High-value use of lignocellulosic-rich eucommia residue for promoting mechanical properties and flame retardancy of poly(butylene succinate)

Cellulose- and lignin-based fillers can significantly enhance the mechanical properties and flame retardancy of biomass polyesters, whereas complicated and high-cost processes may be necessary for the extraction. Thus, we explored the direct use of eucommia residues (ERs), a plantation waste containing rich lignocellulosic substances (ca. 18% cellulose, 13% hemicellulose, and 35% lignin), to reinforce polyesters and improve their flame retardancy. With poly(butylene succinate) (PBS) as the polyester matrix, the ER could enhance the tensile and flexural modulus of polyester-based composite by 87 and 72%, respectively, via a facile melt-mixing method with 30 wt % ER. Such enhancements, accompanying cost reduction, came from the cellulose crystallinity and rigid chemical structure of lignin, along with the strong interaction between ER and PBS. Besides, the carbon residue of PBS/ER composites in the flame-retardant study could maximally increase by 508%, benefited from the immense hex-carbon rings of cellulose and lignin in ERs. The ER also reduced the peak heat release rate and total heat release of PBS by 43 and 20%, respectively. This work reduces the pressure from waste treatment, promotes the high-value application of plantation lignocellulosic-rich wastes in package plastics and membranes, and supports sustainable material development based on biomass multicomponents resources. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48543.     

Application of poly(diphenolic acid‐phenyl phosphate)‐based layer by layer nanocoating in flame retardant ramie fabrics

Poly(diphenolic acid‐phenyl phosphate) [poly(DPA‐PDCP)], obtained from diphenolic acid (a well‐known biomass chemical), was used together with polyethylenimine (PEI) to construct a flame retardant surface coating for ramie fabric using layer‐by‐layer self‐assembly. Attenuated total reflection Fourier transform infrared spectroscopy (ATR‐FTIR) and scanning electron microscope (SEM) equipped with an energy dispersive X‐ray spectrometer (EDX) were used to confirm the successful formation of layer by layer assembly. Assessment of the thermal and flammability properties for poly(DPA‐PDCP)/PEI‐coated ramie fabrics showed that the thermal stability, flame retardancy, and residual char were enhanced as the concentration of poly(DPA‐PDCP) and the BL number in the LbL process increased as well as the treatment of KH550 was applied. SEM and EDX analysis of the char residue confirmed further the intumescent flame retardant mechanism. This work demonstrated the great potentials of poly(DPA‐PDCP)/PEI flame retardant nanocoating constructed by LbL assembly method in the application of ramie fabric. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44795.     

Effect of a novel phosphorus‐containing compound on the flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A novel flame retardant, tetra(5,5‐dimethyl‐1,3‐ dioxaphosphorinanyl‐2‐oxy) neopentane (DOPNP), was synthesized successfully, and its structure was characterized by FT‐IR, ¹H NMR, and ³¹P NMR. The thermogravimetric analysis (TGA) results demonstrate that DOPNP showed a good char‐forming ability. Its initial decomposition temperature was 236.4°C based on 1% mass loss, and its char residue was 41.2 wt % at 600°C, and 22.9 wt % at 800°C, respectively. The flame retardancy and thermal degradation behavior of novel intumescent flame‐retardant polypropylene (IFR‐PP) composites containing DOPNP were investigated using limiting oxygen index (LOI), UL‐94 test, TGA, cone calorimeter (CONE) test, and scanning electron microscopy (SEM). The results demonstrate that DOPNP effectively raised LOI value of IFR‐PP. When the loading of IFR was 30 wt %, LOI of IFR‐PP reached 31.3%, and it passed UL‐94 V‐0. TGA results show that DOPNP made the thermal decomposition of IFR‐PP take place in advance; reduced the thermal decomposition rate and raised the residual char amount. CONE results show that DOPNP could effectively decrease the heat release rate peak of IFR‐PP. A continuous and compact char layer observed from the SEM further proved the flame retardance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Flexible transparent flame‐retardant membrane based on a novel UV‐curable phosphorus‐containing acrylate

A novel phosphorus‐containing acrylate monomer (AOPA) was synthesized starting from 2‐methy‐2,5‐dioxo‐1,2‐oxaphospholane and hydroxyethyl acrylate. The structure of AOPA was characterized with FTIR and ¹H NMR. AOPA shows good compatibility with polyethylene glycol diacrylate (PEGDA) and can polymerize with PEGDA under UV light irradiation at different mass ratios to form membranes with high transparency (above 88.9% of light transmittance in the range of 400‐800 nm) and flexibility. Incorporating 20 wt% of AOPA in PEGDA reduced the total heat release and peak rate by 50.3% and 38.4%, respectively, as measured by micro combustion calorimeter. The membrane containing 40 wt% of AOPA with 0.4 mm thickness can pass the UL94 V0 rating, and limiting oxygen index reaches 33.4%. TG‐FTIR and SEM‐EDX analysis show that the presence of AOPA depresses the thermal degradation and promotes the char formation.     

Novel flame retardant thermosets from nitrogen‐containing and phosphorus‐containing epoxy resins cured with dicyandiamide

A novel phosphorus‐containing epoxy resin (EPN‐D) was prepared by addition reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and epoxy phenol‐ formaldehyde novolac resin (EPN). The reaction was monitored by epoxide equivalent weight (EEW) titration, and its structure was confirmed by FTIR and NMR spectra. Halogen‐free epoxy resins containing EPN‐D resin and a nitrogen‐containing epoxy resin (XT resin) were cured with dicyandiamide (DICY) to give new halogen‐free epoxy thermosets. Thermal properties of these thermosets were studied by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), thermal mechanical analyzer (TMA) and thermal‐gravimetric analysis (TGA). They exhibited very high glass transition temperatures (T_gs, 139–175°C from DSC, 138–155°C from TMA and 159–193°C from DMA), high thermal stability with T_{d,5 wt %} over 300°C when the weight ratio of XT/EPN‐D is ≥1. The flame‐retardancy of these thermosets was evaluated by limiting oxygen index (LOI) and UL‐94 vertical test. The thermosets containing isocyanurate and DOPO moieties showed high LOI (32.7–43.7) and could achieve UL‐94 V‐0/V‐1 grade. Isocyanurate and DOPO moieties had an obvious synergistic effect on the improvement of the flame retardancy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

A novel bio-based charcoal-forming agent based on chitosan and phytate@Mg to improve the flame retardancy of poly(lactic acid)

A novel bio-based carbon forming agent (Mg@PA-CS) containing P and N elements was were synthesized using the complexation characteristics of chitosan (CS) and phytate (PA). The flame retardant behavior of poly(lactic acid) (PLA)/Mg@PA-CS/APP composites (addition of 20 wt% of different ratios of Mg@PA-CS and APP to polylactic acid composites) were investigated by the limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimetry test (CCT), and thermogravimetric analysis (TGA). Due to the biphasic flame retardant and synergistic effect, since the 20 wt% flame retardant system (Mg@PA-CS:APP = 1:2), PLA composites passed the UL-94 test V-0 rating, reached 34% LOI value. The peak heat release rate (PHRR) and total heat release rate (THR) were reduced to 1/2 of the pure PLA, char residue could be as high as 11.49% at 800°C. Moreover, the flame-retardant mechanism of PLA composites during thermal decomposition was analyzed using a scanning electron microscope (SEM) and the coupling techniques of TGA linked with FT-IR (TG-FTIR).     

Biocomposites based on lignin and plasticized poly(L‐lactic acid)

In this research work, biocomposites based on a ternary system containing softwood Kraft lignin (Indulin AT), poly‐L ‐lactic acid (PLLA) and polyethylene glycol (PEG) have been developed. Two binary systems based on PLLA/PEG and PLLA/lignin have also been studied to understand the role of plasticizer (i.e., PEG) and filler (i.e., lignin) on the overall physicomechanical behavior of PLLA. All samples have been prepared by melt‐blending. A novel approach has also been introduced to improve the compatibility between PLLA and PEG by using a transesterification catalyst under reactive‐mixing conditions. In PEG plasticized PLLA flexibility increases with increasing content of PEG and no significant effect of the molecular weight of PEG on the flexibility of PLLA has been observed. Differential scanning calorimetry and size‐exclusion chromatography along with FTIR analysis show the formation of PLLA‐b‐PEG copolymer for high temperature processed PLLA/PEG systems. On the other hand, binary systems containing lignin show higher stiffness than PLLA/PEG system and good adhesion between the particles and the matrix has been observed by scanning electron microscopy. However, a concomitant good balance in stiffness introduced by the lignin particles and flexibility introduced by PEG has been observed in the ternary systems. This study also showed that high temperature reactive melt‐blending of PLLA/PEG leads to the formation of a segmented PLLA‐b‐PEG block copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical,thermal and combustion properties of intumescent flame retardant biodegradable poly (lactic acid) composites

ABSTRACT

Despite extraordinary mechanical properties and excellent biodegradability, poly (lactic acid) (PLA) still suffers from a highly inherent flammability, restricting its applications in the electric and automobile fields. Although a wide range of flame retardants have been developed to reduce the flammability, they normally compromise the mechanical strength of PLA. In this study, a series of composites based on PLA, have been prepared by melt-blending with intumescent flame retardants (IFRs). The morphology, thermal stability and burning behaviour of the composites were investigated using a scanning electron microscope–energy dispersive spectrometer (SEM–EDS), thermogravimetric analysis (TGA), the limiting oxygen index (LOI), vertical burning (UL-94) and the cone calorimeter test (CCT). The LOI value reached 38.5% and UL-94 could pass V-0 for the PLA/IFR composite containing only 12 wt-% IFR. The dispersion of IFR in PLA was observed using SEM–EDS. A significant improvement in fire retardant performance was observed for the PLA/IFR composite from the CCT (reducing the heat release rate and the total heat release). More importantly, compared to pure PLA, the addition of IFR did not seriously deteriorate the mechanical properties of the material.     

The preparation of fully bio‐based flame retardant poly(lactic acid) composites containing casein

In this work, a bio‐based flame retardant, casein, was incorporated into poly(lactic acid) (PLA) matrix by melt compounding in order to improve the fire resistance and sustain the biodegradable character of PLA simultaneously. The fire performance of PLA composites was evaluated by limiting oxygen index, UL‐94 vertical burning, and cone calorimeter tests, respectively. The results indicated that the introduction of 20% casein increased the limiting oxygen index value of PLA composites from 20.0% to 32.2%, upgraded the UL‐94 rating from no rating to V‐0, and decreased the peak heat release rate from 779 to 639 kW/m². The decomposition products of PLA composites were analyzed by Fourier transform infrared, and the morphology of the char after combustion was observed by scanning electron microscopy. It was suggested that casein took effects in both gas phase by releasing non‐flammable gases (such as NH₃ and H₂O) and condensed phase by the formation of protective char layers. However, the presence of casein in PLA induced an unavoidable deterioration in the mechanical performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46599.     

Intrinsic flame retardancy of poly(lactic acid) bead foams

Linear economy models are no longer acceptable for the plastic industry and a change to a sustainable circular plastic economy must take place. In the field of thermoplastic foams, the biopolymer poly(lactic acid) (PLA) is a suitable alternative for fossil based foams like polystyrene. However, the production of PLA bead foams is still a challenge. In regards to circular plastic economy products, a reduction of the needed polymer additives is aspired to simplify the union of end-of-life plastic streams. Flame retardants (FR) are required in many applications and are often the largest proportion of additives. It turns out that the removal of FRs, for example the removal of the REACh registered FR hexabromocyclododecane for polystyrene foams, requires a great effort. This paper shows that PLA bead foams require no FR to achieve a class E classification for construction products. Therefore, nine PLA types are analyzed by differential scanning calorimetry, thermogravimetric analysis, gel permeation chromatography, and rheotens measurements. From five types, PLA bead foams could be produced with two different densities. In addition, PLA bead foams containing 1.5 wt% alkoxy amine FR were produced. The flammability of the PLA bead foams was investigated by LOI, DIN-4102-1-B2, and cone calorimeter tests.     

A novel phosphorus‐containing copolyester with low melting temperature and high flame retardancy

BACKGROUND: The increasing uses of non‐woven fabrics need the development of a kind of novel flame‐retardant polyester with low melting temperature. Neopentyl glycol (NPG) and 3‐(hydroxyphenylphosphinyl)propionic acid (HPPPA) were used as the third and fourth comonomer to synthesize phosphorus‐containing poly[(ethylene terephthalate)‐co‐(neopentyl terephthalate)] (PENT) with both flame retardancy and low melting temperature. RESULTS: The chemical structure of PENT was confirmed using Fourier transform infrared, ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy. PENT displays a monomodal gel permeation chromatography curve. When the content of NPG was kept at 10 wt% and the content of HPPPA increased to 5 wt%, the melting temperature (T_m) of the resulting PENT5/10 decreases to 171.2 °C, a 34.6 °C decrease compared to that of PENT0/10 (containing no HPPPA). The flammability of the PENTs was characterized with the limiting oxygen index (LOI) test, the UL‐94 vertical test and the cone calorimeter test. The incorporation of HPPPA can significantly improve the flame retardancy of the PENTs, the LOI values of the PENTs increasing from 24.4 to 37.6, as the loading of HPPPA increases from 0 to 5 wt%. CONCLUSION: The PENTs possess both low melting temperatures and excellent flame retardancy. HPPPA can be used as fourth comonomer to improve the flame retardancy of the PENTs, while decreasing the T_m value of the copolyester. Copyright © 2009 Society of Chemical Industry     

Preparation and studies of new phosphorus‐containing diols as potential flame retardants

Several new phosphorus‐containing potential flame retardants (FRs) were prepared and evaluated for heat release reduction potential, by incorporation of the molecules into polyurethane samples, generated from methylene diphenyl diisocyanate and 1,3‐propane diol. The potential FRs were all prepared from commercial diisocyanates, with the phosphorus‐containing substructure introduced as a semicarbazone. All of the target structures were diols, to facilitate their incorporation into a polyurethane main chain. The polyurethane samples were prepared via copolymerization, and analysis clearly demonstrated that the potential FRs were chemically incorporated, prior to heat release testing. The heat‐release reduction potential of these substances was evaluated using the microcombustion calorimeter. Results demonstrated that both heat release reduction potential and char formation were structure dependent. Some of the compounds containing an aromatic core had more effect on char formation (higher char yields) and peak heat‐release rate (lowered heat release) than just phosphorus content alone.     

Improving the flame retardance and melt dripping of poly(lactic acid) with a novel polymeric flame retardant of high thermal stability

A polymeric flame retardant containing phosphorus and nitrogen (PCNFR) was synthesized and characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography. The thermal decomposition temperatures at 10% weight loss (T_{10 wt%}) of PCNFR were around 358 °C, and the char yield at 600 °C reached about 60 wt% both in nitrogen and air by thermogravimetric analysis. The flame retarded poly(lactic acid) (PLA) composites with PCNFR were prepared. The thermogravimetric analysis results showed that PCNFR could improve the thermal stability of the flame retarded PLA composites with low loading (≤10 wt%) and at high temperature zone (≥390 °C). The condensed products from the decomposition of the flame retarded composites at 380 °C and 450 °C for different intervals were analyzed by Raman spectroscopy, and the results showed that time and temperature influenced the structure of the char residue evidently. When incorporating 30 wt% PCNFR into PLA, the limited oxygen index of the flame retarded composites reached 25.0%, and V‐0 rating was achieved. The char residues were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy in detail. Copyright © 2016 John Wiley & Sons, Ltd.     

Halogen Free flame retardant rigid polyurethane foam with a novel phosphorus−nitrogen intumescent flame retardant

A novel phosphorous‐nitrogen containing intumescent flame retardant, toluidine spirocyclic pentaerythritol bisphosphonate (TSPB), was synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR). Flame retardant rigid polyurethane foams (TSPB‐RPUF) were prepared by using TSPB. The flame retardancy of TSPB on rigid polyurethane foams (RPUF) was investigated by the limiting oxygen index (LOI), vertical burning test, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and FTIR. The results showed TSPB exhibited better compatibility with RPUF and lesser negative influence on the mechanical properties of TSPB‐RPUF. When the content of TSPB was 30 pph, the LOI of TSPB‐RPUF could reach 26.5%, and a UL‐94 V‐0 rating was achieved. Furthermore, the TSPB‐RPUF exhibited an outstanding water resistance that it could still obtain a V‐0 rating after water soaking. TGA showed the charring ability of RPUF was relatively poor, However, the residual weight of TSPB‐RPUF was improved greatly. SEM and FTIR indicated the intumescent chars formed from TSPB‐RPUF were compact and smooth, which was a critical factor for protecting the substrate material from burning. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39581.     

Modification of polyethylene and incorporation of fillers for effective reinforcement of mechanical and better flame retardant properties

The effect of incorporation of the two different fillers, i.e. calcium carbonate and magnesium hydroxide, over a concentration range of 0–35% w/w on mechanical and burning properties and hot set test of polyethylene (PE) has been studied. The incorporation of either of these fillers deteriorates mechanical properties such as percent elongation at break and tensile strength of PE. However, modification of PE not only mitigates the reduction in these properties, but brings enhancement in all the aforementioned properties. A clear difference in these properties for the incorporation of each of these fillers to just PE, silane‐grafted but uncured PE, and silane cross‐linked PE has been found. These properties follow the order of superiority as: cross‐linked PE > silane‐grafted uncured PE > physically filled PE. The different properties due to physical bonding of filler, physical bonding in the presence of polar silane grafted onto PE, and that of chemical bonding of filler in cross‐linked PE has been discussed and analyzed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1928–1933, 2006     

An efficient approach to improving fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene composites via incorporating organo‐modified sepiolite

In this work, an efficient approach to improving the fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene (PP) composites is developed via incorporating functionalized sepiolite (organo‐modified sepiolite [ONSep]). The PP composites with different amounts of intumescent flame retardants and ONSep were prepared by melt compounding. The morphology, thermal behavior, fire retardancy, smoke suppression, and mechanical property of flame‐retardant PP composites were studied. The results indicate an appropriate amount of ONSep in the flame‐retardant PP composites can increase thermal degradation temperature and char formation as well as a reduction of the peak heat release rate and total heat release; moreover, the addition of ONSep significantly decreases the CO production, total smoke production, smoke production rate, and smoke temperature. Simultaneously, the impact strength of intumescent flame‐retardant PP composite is also maintained by introducing an appropriate amount of ONSep as compared with that without ONSep.     

Synthesis of modified graphene oxide and its improvement on flame retardancy of epoxy resin

In this work, the small molecule with double-phosphaphenanthrene structure was successfully grafted on the surface of graphene oxide (GO), which is called functionalized graphene oxide (FGO). The introduction of FGO improved the poor interfacial compatibility between graphene and epoxy matrix. And FGO could be used as the highly effective flame retardant. The thermogravimetric analysis results showed a significant improvement in the char yield of cured FGO/EP. When the content of FGO was 3 wt %, the limiting oxygen index value reached 30.4%. At the same time, the three-point bending and thermomechanical tests confirmed that the mechanical properties of the epoxy resin composites were improved. Based on the char analyses of SEM images and Raman spectroscopy, the flame retardant could promote the formation of a stable carbon layer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47710.     

Improvement in the flame retardancy of cotton fabric by admicellar polymerization of 2‐acryloyloxyethyl diethyl phosphate using an anionic surfactant

The phosphorus‐containing acrylate monomer, 2‐acryloyloxyethyl diethyl phosphate (ADEP), was synthesized and applied to cotton fabric by using admicellar polymerization. Sodium dodecylbenzene sulfonate was used as the anionic surfactant. The film of polymerized monomer (PADEP) formed on the cotton surface was characterized by FTIR‐ATR spectroscopy and SEM. Thermal and flame retardant properties of PADEP‐coated cotton were investigated by TGA and flammability tests. Results showed that PADEP polymer film was successfully formed on the cotton fabric. The TGA and DTG analyses showed that the phosphorus‐containing PADEP lowered the decomposition temperature of the treated fabric resulting in a higher char yield than in the case of untreated cotton. The flammability tests showed that the treated cotton had much improved flame retardancy property after the treatment. The treated fabric also retained its good pliability and soft touch with good air permeability. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synergistic effect of MXene on the flame retardancy and thermal degradation of intumescent flame retardant biodegradable poly (lactic acid) composites

The effect of Ti₃C₂ MXene nanosheets on the intumescent flame retardant (IFR) poly (lactic acid) (PLA) composites was investigated among a series of PLA/IFR/MXene, which were prepared by melt blending 0-2.0 wt% MXene, 10.0 wt%-12.0 wt% IFR and PLA together. The results of limiting oxygen index (LOI) and vertical burning (UL-94) discover that the combination of 0.5 wt% MXene and 11.5 wt% IFR synergistically improves the fire safety of PLA to reach UL-94 V-0 rating with LOI value of 33.0%. The PLA/IFR/MXene composites perform an obvious reduction in peak of heat release rate (HRR) in cone calorimeter tests (CCTs). Furthermore, the carbon residues after CCTs were characterized by scanning electron microscope (SEM), laser Raman spectroscopy (LRS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It is demonstrated that both the titanium composition of the MXene structure and the characteristics of the two-dimensional material enhance the PLA/IFR/ MXene composite materials' ability to produce a dense barrier layer to resist burnout during thermal degradation.