Fully bio-based and intrinsically flame retardant unsaturated polyester cross-linked with isosorbide-based diluents.

Unsaturated polyester resins (UPR) are composed of prepolymers and styrene diluents, while the former are produced by co-polycondensation between diol, unsaturated diacid and saturated diacid. In this work, bio-based UPR prepolymers were synthesized from bio-based oxalic acid, itaconic acid, and ethylene glycol, which were then diluted with bio-based isosorbide methacrylate (MI). Meanwhile, the phenylphosphonate were introduced into the molecular chains of prepolymers to achieve intrinsic flame retardancy of bio-based UPR. The potential of the reactive MI diluents as substitutes of volatile styrene, was also assessed through the volatility test, curing kinetics and gel contents analysis. For UPR materials with styrene diluents, the UPR materials can achieve UL-94 V0 level and the 28% of limiting oxygen index (LOI) with 2.63 wt% of phosphorus contents. By contrast, the UPR materials with MI diluents can reach UL-94 V0 level with only 2.14 wt% of phosphorus contents. As the phosphorus contents were further increased to 2.63 wt%, UPR materials can achieve highest 29%, while the peak of heat release rate (PHRR) and total heat release (THR) were decreased by 68.01% and 48.62%, respectively. The Flame Retardancy Index (FRI) was also used to comprehensively evaluate the flame retardant performance of UPR composites. Compared with neat UPR, the composites with MI diluents and phosphorus containing structures increased from 1.00 to 6.46. The mechanism for improved flame retardancy was analyzed from gaseous and condensed phase. Additionally, the tensile strengths of bio-based UPR materials with styrene and MI diluents were studied. This work provides an effective method to prepared high-performance and fully bio-based UPR materials with improved flame retardant properties and safety application of reactive diluents.

A rational design of functionalized black phosphorus cooperates with piperazine pyrophosphate to significantly suppress the fire hazards of polypropylene.

The flammability of polypropylene (PP) not only has negative effects on human health but also causes environmental pollution. Herein, from the molecular polarity point of view, rationally designed hyperbranched charring foaming agents (HCFA) modified black phosphorus nanosheets by in situ polymerization to solve the fire hazards of PP. Based on the UL-94 test V-0 rating, the conventional flame retardant of piperazine pyrophosphate (PAPP) is substituted partly by the BP@PPC. Surprisingly, compared with 27 wt% of PAPP/PP, composites consisting of only 2 wt% of BP@PPC and 20 wt% PAPP/PP also passes the V-0 rating. The results of the cone calorimeter test confirmed that adding BP@PPC decreases the total heat release (THR) and peak heat release (PHRR) by a large amount, which are decreased by 23.4%, 85.8% respectively compared with PP. Moreover, it is uncommon for the fire growth index of BP@PPC composites to be 66.7% lower than that of PAPP/PP composites. In addition, the incorporation of BP@PPC has almost no impact on the mechanical characteristics of PP composites. This study offers a reference for combining established flame retardants with novel compounds to modify the burning behaviors of PP.

Construction of bismaleimide resin with enhanced flame retardancy and mechanical properties based on a novel DOPO-derived bismaleimide monomer.

It's known that the application of bismaleimide resins (BMI) is limited due to its brittleness and poor flame retardancy. A novel type of BMI monomer (MADQ) based on the typical phosphorus series flame retardant DOPO is designed to improve the fire safety of BMI. Besides, aliphatic long chain structure is introduced in MADQ, which is supposed to be conducive to reducing the rigidity of the BMI cross-linked network and thus to improve the toughness of BMI. It's seen that with the incorporation of 5.24 wt% MADQ, the peak of heat release rate (PHRR) and total heat release (THR) of resultant BMI/MADQ-5 is reduced by 37.7% and 33.9%, respectively. Meanwhile, with modification of 1.07 wt% MADQ, BMI/MADQ-1 possesses UL-94V-0 rating. The relevant mechanism analysis reveals that the phosphaphenanthrene group in MADQ can exert flame retardancy effect both in condensed and gas phase. Besides, the impact strength of the BMI/MADQ is maximally increased by nearly 90.1%. Furthermore, the BMI/MADQ still maintains high tensile strength and thermal stability, which indicates the modification of MADQ did not deteriorate other properties of BMI. An innovative research idea and research basis for the preparation of intrinsic flame-retardant and toughened BMI is provided in this work.

Exploration on structural rules of highly efficient flame retardant unsaturated polyester resins.

Owing to the lack of research on structure-activity relationship and interaction mechanism between unsaturated polyester resins (UPR) and flame retardants, it has been a big challenge to prepare high-efficiency flame retardants for UPR in industry. In this research, to explore structural rules of high-efficiency flame retardants, several polymeric flame retardants were synthesized with varied main-chain, side-chain, phosphorus valence states and contents of flame retardant elements. The thermal stabilities of flame retardants and UPR composites were firstly assessed. It has been found the interaction existed between flame retardants and UPR, through transesterification reaction and ß scission pathway in polyester and polystyrene chains. With only 15 wt% of PCH3-S, UPR composites can reach V0 rating in UL-94. The PHRR and THR values can be maximumly decreased by 71.66 % and 77.67 %, with 20 wt% of PB-S. It has been found flame retardants with sulfone group and + 3 valence state of phosphorus in molecular backbone can release SO2 and phosphorus containing compounds in gaseous phase, which diluted fuel fragments and catalyzed H⋅ and HO⋅ radical removal. The mechanism for improved flame retardancy of UPR composites with various polymeric flame retardants were discussed in detail. Some general rules for highly efficient flame retardant UPR can be summarized: First, gaseous phase flame retardant mechanism plays the major role in improvement of flame retardant performance of UPR composites; Second, the combination of + 3 valence state of phosphorus structures, higher phosphorus contents and sulfone groups effectively improves the flame retardant efficiency of flame retardants.

Natural antioxidant functionalization for fabricating ambient-stable black phosphorus nanosheets toward enhancing flame retardancy and toxic gases suppression of polyurethane.

Herein, as a natural antioxidant, tannin (TA) is firstly used to functionalize black phosphorous (BP) nanosheets to improve the ambient stability and toxic suppression, thus decreasing the fire hazards of polymer materials. Compared to pure BP nanosheets, higher temperature for thermal oxidation decomposition is achieved for TA-BP nanosheets, directly confirming the ambient stability of TA-BP nanosheets. Meanwhile, from high resolution TEM and XPS results, TA-BP nanosheets after being exposed at air for 10 days present well-organized crystal structure and low POx bonds content. Cone calorimeter results illustrate that the incorporation of 2.0 wt% TA-BP nanosheets significantly decreases the peak value of heat release rate (-56.5 %), total heat release (-43.0 %), CO2 concentration (-57.3 %) of TPU composite. Meanwhile, with addition of low to 1.5 wt%, the release of highly-toxic CO gas is significantly suppressed, confirmed by lower peak value (0.52 mg/m3) and decreased total release amount (-55.1 %). The obviously enlarged tensile strength (36.7 MPa) and desirable elongation at break (622 %) are also observed. This strategy not only firstly adopts bio-based antioxidant to impart excellent environmental stability for BP nanosheets, but also promotes the promising potentials of BP nanosheets in the fire safety application of polymer composites.