Flame Retardant Research Articles

A novel biobased prepreg from flax and thermosetting poly(lactic acid): Synthesis, curing and processing

Flax fiber-reinforced thermosetting poly (lactic acid) (PLA) composites, a fully degradable plant fiber-reinforced composites, were prepared by hot-melt pre-impregnation, which consists of two processes, the preparation and curing of the prepreg. Firstly, thermosetting PLA with intrinsic flame-retardancy was synthesized and its molecular structure was verified by Fourier transform infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy. The non-isothermal viscosity of the thermosetting PLA resin system was investigated to determine the film-formation temperature (55°C) and the impregnation temperature (65°C) during the preparation of the prepreg. On this basis, novel flax fiber-reinforced thermosetting PLA prepreg was prepared and its curing kinetics was investigated using differential scanning calorimetry (DSC). A curing simulation model of the prepreg was developed using the finite difference method, which was used to design and optimize the curing cycle of the flax fiber-reinforced thermosetting PLA prepreg. Finally, the flax fiber-reinforced thermosetting PLA composites with different lay-ups were prepared using the optimal curing cycles and their mechanical and flame retardant properties were investigated, with tensile and flexural strengths up to 128 MPa and 98.8 MPa, and flame retardant ratings up to UL-94 V-1. Overall, the results of this study can provide an important basis for expanding the application of flax fiber reinforced thermosetting PLA composites.

Constructing piperazine pyrophosphate@LDH@rGO with hierarchical core-shell structure for improving thermal conductivity, flame retardancy and smoke suppression of epoxy resin thermosets

The integration and miniaturization development of electronic devices placed the great demand for epoxy resin (EP) thermosets with excellent thermal management, flame retardancy and electrical insulation. Herein, a multifunctional additive piperazine pyrophosphate@layered double hydroxide@reduced graphene oxide (PPAP@LDH@rGO) with hierarchical core-shell structure was constructed by solvothermal and electrostatic self-assembly methods to meet the above requirements. Profiting from the distinct structure of PPAP@LDH@rGO, the thermal conductivity of EP/PPAP@LDH@rGO reached 0.951 W m−1 K−1 at 7 wt% addition (3 wt% rGO containing), which is 320.8 % increment compared to pristine EP. Meanwhile, when 4 wt% PPAP@LDH@rGO was added, the EP thermoset reached UL-94 V-0 rating during vertical burning tests with the limiting oxygen index of 29.8 % due to the synergistic effect of PPAP, LDH and rGO. The release of hazard products including smoke and carbon monoxide for EP/PPAP@LDH@rGO visibly declined during combustion. Besides, the EP thermosets also well-maintained the electrical insulation and mechanical properties. This work provided an alternative approach for preparing high performance EP thermosets which was suitable to be applied in electronics and electrical fields.

High mechanical strength, flame retardant, and waterproof silanized cellulose nanofiber composite foam for thermal insulation

High mechanical strength, flame retardant, and waterproof silanized cellulose nanofiber composite foam for thermal insulation

A New Approach for Improving Flame Retardancy of Automotive Interior Upholstery

This study presents the flame retardant (FR) performance of chemically treated automotive upholstery fabrics using two different impregnation methods of Resin Transfer Molding (RTM) and supercritical carbon dioxide (scCO2). Referring to the related standards, untreated seat fabric obtained from seat upholstery of a bus (neat fabric, NF) and treated fabric samples underwent burning rate (BR) and limiting oxygen index (LOI) tests to compare effect of treatment and impregnation methods on FR performance. Thermal analysis was also conducted on the samples considering onset degradation temperatures and char yields. The results showed that BR and LOI of all samples were in acceptable range and treatment provided enhancement in FR performance of NF. The treated sample using scCO2 method gave the highest LOI value of 32% and the lowest BR of 21 mm/min subtending to 18.5% increase in LOI and 30% reduction in BR compared to those of NF. The performance of treatment in RTM was worse than that of scCO2 and better than that of NF. The results confirm that both treatment and methods used in this study give promising results for safety against fire in transportation vehicles.

Dual Cross-Linked Networks Reinforced Polyimide Foams with Outstanding Piezoelectric Properties and Heat Resistance Performance.

The application of traditional isocyanate-based polyimide (PI) foams is highly hindered due to limited flame retardancy, poor mechanical properties, and relatively single functionality. Herein, we propose an effective method to fabricate dual cross-linked polyimide/bismaleimide (PI-BMI) foams with outstanding heat resistance and enhanced mechanical properties by incorporating bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (ME-BMI) as the interpenetrating network. The results show that the prepared PI-BMI composite foams exhibit enhanced mechanical properties with lightweight characteristics (23-80 kg·m-3). When the ME-BMI loading reached 120 wt %, the tensile and compressive strength of PI-BMI composite foam can reach 1.9 and 7.8 MPa, which are 9.6 and 63.3 times higher than that of pure PI foam, respectively. In comparison with PIF-0, the 10% heat loss temperature (Td,10%) of PIF-90 improved by 156 °C. Moreover, the PI-BMI foam piezoelectric sensor containing fluorine groups presents a short response time (14.22 ms), high sensitivity (0.266 V/N), and outstanding stability (10 000 cycles). Besides, the sensor can accurately monitor human activity in different states. This work provides a promising strategy for designing multifunctional PI foams, making them suitable for applications in aerospace and microelectronics.

Protocatechualdehyde-based epoxy vitrimer with low dielectric, excellent flame retardancy, and recyclability

Conventional bisphenol A epoxy resins cannot meet the requirements of the new generation of electronic/electrical industries in terms of dielectric properties and flame retardancy and are challenging to reprocess after molding, resulting in waste of resources and environmental hazards. Therefore, a tetrafunctional active ester curing agent (TIE) was successfully synthesized by a one-pot method using biomass protocatechualdehyde as raw materials, followed by curing DGEBA to prepare an epoxy vitrimer (TIE/DGEBA). MHHPA/DGEBA was chosen for comparison since the –OH was also absent after curing. The results showed that TIE/DGEBA had good combinatorial performance, thanks to the unique structure of TIE, including active ester units, siloxane chains, and aromatic Schiff base groups. TIE/DGEBA possessed a lower dielectric constant (2.9 vs. 4.0) compared to MHHPA/DGEBA, which was attributed to the synergistic effect of the less-polar siloxane chain segments, bulky benzene structure, and lower cross-linking density (1971 vs. 733 mol/cm3) of TIE/DGEBA. The aromatic Schiff base not only imparted good thermal stability (T30% = 418.0 vs. 422.2 °C) to TIE/DGEBA but ensured that it allowed for recycling and reprocessing. After solvent recycling, the resin can be remolded without significant change in tensile strength (53.0 vs. 46.3 MPa). TIE/DGEBA displayed better flame retardancy with higher residual weight (28.2 % vs. 5.5 %), lower total heat release (29.6 vs. 43.5 kJ/g), and good resistance to thermal oxidization. The structural and performance characteristics of TIE/DGEBA offer a strategy for designing multifunctional epoxy-based materials in electrical/electronic applications.

Effect of functionalized halloysite nanotubes on fire resistance and water tolerance of intumescent fire-retardant coatings for steel structures

To improve the comprehensive performance of intumescent fire-retardant coatings, the functionalized halloysite nanotubes (HNTs-D, HNTs@Fe3O4, and HNTs-D@Fe3O4) were synthesized as synergistic flame retardants and incorporated into intumescent fire-retardant coatings (IFRC) for steel structures, demonstrating significant flame retardant properties. Among these modified halloysite nanosheets, HNTs-D@Fe3O4 showed the best flame retardancy and water resistance. Adding the optimal addition amount (3 wt%) of HNTs-D@Fe3O4 can increase the residual weight of coating from 28.10 % to 38.40 % and reduce the backside temperature of the coated steel plate from 288 °C to 177 °C, indicating that HNTs-D@Fe3O4 can effectively improve the thermal stability and insulation performances of intumescent fire-retardant coatings. Cone calorimetric analysis showed HNTs-D@Fe3O4 can effectively suppress the heat and smoke release of the intumescent fire-retardant coatings. Compared with the unmodified coating sample, the total heat release (THR) and total smoke release (TSR) of the HNTs-D@Fe3O4-containing coating sample were reduced by 66.04 % and 11.36 %. HNTs-D@Fe3O4 facilitates the formation of dense char layers confirmed by the micro morphology characterization. Further mechanism analysis shows that HNTs-D@Fe3O4 has obvious catalytic carbonization effect and is helpful to construct the dense expanded char layer with higher graphitization degree. The uniformly dispersed HNTs-D@Fe3O4 improved the water resistance of intumescent fire-retardant coatings, which is mainly due to the hydrophobicity and barrier effect, thus effectively preventing the loss of water-soluble components.

Sustainable full-cell NCM||Graphite system with superior stability: The hybrid impact of sulfone-containing and flame-retardant additives on interface formation and cyclability

S-containing additives improve the performance, lifetime, and sustainability of lithium-ion batteries (LIBs) through the stabilization of electrode-electrolyte interfaces, modification of electrolyte properties, and facilitating the efficient resource utilization and rapid Li+ migration. Non-etheless, fire safety, extended shelf life, and capacity maintenance are critical concerns for commercial LIBs. Herein, a S-containing film-forming additive, including 4,4-diaminodiphenylsolfon (DADP) by incorporating flame retardancy of dimethyl methyl phosphonate (DMMP) was considered toward taking the barriers of above-mentioned challenges. Based on the calculation, the additives decompose sequentially to produce a distinct SEI via a narrower energy gap under both cathodic and anodic conditions. The NCM532||Graphite with DADP/DMMP showed the enhanced preservation and stability of structure, defined by XRD, Rietveld refinement pattern, SEM, and FT-IR. While the DMMP decreased the fire risk and lowered the capacity due to side reactions, the DADP improved the capacity loss, where the retention rate was 94.91%, 92.01%, 81.29%, and 76.22% within 100, 200, 300, and 400 cycles, respectively. The additive also maintained a capacity of 1123.115 mAhg−1 for 650 cycles, demonstrating excellent cyclability. Therefore, DADP/DMMP facilitate the formation of stable SEI layer, reduce fire risk, improve cycle stability, and offer an achievable path to develop the safe and long-lasting commercial batteries.

Extrusion 3D Printing of Intrinsically Fluorescent Thermoplastic Polyimide: Revealing an Undisclosed Potential.

Thermoplastic polyimides (TPIs) are promising lightweight materials for replacing metal components in aerospace, rocketry, and automotive industries. Key TPI attributes include low density, thermal stability, mechanical strength, inherent flame retardancy, and intrinsic fluorescence under UV light. The application of advanced manufacturing techniques, especially 3D printing, could significantly broaden the use of TPIs; however, challenges in melt-processing this class of polymer represent a barrier. This study explored the processability, 3D-printing and hence mechanical, and fluorescence properties of TPI coupons, demonstrating their suitability for advanced 3D-printing applications. Moreover, the study successfully 3D-printed a functional impeller for an overhead stirrer, effectively replacing its metallic counterpart. Defects were shown to be readily detectable under UV light. A thorough analysis of TPI processing examining its rheological, morphological, and thermal properties is presented. Extruded TPI filaments were 3D-printed into test coupons with different infill geometries to examine the effect of tool path on mechanical performance. The fluorescence properties of the 3D-printed TPI coupons were evaluated to highlight their potential to produce intricately shaped thermally stable, fluorescence-based sensors.

Diethyl ethylphosphonate retardants disturbed the gut microbiome and metabolite SCFAs in vitro based on simulator of the human intestinal microbial ecosystem

Diethyl ethylphosphonate (DEEP) as a novel organophosphorus flame retardant received increasing attention and its structure was discovered. But there are currently insufficient studies on how DEEP exposure affects the gut microbiome. In this study, the effects of DEEP on the structure and function of the human gut microbiota were examined using the SHIME system. Results from high-throughput sequencing of the 16S rRNA gene show that the high dose DEEP exposure reduced the Shannon and Simpson index in the transverse and descending colon. The Bacillota had the highest proportion while the proportion of Proteobacteria gradually decreased at the phylum level. The abundance of Escherichia, Prevotella, and Bilophila at the genus level increased with increasing doses of DEEP exposure. On the contrary, the abundance of Megasphaera, Klebsiella, and Phascolarctobacterium decreased. The short-chain fatty acids had a significant shift. With increasing doses of DEEP exposure, the concentration of acetic acid and propionic acid increased, while the concentration of butyric acid reached the highest at the medium dose of exposure. In addition, Bilophila, Psychrobacter, Escherichia, and Nostoe showed strong beneficial associations with acetic and propionic acids under DEEP exposure. Phocaeicola, Agathobacter, Klebsiella, Megasphaera, Phascolarctobacterium, and Bacteroides were negatively association with acetic and propionic acids. In a word, the study verified that exposure to different doses of DEEP can cause changes in the composition of the gut microbiome and metabolite SCFAs, which provides ideas for the investigation of other potential hazards of DEEP on human beings.

Cotton fabric with durable flame retardancy, robust superhydrophobicity and reliable UV shielding

Cotton fabric with durable flame retardancy, robust superhydrophobicity and reliable UV shielding

Eco-friendly flame retardant comprising chitosan-based effectively enhances the flame retardancy of wood with low weight percent gain

Nowadays, there are many types of flame retardants, whether halogenated or halogen-free, that can improve the flame retardancy of wood. However, they continue to pose a significant threat to our environment and cause a substantial increase in the weight gain rates after treatment. It is highly desirable yet challenging to develop an eco-friendly and efficient flame retardant with low weight gain rates. Here, we report a simple and fast process for making eco-friendly flame retardants (chitosan, gelatin, sodium phytate and clay) with weight gain rates of 3.7 %, which form excellent flame retardancy systems. This method can be used to create a 53.5 % reduction in peak heat release rate (pHRR) an 189 % increase in ignition time (cone colorimeter), and a 71.9 % reduction in peak temperature (alcohol spray lamps) compared to raw wood. The results displayed that the effect of flame retardancy (Decreased ratio for pHRR/Weight percent gain) was the best in the past three years. In addition, the flame retardancy mechanism is thoroughly analyzed using the techniques of Raman and so on. This study proposes a novel strategy featured by eco-friendly and simple preparation process for enhancing the flame retardancy of wood in important areas.

Efficient flame retardancy of polypropylene by cobalt ions doped phytate melamine synergized with expandable graphite

Maintaining a delicate balance between flame retardancy and amount of expandable graphite (EG) in flame retardant polypropylene (PP) is still a formidable challenge, primarily due to the lower flame-retardant efficiency of EG. In order to address this concern, a novel cobalt-doped nanosheet flame retardant (PAMA-Co) was fabricated by a hydrothermal method utilizing phytic acid (PA) and melamine (MA), exhibiting a promising potential in constructing synergistic EG flame retardant PP. Significantly, the incorporation of only 7 wt% PAMA-Co/23 wt% EG system raises the limiting oxygen index (LOI) of PP to 27.3% and UL-94 V0 level, which indicates the excellent synergistic flame-retardant efficiency of PAMA-Co. Furthermore, both the peak heat release rate (PHRR) and the peak smoke production rate (PSPR) of PP composites with 7 wt% PAMA-Co/23 wt% EG are substantially reduced, exhibiting an 81.6% lower PHRR and 87.8% PSPR compared to pure PP. The excellent flame-retardant efficiency is attributed to the following mechanisms: Gas-phase dilution, catalytic cross-linking charring effect, and the suppression of the EG "popcorn effect" of PAMA-Co. In summary, this work not only advances an understanding of flame-retardant mechanisms but also offers a practical, green strategy for enhancing the safety and utility of PP in various applications.

A novel bio-based ferric flame retardant effectively improving the flame retardancy and mechanical properties of polylactic acid

PTDF is prepared by a convenient ionic reaction of phytic acid, terephthalic dihydrazide and iron salts in water. PTDF has high phosphorus and nitrogen content and good thermal stability, which can effectively improve the flame retardancy of PLA. PTFE is an anti-drip agent and is often used to improve the flame retardancy of PLA together with flame retardants. The addition of 4 wt% PTDF and 0.1 wt% PTFE made PLA reach V-0 flame retardant grade from non-flame retardant, and the oxygen index increased from 19.5 % to 24.5 %. With the increase of PTDF content, the performance of PLA improved significantly. The peak heat release rate (PHRR) and THR of PLA/6PTDF composites decrease by 27.4 % and 16.2 %, respectively, and the flame retardant index FRI increase by 232 %, showing excellent flame retardant efficiency. 6 wt% PTDF can increase the crystallinity of PLA by 25.9 %, tensile strength, maximum force required for impact fracture and notch impact strength by 12 %, 37 % and 129 %, respectively, and effectively improve the mechanical properties and toughness of the composite. The bio-based flame-retardant PLA/PTDF composites reported in this paper can be applied to office equipment.

Application of aluminum diethyl hypophosphite, iron-based metal organic framework-NH2-MIL-53(Fe), and expandable graphite complexes as flame retardants for high-density polyethylene

High-density polyethylene (HDPE) composites are made by melt blending HDPE with MIL-53(Fe), amino-functionalized NH2-MIL-53(Fe), aluminum diethyl hypophosphite (ADP), and expandable graphite (EG). The experimental disclosed showed that the aminated NH2-MIL-53(Fe) could improve residual carbon quality and exert a better flame retardant effect than MIL-53(Fe). When 25 wt% of EG/ADP/NH2-MIL-53(Fe) was added and the ratio of EG to ADP/ NH2-MIL-53(Fe) was 1:1, HDPE/EG/ADP/NH2-MIL-53(Fe) composites could achieve a limiting oxygen index of 31.1 %, which passed UL-94 testing and was rated V-0. This results in a considerable improvement in flame retardant efficiency as the peak heat release rate was lowered by 83.4 % and the total heat release was reduced by 35.8 % when compared to the pure HDPE material. Therefore, NH2-MIL-53(Fe)/ADP/EG synergistic flame retardancy can lead to high flame retardancy efficiency in HDPE. This provided a new potential direction for the preparation of highly efficient flame retardants.

Synergistic effect of Co-MOF/epoxy modified tannic acid/ammonium polyphosphate on flame retardancy, anti-melt dripping and mechanical properties of polylactic acid

Achieving flame retardancy and anti-dripping properties in polylactic acid (PLA) while preserving its mechanical integrity remains a significant challenge. In this study, a novel organic ligand rich in phosphorus (P) and nitrogen (N) was synthesized and coordinated with Co2+ions to form a cobalt-based metal–organic framework (Co-MOF) with a multilayer mesoporous structure, acting as an effective carbonization agent. This Co-MOF was then compounded with epoxy-modified tannic acid (eTA) and ammonium polyphosphate (APP) to create a synergistic flame-retardant system for PLA (PLA/MAT). The Co-MOF provides numerous active sites for catalytic oxidation, promoting the formation of a uniform, hill-like expanded carbon layer. During pyrolysis, the Co-MOF and APP yield cobalt oxides and polyphosphates, which catalyze the dehydration of PLA and eTA, facilitating carbonization and forming a continuous, dense protective layer. Consequently, the PLA/MAT system exhibits both robust mechanical properties and excellent flame retardancy, as demonstrated by a limiting oxygen index (LOI) of 27.0 % and a UL-94 V-0 rating, with no melt dripping observed during combustion tests. This work offers a novel approach for enhancing the flame retardancy and anti-dripping performance of PLA, with potential applications in engineering, electronics, and the automotive industry.

Phosphorus-nitrogen-containing flame-retardant plasticizers derived from L-lactic acid for poly (lactic acid) improved toughness, flame retardancy and crystallization

Designing highly-effective and environmentally friendly biobased flame-retardant plasticizers for polylactic acid (PLA) remains a formidable challenge. In this study, we synthesized four novel phosphorus-nitrogen-containing L-lactic acid-based flame-retardant plasticizers with adjustable chemical structures and phosphorus content, designated as NPDL-Cn, where ’n’ corresponds to the alkyl groups numbers in the alkylamine chain (with n = 4, 6, 8, and 10). Incorporating NPDL-Cn into the PLA matrix offered a twofold benefit, significantly enhancing both the flame retardancy and toughness of PLA. Remarkably, as incorporating 20 phr NPDL-Cn, the resulting blends all achieved UL-94 V-0 grade, and their limiting oxygen index reached about 30.8 %, 29.5 %, 28.3 % and 27.2 %, respectively. A comprehensive analysis of the volatile gases and char layer generated during combustion showed that the flame-retardant mechanism of NPDL-Cn in PLA significantly influenced both the condensed-phase and gas-phase behavior. Meanwhile, NPDL-Cn effectively overcame the brittleness and rigidity of PLA, thus realizing the enhancement of its toughness. In particular, as compared to a mere 3.7 % and 1.7 MJ/m3 for neat PLA, when the methylene numbers of NPDL-Cn were 4, the elongation at break and tensile toughness of the PLA/NPDL-C4 exhibited a substantial increase to 180.1 % and 43.4 MJ/m3, respectively, due to the best interfacial tension of NPDL-C4 with PLA matrix. Additionally, while the tensile strength of neat PLA is notably high at 50.7 MPa, the introduction of PLA/NPDL-C4 results in a significant decrease to 26.3 MPa. Interestingly, biodegradation experiments showed that NPDL-C4 was decomposed into non-toxic and harmless small molecules. This study presents a method for constructing toughened and flame-retardant PLA blends by modulating the alkyl chain length of flame-retardant plasticizers and elucidating their structure–property relationships.

A novel macromolecular flame retardant based on sulfonyl diphenol monomer for simultaneous fire safety, transparency and high performance of thin-walled polycarbonate

In order to further advance the development of transparency, fire safety, and high-performance thin-walled polycarbonate (PC), it is essential to avoid the negative impact of traditional flame retardants on the overall performance of PC. In this work, a new copolymer polycarbonate (ASPC) containing sulfonyl diphenol monomer was synthesized by interfacial polycondensation, and it was used as a flame retardant for PC. Due to the fact that the compounds containing sulfonic acid groups produced by the decomposition of ASPC in a high temperature environment promote the crosslinking and rearrangement of PC, the PC can generate a denser char layer during combustion, thus effectively preventing the exchange of heat and gas inside and outside the matrix. To addition of 20 wt% ASPC can make PC with a thickness of 1.5 mm to pass the UL 94 V-0 rating and LOI increased to 33.5 %. The peak of heat release rate (PHRR) and smoke produce rate (PSPR) of PC/ASPC-20 was decreased by 32.4 % and 38.4 %, respectively. More importantly, the addition of ASPC can delay the speed of flame spread, provide people with more escape time and reduce the fire hazard. Furthermore, the ASPC is good compatibility with PC due to the structural similarity between ASPC and PC. Therefore, PC/ASPC maintains the comparable transparency and tensile properties of PC. The transmittance of PC/ASPC-20 is 87.7 %, and the elongation at break is 32.5 % higher than that of PC. This work provides a new solution for the preparation of flame-retardant modification of transparent and thin-walled PC, and expands the application scope of PC composites.

Flexible and Flame Retardant Cotton Fiber-reinforced CS/CNF/EP Composites For a Sensitive Fire Warning

Enhancing fire safety performance in resin-based composites is critical for mitigating fire hazards. Composites that provide early warnings during initial fire stages and maintain prolonged alarm capabilities under flame exposure are essential for minimizing injuries and property damage. This study employs chitosan (CS) as a cross-linking and char-forming agent, while carbon nanofiber (CNF) acts as a flame retardant and conductive component. Cotton fiber-reinforced chitosan/carbon nanofiber composites with varying epoxy and CNF contents (CS/CNF/EP) were prepared through a straightforward low-temperature curing process (40 °C, 4 h). Crosslinking polymerization between chitosan and epoxy was confirmed via Fourier Transform Infrared Spectroscopy (FTIR). The presence of the tough structure of CS and the rigid structure of EP results in a synergistic toughening and reinforcement effect in the CS/CNF/EP composites. Additionally, due to the carbon facilitating properties of CS and the enhanced conductivity of CNF, the composites exhibit a sensitive fire alarm functionality. At 35 % epoxy content, the CS/CNF/EP composites demonstrated exceptional properties, including mechanical flexibility (tensile strength of 7.09 MPa and breaking elongation of 129.05 %) and outstanding flame retardancy (LOI of 32.3 % and UL-94 V-0 rating). These composites provided a rapid alarm (∼1 s), sustaining a 263 s warning under flame exposure and over 35 min post-flame removal. These findings indicate that CS/CNF/EP composites, integrating mechanical flexibility, flame retardancy, and superior fire warning properties, present significant potential applications in fire safety engineering.

Preparation and characterization of HNTs@ZIF enhanced intrinsic flame retardant RTV silicone rubber

Phenylphosphonyl dichloride (BPOD) and 3-aminopropyltriethoxysilane (APTES) were used to prepare phosphorus-nitrogen hexaethoxysilane (BPTES). BPTES was then used for cross-linking and curing hydroxyl-terminated room-temperature vulcanized (RTV) silicone rubber, providing intrinsic flame retardancy. In addition, halloysite (HNTs) is a kind of tubular silicate, taking advantage of its large aspect ratio, HNTs were used as a template to load ZIF67 on the surface of halloysite to obtain HNTs@ZIF tubular filler. It was added to the above system as a reinforcing and flame-retardant filler by physical blending, and the RTV elastomer with excellent performance was prepared. The successful preparation of phosphorus-containing crosslinkers (BPTES) was demonstrated by FT-IR. After the introduction of the new crosslinker, RTV not only has improved flame retardant performance, but also improved mechanical properties. The tensile strength and elongation at break of RTV with 20 wt.% BPTES are increased by 151% and 211%, respectively. The peak heat release rate (pHRR) and the peak of smoke production rate (pSPR) are reduced by 55.9% and 48.6%, respectively, and the thermal stability is also improved. In addition, the successful preparation of HNTs@ZIF was confirmed by FT-IR, XRD, XPS, and TEM. By introducing 2 wt.% HNTs@ZIF into 20 wt.% BPTES cured RTV, the intrinsically flame-retardant RTVs with enhanced performance were prepared. It is worth noting that when 2 wt.% HNTs@ZIF is added, the flame retardant and smoke suppression properties of phosphorus-containing silicone rubber are further improved. Because the ZIF contains cobalt metal ions that can be catalyzed into carbon. The pHRR and pSPR decrease by 18.3% and 16.3%, respectively, and the total heat release (THR) and total smoke production (TSP) decrease by 23.6% and 24.4%, respectively. This work will provide enlightenment for the study of intrinsic flame-retardant RTVs enhanced by modified halloysite.