalent metal-mediated controlled radical polymerization (SI-Mt0CRP). In the SI-Mt0CRP setup, a metal(0) plate (Cu, Fe, Zn, or Sn) is placed proximately to an initiator-functionalized substrate and forms a confined polymerization system which considerably simplifies the synthesis of a wide range of polymer brushes with high grafting densities over large areas (up to the meter scale).In comparison to classical SI-ATRP (catalyzed by metal salts), SI-Mt0CRP demonstrates oxygen tolerance, high controllability, good retention of chain-end functionality, and facile recyclability of the metal catalysts (i.e., metal foil/plate). Taking advantage of the confined geometry of the SI-Mt0CRP setup, polymer brushes with various conformations and architectures are easily accessible while consuming only microliter volumes of monomer solution and without complicated operations under ambient conditions. Owing to these attractive characteristics, SI-Mt0CRP has become a versatile technique for functionalizing materials for targeted applications, ranging from the areas of surface science to materials science and nanotechnology.In this Account, we summarize the recent advances of SI-Mt0CRP catalyzed by zerovalent metals (e.g., Cu, Fe, Zn, and Sn) and highlight the intrinsic advantages of the featured experimental setup, compared with the "classical" SI-CRP in which metal salt, powder, or wire is applied. We further discuss the synthetic features and proposed mechanism of SI-Mt0CRP while emphasizing the various external technologies' (including "on water" reaction, galvanic replacement, lithography, and capillary microfluidic) integrated polymerization systems. We also describe structural polymer brushes, including block copolymers, patterned and gradient structures, and arrayed and binary polymer brushes. Finally, we introduce the diverse polymer brushes that have been prepared using these techniques, with a focus on targeted and emerging applications. We anticipate that the discussion presented in this Account will promote a better understanding of the SI-Mt0CRP technique and advance the future development of practical surface brushing.

Porous cyclopentadiene unit-incorporated graphitic carbon nitride nanosheets for efficient photocatalytic oxidation of recalcitrant organic micropollutants in wastewater

For the purpose of searching for efficient photocatalysts to deal with recalcitrant organic micropollutants in wastewater, here an in-situ supramolecule self-assembly-thermal polymerization strategy is developed to prepare a series of porous cyclopentadiene (CPD) unit-incorporated g-C3N4 ultrathin nanosheets (CCPD-g-C3N4). The CCPD-g-C3N4 demonstrate CPD unit doping level-dependent and remarkably enhanced visible-light photocatalytic oxidation efficiency towards two organic micropollutants, acetaminophen and methylparaben, in which the optimized CCPD-g-C3N4-2 shows 6.1 and 3.5 times higher acetaminophen and methylparaben degradation rate than bulk g-C3N4; moreover, CCPD-g-C3N4-2 is still robust and efficient in the treatment of five mixed organic micropollutants in pharmaceutical wastewater, and the satisfactory micropollutant removal efficiency is obtained in a wide pH window and the presence of high concentrations of inorganic anions and cations as well as dissolved organic matters. Theoretical calculation combined with experimental test reveal that CCPD-g-C3N4 can significantly reduce ecological risk of the target pollutant after the photocatalytic degradation reaction. Such enhanced photocatalytic oxidation efficiency is dominated by the accelerated charge carrier separation dynamics and extended visible-light response region due to the incorporation of CPD units, which finally lead to the generation of abundant reactive oxygen species to degrade and mineralize target micropollutants efficiently.

Tailoring surface topography of biochar-based hydrogel for hazardous pollutants removal from contaminated seawater through simultaneous steam-electricity generation

Although solar steam generation (SSG) is a promising strategy for solving global freshwater scarcity, some technological gaps remain such as the generally costly and delicate nanostructures. Herein, multifunctional Biochar/PAAm hydrogels with excellent resilience, openly porous structure, fast water-transfer, and enhanced light-trapping performances were fabricated from the strong attraction of the biochar functional groups and the abundant amido groups of the backbone chain of hydrogel through a facile polymerization strategy. Under 1 sun irradiation, the composite exhibited a high and long-term evaporation rate of 2.22 kg m−2 h−1 due to the synergistic effect of excellent light absorption of biochar and fast water transmission in hydrogel structure which decrease the evaporation enthalpy. Furthermore, the hydrogel surface topography was controlled by template-assisted gelation producing a sharply dimpled surface (SDS) that exhibited a high evaporation rate of 2.71 kg m−2 and an efficiency of 98.7 % owing to the light trapping effect on the sharped surfaces. The high adsorption capacity of the hydrogel enables the removal of hazardous pollutants from the bulk water preventing their concentration in the brine after the solar desalination process. Besides, a thermoelectric (TE) generator can be integrated with the membrane producing a simultaneous power density of 728.2 mW/m2.

Metal-organic frameworks engaged formation of FeSe2/N-doped carbon as anode enables high-performance sodium-ion batteries

Sodium-ion batteries (SIBs) have great potential for large-scale energy storage, whereas the development of satisfactory anode material is still a challenge. Herein, the nitrogen-doped carbon encapsulated FeSe2 (FeSe2@NC) with spindle-like nanostructures are proposed by polymerization, carbonization and selenization strategies. The N-doped carbon layer effectively improves the electronic conductivity, provides more activity sites, and alleviates the volume expansion. As expected, the prepared FeSe2@NC delivers excellent rate performance (232.3 mAhg−1 at 1.0 Ag−1) and superior cycle stability (269.8 mAhg−1 after 500 cycles). Significantly, this work proposes an effective material engineering approach for designing transition metal selenides for high-performance SIBs.

Guanidinium manipulated interfacial polymerization for polyamide nanofiltration membranes with ultra-high permselectivity

Polyamide (PA) nanofiltration (NF) membranes with excellent permeability and selectivity have always been the ultimate pursuit of desalination technology. Herein, we present a guanidinium manipulated interfacial polymerization strategy to develop guanidyl-integrated PA NF membranes with ultra-high permselectivity. A nylon microfiltration membrane is utilized as the support to conduct spatial-temporal regulation of amine monomers along with controllable diffusion reaction. Through introducing 1,3-diaminoguanidine (DAG) or triaminoguanidine (TAG) into the aqueous piperazine solution, the free volumes of PA membranes could be well modulated at the sub-angstrom scale. Consequently, the TAG-integrated PA membrane exhibited high water permeance of 33.1 LMH bar−1 and superior Na2SO4 rejection of 99.2%. Meanwhile, this membrane achieved outstanding anion sieving capability (Cl−/SO42− ∼ 343) and nearly 100% tetracycline removal, which is superior to the “state-of-the-art” PA NF membranes. The DAG-integrated PA membrane attained ultra-high water permeance of 46.5 LMH bar−1 due to its relatively large free volume. In addition, the nylon composite PA membranes displayed desirable anti-pressure and organic solvent-resistant abilities. This study provides a convenient and scalable preparation strategy for highly permselective NF membranes, which holds great application potential in desalination and resource recovery.

Rapid on-demand in-situ gelling and dissociation of PEG bottlebrush hydrogel via light-mediated grafting-through polymerization for full-thickness skin wound repair

Developing light-triggered in situ forming dynamical hydrogels with on-demand dissolvable and antioxidation capacities to promote wound healing is highly desired yet challenging. Herein, we prepared an in situ forming bottlebrush hydrogel with on-demand dissolution capacity from two thioctic acid (TA)-functionalized poly(ethylene glycol)s (PEGs) telechelic (TA-PEGs) prepolymers via a light-mediated grafting-through polymerization strategy. In response to light irradiation, TA-PEGs could undergo rapid ring-opening polymerization to generate a highly branched bottlebrush network with dynamic disulfide bonds and simultaneously load water-soluble curcumin complexes with excellent antioxidant activity, enabling fast in situ gelation in 3 min to achieve perfect coverage of wound sites with different shapes. Furthermore, the resulting bottlebrush hydrogel dressing can achieve facile and painless removal of the dressing via rapid on-demand dissolution of the hydrogel during dressing changes. Meanwhile, thanks to its dynamical feature of the disulfide-based network, the hydrogel possesses excellent self-healing ability and shape adaptability that can maintain the interiority of the dressing during application and thus prolong its service life. In vitro evaluation demonstrates that this PEG bottlebrush hydrogel possesses favorable hemocompatibility, cytocompatibility, and antioxidant capacity. More importantly, in vivo experiments confirmed that the hydrogel promotes angiogenesis, dermal collagen synthesis, and alleviates the excessive ROS damage, thus providing more beneficial conditions to accelerate full-thickness skin wound healing.

Development of novel nanocomposite-modified photoelectrochemical sensor based on the association of bismuth vanadate and MWCNT-grafted-molecularly imprinted poly(acrylic acid) for dopamine determination at nanomolar level

This study proposes the development of a new photoelectrochemical (PEC) sensor for the determination of dopamine (DA) at nanomolar levels. The PEC sensor was based on a physical mixture of bismuth vanadate (BiVO4) with nanocomposite molecularly imprinted poly(acrylic acid) (MIP-AA) grafted onto MWCNTox by using the surface-controlled radical polymerization strategy with an INIFERTER reagent. XRD, diffuse reflectance spectroscopy (DRE), SEM, TEM, and TGA were employed to characterize the materials. Photoelectrochemical analyses were carried out with GCE/BiVO4/MIP-AA sensor under visible light using a potential of 0.6 V, phosphate buffer (0.1 mol L−1) at pH 7.0, and modifying the GCE with a film composed of monoclinic BiVO4 at 3.5 mg mL−1 and nanocomposite MIP prepared with acrylic acid (MIP-AA) at 0.1 mg mL−1. The proposed method using the GCE/BiVO4/MIP-AA sensor presented a limit of detection (LOD) of 2.9 nmol L−1, a linear range from 9.7 to 150 nmol L−1 and it was successfully applied for analysis of DA in urine samples using external calibration curve yielding recovery values of 90–105%. Additionally, the proposed PEC sensor allowed DA determination without interference from uric acid, ascorbic acid, epinephrine, norepinephrine, and other unwanted interferences.

Synchronous Ultraviolet Polymerization Strategy to Improve the Interfacial Toughness of Bilayer Hydrogel Actuators

Synchronous Ultraviolet Polymerization Strategy to Improve the Interfacial Toughness of Bilayer Hydrogel Actuators

Fabrication of an anti-fouling coating based on epoxy resin with a double antibacterial effect via an in situ polymerization strategy

The hull and subsea equipment are often plagued by widespread marine biofouling, so developing a sustainable environmental protection antifouling paint is urgent. The study designed and developed an antifouling composite coating system (E44-Ag-PGI) with a synergistic antibacterial effect based on the dual strategy of the bacteriostatic effect of stereochemical structure on polymer surface and release sterilization of metal nanoparticles. Firstly, an antifouling agent (PGI) was prepared by simple radical polymerization by combining glycidyl methacrylate with borneol, a complex bicyclic monoterpene structure extracted from plants. Then bisphenol A epoxy resin with strong adhesion to metal was selected as the base material. The synthetic antifouling agent with epoxy groups was polymerized in situ into the epoxy resin network, and compared with pure epoxy resin, the elongation at break of E44-Ag-PGI coating with 20 % PGI content increased from 40.37 % to 124.8 %, which was mainly attributed to the introduction of a soft chain of antifouling agent polymer, which improved the flexibility of the coating. Meanwhile, the antibacterial efficiency of the coating against Pseudomonas aeruginosa and Staphylococcus aureus was 97.69 % and 95.9 %, respectively. This excellent antibacterial performance was mainly attributed to the synergistic antibacterial action of natural borneol and AgNPs. In addition, the biofilm and diatom resistance experiments of the coating showed that the coating also has an excellent antifouling effect. This provided a new research idea for environmentally friendly antifouling coatings.

Electrochemical biosensor for highly sensitive detection of cTnI based on a dual signal amplification strategy of ARGET ATRP and ROP

Cardiac troponin I (cTnI), a gold biomarker for the diagnosis of acute myocardial infarction (AMI), plays a vital role in the early diagnosis, treatment and prognosis analysis of AMI. In this paper, an electrochemical biosensor for the highly sensitive determination of cTnI was fabricated based on the dual signal amplification strategy of electron transfer atom transfer radical polymerization (ARGET ATRP) and ring-opening polymerization (ROP) for the first time. Briefly, the thiolate cTnI-aptamer 1, which was bonded to the electrode via Au–S bonds, specifically captured cTnI to the electrode surface. Then, cTnI-aptamer 2 (Apt2) was successfully introduced to the electrode surface to form Apt-cTnI-Apt sandwich structure. Subsequently, the initiator BIBB was connected to Apt2 through bromination reaction, and then the resulting ATRP polymer was employed as a macromolecular initiator for the succeeding reaction. Next, the monomers, α-amino acid-N-carboxylic acid anhydride ferrocene derivatives (NCA-Fc), used for the ROP reaction produced numerous electroactive polymers on the electrode surface. The dual action of ARGET ATRP and ROP significantly improved sensitivity of cTnI biosensor assay, the prepared biosensor displayed a wide linear detection range from 100 fg mL−1 to 100 ng mL−1, with a detection limit of 32.24 fg mL−1. The method exhibited favorable selectivity, simple operation and excellent stability. Furthermore, the biosensor still rendered satisfactory analytical performance in the detection of clinical serum samples, indicating the application potential in clinical diagnosis.

High-performance thin film composite nanofiltration membranes with MoS2 nanosheet interlayer

High-performance polyamide thin film composite (TFC) nanofiltration membranes have received great attention in recent years. Herein, we report the preparation of TFC nanofiltration membranes by interfacial polymerization using MoS2 nanosheets as the nanomaterial interlayer. The aqueous monomer and MoS2 nanosheets are distributed on the surface of microporous membrane substrates by a one-step method. The MoS2 interlayer improves the uniformity and smoothness of the microporous substrates, helping to form polyamide nanofilms at ultralow monomer concentration. Moreover, the hydrophilic and negatively-charged MoS2 nanosheets enhance the water permeability and negative charges of the nanofiltration membranes. The composite membranes show both high water permeance of 33.5 L m−2 h−1 bar−1 and Na2SO4 rejection of 97.5%, as well as significantly improved mono-/divalent anions selectivity and antifouling property. It is proved that the interfacial polymerization strategy assisted by the MoS2 interlayer is effective for preparing high-performance nanofiltration membranes.

Interface-induced polymerization strategy for constructing titanium dioxide embedded carbon porous framework with enhanced chemical immobilization towards lithium polysulfides

Interface-induced polymerization strategy for constructing titanium dioxide embedded carbon porous framework with enhanced chemical immobilization towards lithium polysulfides

Adjustable boron nitride segregated framework in epoxy resin for high performance thermal management and flame retardant applications

Excess heat production in miniaturized and integrated of electronic devices has created a strong demand for polymeric thermal management materials with superior thermal conductivity and flame retardancy. For the reason, a phytate-assisted ball-milling method was used to exfoliate and functionalize the boron nitride nanosheets (f-BNNS) with flame retardancy, which was further modified using KH560. Then, EP composites with f-BNNS@KH560 frames were prepared by emulsion polymerization, adhesive self-assembly and hot-pressing strategies. The mass ratio of EP to water in the emulsion polymerization process is closely related to the structure of f-BNNS@KH560 framework. The smaller the ratio of EP to water, the more complex the structure of the framework and the more paths for heat transfer of the obtained EP composites. Ultimately, f-BNNS@KH560/EP-3 exhibits a high K value of 2.4 W m−1 K−1 at a loading of 30 wt% due to more abundant heat transfer paths and good compatibility. In the cooling performance test of LED lamp, f-BNNS@KH560/EP-3 works at a temperature 16.5 °C lower than that of conventional f-BNNS@KH560/EP composites. Besides, the superior flame retardancy of f-BNNS@KH560/EP is mainly attributed to the strong barrier effect of adjustable f-BNNS@KH560 framework. Undoubtedly, f-BNNS@KH560/EP-3 provides ideas for industrial applications of high power devices.