Phosphorus and nitrogen supramolecule for fabricating flame-retardant, transparent and robust polyvinyl alcohol film.

Supramolecular flame retardants have attracted increasing attention recently due to their simple and eco-friendly preparation process. In this study, a novel flame retardant HEPFR was prepared using supramolecular self-assembly technology between piperazine and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP). It was introduced into polyvinyl alcohol (PVA) matrix to form PVA/HEPFR composite film. Subsequently, the transparency, mechanical properties, thermal stability, and flame retardancy of PVA/HEPFR films were studied. Due to the hydrogen bonded cross-linked network structure between PVA and HEPFR, the mechanical properties of PVA/HEPFR films have been improved, while maintaining good transparency. With 10 wt% addition of HEPFR, PVA films can reach the VTM-0 level in UL-94 testing. And the limiting oxygen index can be increased from 18.5% of pure PVA to 26.5%. The peak heat release rate was reduced by 61.5%. The flame retardancy and thermal stability of PVA/HEPFR films have been greatly improved. This study provides a "one stone, three birds" strategy for preparing flame-retardant, transparent, and robust PVA film.

Eco-Friendly One-Pot Supramolecular-Assembly of P-N Flame Retardant for Fire-Safe Epoxy Resin.

Flame retardant treatment of epoxy resins (EP) to reduce their flammability for extending their range of applications attracts considerable attention. However, the synthesis process of conventional flame retardants is complicated and involves organic hazardous solvents. Meanwhile, how to ensure both the flame-retardant and mechanical properties is a long-standing and actual difficult problem. In this work, a supramolecular flame retardant (named ATPFR) is facilely created by one-pot reaction, using cheap and accessible raw materials in an ecologically benign aqueous solvent. ATPFR is applied to improve the fire safety of EP. With only 5 wt% ATPFR addition, EP can reach the limiting oxygen index of 28.5% and the UL-94 V-0 rating with a significant "blow-out effect." The cone calorimetry test reveals that the EP thermoset with 5 wt% ATPFR has a 75.8% reduction in the peak heat release rate (p-HRR) and a 67.3% reduction in the peak smoke production rate (p-SPR), respectively, compared with the pure EP. Additionally, EP composites with the small amount of ATPFR exhibit a slight decrease and maintain good mechanical properties. Therefore, the facile synthesis and application of this supramolecular flame retardant provide a reliable way for the construction of polymer materials with environment-friendly and effective flame-retardant system.

Konjac Glucomannan Aerogels Modified by Hydrophilic Isocyanate and Expandable Graphite with Excellent Hydrolysis Resistance, Mechanical Strength, and Flame Retardancy.

At present, biomass foamlike materials are a hot research topic, but they need to be improved urgently due to their defects such as large size shrinkage rate, poor mechanical strength, and easy hydrolysis. In this study, the novel konjac glucomannan (KGM) composite aerogels modified with hydrophilic isocyanate and expandable graphite were prepared by a facile vacuum freeze-drying method. Compared with the unmodified KGM aerogel, the volume shrinkage of the KGM composite aerogel (KPU-EG) decreased from 36.36 ± 2.47% to 8.64 ± 1.46%. Additionally, the compressive strength increased by 450%, and the secondary repeated compressive strength increased by 1476%. After soaking in water for 28 days, mass retention after hydrolysis of the KPU-EG aerogel increased from 51.26 ± 2.33% to more than 85%. The UL-94 vertical combustion test showed that the KPU-EG aerogel can achieve a V-0 rating, and the limiting oxygen index (LOI) value of the modified aerogel can reach up to 67.3 ± 1.5%. To sum up, the cross-linking modification of hydrophilic isocyanate can significantly improve the mechanical properties, flame retardancy, and hydrolysis resistance of KGM aerogels. We believe that this work can provide excellent hydrolytic resistance and mechanical properties and has broad application prospects in practical packaging, heat insulation, sewage treatment, and other aspects.

Surface Flame-Retardant Systems of Rigid Polyurethane Foams: An Overview.

Rigid polyurethane foam (RPUF) is one of the best thermal insulation materials available, but its flammability makes it a potential fire hazard. Due to its porous nature, the large specific surface area is the key factor for easy ignition and rapid fires spread when exposed to heat sources. The burning process of RPUF mainly takes place on the surface. Therefore, if a flame-retardant coating can be formed on the surface of RPUF, it can effectively reduce or stop the flame propagation on the surface of RPUF, further improving the fire safety. Compared with the bulk flame retardant of RPUF, the flame-retardant coating on its surface has a higher efficiency in improving fire safety. This paper aims to review the preparations, properties, and working mechanisms of RPUF surface flame-retardant systems. Flame-retardant coatings are divided into non-intumescent flame-retardant coatings (NIFRCs) and intumescent flame-retardant coatings (IFRCs), depending on whether the flame-retardant coating expands when heated. After discussion, the development trends for surface flame-retardant systems are considered to be high-performance, biological, biomimetic, multifunctional flame-retardant coatings.

Facile synthesis of a novel transparent hyperbranched phosphorous/nitrogen-containing flame retardant and its application in reducing the fire hazard of epoxy resin.

In this study, a novel hyperbranched phosphorus/nitrogen-containing flame retardant (HPNFR) was facilely synthesized via the transesterification reaction of dimethyl methylphosphonate and tris (2-hydroxyethyl) isocyanurate and characterized successfully by 1H NMR and FTIR. The sample with 4 wt% HPNFR can achieve V-0 rating in UL-94 test and possess a LOI value as high as 34.5%. Conspicuous blowing-out effect was observed during the vertical burning test. TG results indicated that the presence of HPNFR significantly improved the thermal stability of EP thermosets. From cone test, THR, p-HRR, p-SPR and TSP values of HPNFR/EP composites were decreased in comparison to those of pure EP, revealing the reduced fire hazard of EP composites with HPNFR. SEM images of EP thermoset with 4 wt% of HPNFR after cone test exhibited compact and continuous char layers, while those of pure EP are fragmentary and broken. From TG-IR test, the yield of toxic CO and other pyrolysis products was significantly reduced, indicating a decrease in toxicity. Phosphorus-containing compounds were detected in gas phase, which verified the gaseous phase flame retardant effect of HPNFR. Besides, HPNFR would not significantly damage the transparence of EP thermosets, consequently reserved it's application value in some special fields.

Density Effect on Flame Retardancy, Thermal Degradation, and Combustibility of Rigid Polyurethane Foam Modified by Expandable Graphite or Ammonium Polyphosphate.

The current study aims at comparatively investigating the effect of apparent density on flame retardancy, thermal degradation and combustion behaviors of rigid polyurethane foam (RPUF), RPUF/ expandable graphite (EG) and RPUF/ ammonium polyphosphate (APP). A series of RPUF, RPUF/EG and RPUF/APP samples with different apparent densities (30, 60 and 90 kg/m³) were prepared. The flame retardancy, thermal degradation, and combustion behaviors of each sample were investigated. Limiting oxygen index (LOI) results indicated that increasing apparent density was beneficial to the flame retardancy of all foam systems. The effect of apparent density on the enhancement of flame retardancy followed the sequence of RPUF < RPUF/APP < RPUF/EG. Thermogravimetric analysis (TGA) results showed that an increase in the apparent density can cause more weight loss in the first degradation stage and less weight loss in the second degradation stage for all foam systems. The combustion behaviors also showed significant differences. The samples with a higher apparent density showed a longer duration of heat release and higher total heat release (THR). The findings in this study demonstrated that apparent density played an important role in flame retardancy, thermal degradation, and combustion behaviors of RPUF, which must be paid more attention in the studies of flame-retardant RPUF.

Mechanical, thermal and fire performance of an inorganic-organic insulation material composed of hollow glass microspheres and phenolic resin.

HYPOTHESIS: Organic foamy materials possess good thermal insulation properties and inorganic materials are non-combustible. Hence, it is possible to develop a kind of organic-inorganic lightweight thermal insulation materials with excellent fire safety. EXPERIMENTS: Hollow glass microsphere (HGM), as one kind of lightweight noncombustible inorganic material, was chosen as the filling material. Phenolic resin (PR), as the flame retardant polymeric material, was used as binding material. A series of HGM/PR composites with various PR/HGM mass ratio were prepared. Properties, such as apparent density, microstructure, mechanical strength, thermal conductivity, burning behavior and flame retardancy of the specimens were determined, respectively. FINDINGS: The results show that the surface of HGM particles is coated by a layer of cured PR and the HGM powder is glued together firmly from the scanning electron microscope (SEM) images. With the increase of PR/HGM mass ratio, both of apparent density and mechanical strength of HGM/PR composites increase, but thermal conductivity and limiting oxygen index (LOI) values decrease, all of the specimens still possess high LOI value (>50%). What's more, no flaming combustion (merely partial carbonization) and hardly any smoke can be observed during the burning process, which indicates the HGM/PR composites possess excellent flame retardant property and fire safety.