Fire retardant polymers : recent developments and opportunities

In this Feature Article, we discuss recent developments of flame retardant polymers. Three approaches are considered: (i) inherently flame retardant polymers, (ii) chemically modified polymers and (iii) flame retardants as additives for polymers. We have tried to show the new directions and concepts emerging in the field of flame retardancy. We have mainly focused our comments on flame retardants, nanofillers and surface treatment because very promising concepts appeared recently in the published literature. Synergistic aspects are also fully discussed.

[1]  J. A. Rhys Intumescent coatings and their uses , 1980 .

[2]  J. F. Wolfe,et al.  Rigid-rod polymers. 2. Synthesis and thermal properties of para-aromatic polymers with 2,6-benzobisthiazole units in the main chain , 1981 .

[3]  E. Choe,et al.  Synthesis, spinning, and fiber mechanical properties of poly(p-phenylenebenzobisoxazole) , 1981 .

[4]  Vytenis Babrauskas,et al.  Development of the cone calorimeter—A bench-scale heat release rate apparatus based on oxygen consumption† , 1982 .

[5]  E. Scamporrino,et al.  Intumescent flame retardants for polymers. II. The polypropylene‐ammonium polyphosphate‐polyurea system , 1983 .

[6]  Y. Halpern,et al.  Fire retardancy of thermoplastic materials by intumescence , 1984 .

[7]  G. Camino,et al.  Study of the mechanism of intumescence in fire retardant polymers. Part II: Mechanism of action in polypropylene - ammonium polyphosphate - pentaerythritol mixtures , 1984 .

[8]  Giovanni Camino,et al.  Study of the mechanism of intumescence in fire retardant polymers: Part VI—Mechanism of ester formation in ammonium polyphosphate-pentaerythritol mixtures , 1984 .

[9]  W. J. Kroenke Low-melting sulphate glasses and glass-ceramics, and their utility as fire and smoke retarder additives for poly(vinyl chloride) , 1986 .

[10]  F. Arnold The Birth of Ordered Polymer Technology for Air Force Applications , 1988 .

[11]  René Delobel,et al.  Thermal Behaviours of Ammonium Polyphosphate-Pentaerythritol and Ammonium Pyrophosphate-Pentaerythritol Intumescent Additives in Polypropylene Formulations , 1990 .

[12]  J. Lichtenhan,et al.  Linear Hybrid Polymer Building Blocks: Methacrylate-Functionalized Polyhedral Oligomeric Silsesquioxane Monomers and Polymers , 1995 .

[13]  Mark S. Jones,et al.  Chemical modification of polymers to improve flame retardance—I. The influence of boron-containing groups , 1996 .

[14]  J. Brosse,et al.  Chemical modification of epoxy resins by dialkyl(or aryl) phosphates: Evaluation of fire behavior and thermal stability , 1996 .

[15]  S. Bourbigot,et al.  SYNERGISTIC EFFECT OF ZEOLITE IN AN INTUMESCENCE PROCESS : STUDY OF THE CARBONACEOUS STRUCTURES USING SOLID-STATE NMR , 1996 .

[16]  Young Hee Lee,et al.  Crystalline Ropes of Metallic Carbon Nanotubes , 1996, Science.

[17]  J. Gilman,et al.  Thermolysis of Polyhedral Oligomeric Silsesquioxane (POSS) Macromers and POSS−Siloxane Copolymers , 1996 .

[18]  Emmanuel P. Giannelis,et al.  Polymer Layered Silicate Nanocomposites , 1996 .

[19]  Y. L. Tallec,et al.  New intumescent formulations of fire-retardant polypropylene : Discussion of the free radical mechanism of the formation of carbonaceous protective material during the thermo-oxidative treatment of the additives , 1996 .

[20]  B. Costes,et al.  Synthesis and formulation of novel phosphorylated flame retardant curatives for thermoset resins , 1996 .

[21]  S. Bourbigot,et al.  Zeolites : New synergistic agents for intumescent fire retardant thermoplastic formulations : Criteria for the choice of the zeolite , 1996 .

[22]  S. Bourbigot,et al.  Synergistic effect of zeolite in an intumescence process. Study of the interactions between the polymer and the additives , 1996 .

[23]  Kathryn M. Butler Physical Modeling of Intumescent Fire Retardant Polymers | NIST , 1997 .

[24]  Zhi-Ling Ma,et al.  Synthesis and properties of intumescent, phosphorus‐containing, flame‐retardant polyesters , 1997 .

[25]  Ying‐Ling Liu,et al.  Flame-retardant polyurethanes from phosphorus-containing isocyanates , 1997 .

[26]  Takashi Kashiwagi,et al.  NANOCOMPOSITES : A REVOLUTIONARY NEW FLAME RETARDANT APPROACH , 1997 .

[27]  P. Balaguru,et al.  FIRE RESISTANT ALUMINOSILICATE COMPOSITES , 1997 .

[28]  Gasification of silicone fluids under external thermal radiation. Part I. Gasification rate and global heat of gasification , 1998 .

[29]  S. Bourbigot,et al.  Combustion behaviour of ethylene vinyl acetate copolymer‐based intumescent formulations using oxygen consumption calorimetry , 1998 .

[30]  G. Camino,et al.  Epoxy resins cured with aminophenylmethylphosphine oxide—II. Mechanism of thermal decomposition , 1998 .

[31]  M. Northolt,et al.  Mechanical properties and structural transitions in the new rigid-rod polymer fibre PIPD (`M5') during the manufacturing process , 1998 .

[32]  S. Bourbigot,et al.  Recent advances in the use of zinc borates in flame retardancy of EVA , 1999 .

[33]  Sophie Duquesne,et al.  Modeling of Heat Transfer of a Polypropylene-Based Intumescent System during Combustion , 1999 .

[34]  M. Lewin Synergistic and Catalytic Effects in Flame Retardancy of Polymeric Materials— An Overview , 1999 .

[35]  Jeffrey W. Gilman,et al.  Flammability and thermal stability studies of polymer layered-silicate (clay) nanocomposites , 1999 .

[36]  S. Bourbigot,et al.  New approach to flame retardancy using plasma assisted surface polymerisation techniques , 1999 .

[37]  S. Bourbigot,et al.  New approach to the dynamic properties of an intumescent material , 1999 .

[38]  Stéphanie Roualdes,et al.  Organic/inorganic thin films deposited from diethoxydimethylsilane by plasma enhanced chemical vapor deposition , 1999 .

[39]  S. Bourbigot,et al.  Rheological investigations in fire retardancy: application to ethylene–vinyl‐acetate copolymer–magnesium hydroxide/zinc borate formulations , 2000 .

[40]  Serge Bourbigot,et al.  Use of polyurethanes as char‐forming agents in polypropylene intumescent formulations , 2000 .

[41]  M. E. Hall,et al.  Flame retardant textile back-coatings. Part 2. Effectiveness of phosphorus-containing flame retardants in textile back-coating formulations , 2000 .

[42]  Richard H. Harris,et al.  Flammability Properties of Polymer - Layered-Silicate Nanocomposites. Polypropylene and Polystyrene Nanocomposites , 2000 .

[43]  C. A. Wilkie,et al.  Thermal and Fire Studies on Polystyrene-Clay Nanocomposites , 2000 .

[44]  Serge Bourbigot,et al.  Thermoplastic Polyurethanes as Carbonization Agents in Intumescent Blends. Part 2: Thermal Behavior of Polypropylene/Thermoplastic Polyurethane/Ammonium Polyphosphate Blends , 2000 .

[45]  S. Bourbigot,et al.  The Use of Clay in an EVA-Based Intumescent Formulation. Comparison with the Intumescent Formulation Using Polyamide-6 Clay Nanocomposite As Carbonisation Agent , 2001 .

[46]  W. Chow,et al.  Flammability Studies of Fire Retardant Coatings on Wood , 2001 .

[47]  Günter Beyer,et al.  Flame retardant properties of EVA‐nanocomposites and improvements by combination of nanofillers with aluminium trihydrate , 2001 .

[48]  R. Farris,et al.  Novel polyolefin nanocomposites: Synthesis and characterizations of metallocene-catalyzed polyolefin polyhedral oligomeric silsesquioxane copolymers , 2001 .

[49]  C. A. Wilkie,et al.  Studies on the Mechanism by Which the Formation of Nanocomposites Enhances Thermal Stability , 2001 .

[50]  C. A. Wilkie,et al.  Fire Properties of Polystyrene-Clay Nanocomposites , 2001 .

[51]  T. Kashiwagi,et al.  Fire Retardancy and Thermal Stability of Materials Coated by Organosilicon Thin Films Using a Cold Remote Plasma Process , 2001 .

[52]  Menachem Lewin,et al.  Synergism and catalysis in flame retardancy of polymers , 2001 .

[53]  I. Hamerton,et al.  RECENT DEVELOPMENTS IN THE CHEMISTRY OF HALOGEN-FREE FLAME RETARDANT POLYMERS , 2002 .

[54]  R. Farris,et al.  Synthesis and thermal properties of hybrid copolymers of syndiotactic polystyrene and polyhedral oligomeric silsesquioxane , 2002 .

[55]  C. A. Wilkie,et al.  An XPS study of the thermal degradation and flame retardant mechanism of polystyrene-clay nanocomposites , 2002 .

[56]  R. Delobel,et al.  Elaboration of fire retardant coatings on polyamide-6 using a cold plasma polymerization process , 2002 .

[57]  W. Fan,et al.  Preparation and flammability of ethylene-vinyl acetate copolymer/montmorillonite nanocomposites , 2002 .

[58]  S. Duquesne,et al.  A comparative study of the mechanism of action of ammonium polyphosphate and expandable graphite in polyurethane , 2002 .

[59]  Hongyao Xu,et al.  Preparations, Thermal Properties, and Tg Increase Mechanism of Inorganic/Organic Hybrid Polymers Based on Polyhedral Oligomeric Silsesquioxanes , 2002 .

[60]  S. Bourbigot,et al.  Crystallization behavior of PA-6 clay nanocomposite hybrid , 2002 .

[61]  R. Delobel,et al.  Thermal stability and flammability studies of coated polymer powders using a plasma fluidized bed process , 2002 .

[62]  T. Kashiwagi,et al.  Thermal Degradation and Flammability Properties of Poly(propylene)/Carbon Nanotube Composites , 2002 .

[63]  A. Hirsch Functionalization of single-walled carbon nanotubes. , 2002, Angewandte Chemie.

[64]  S. Bourbigot,et al.  Heat resistance and flammability of high performance fibres: A review , 2002 .

[65]  T. Cheng,et al.  Fire-resistant geopolymer produced by granulated blast furnace slag , 2003 .

[66]  T. Kashiwagi,et al.  Thermal and flammability properties of a silica-poly(methylmethacrylate) nanocomposite , 2003 .

[67]  C. A. Wilkie,et al.  Investigation of nanodispersion in polystyrene–montmorillonite nanocomposites by solid‐state NMR , 2003 .

[68]  C. A. Wilkie,et al.  Nanocomposites based on poly (ϵ-caprolactone) (PCL)/clay hybrid: polystyrene, high impact polystyrene, ABS, polypropylene and polyethylene , 2003 .

[69]  R. Laine,et al.  Organic/inorganic hybrid composites from cubic silsesquioxanes. Epoxy resins of octa(dimethylsiloxyethylcyclohexylepoxide) silsesquioxane , 2003 .

[70]  G. Marosi,et al.  Fire retardancy effect of migration in polypropylene nanocomposites induced by modified interlayer , 2003 .

[71]  S. Bourbigot,et al.  Expandable graphite: A fire retardant additive for polyurethane coatings , 2003 .

[72]  Bin Zhao,et al.  Thermal stability and flammability of polyamide 66/montmorillonite nanocomposites , 2003 .

[73]  Michel Couzi,et al.  Characterization of multiwall carbon nanotubes and influence of surfactant in the nanocomposite processing , 2003 .

[74]  S. Duquesne,et al.  Elaboration of EVA–nanoclay systems—characterization, thermal behaviour and fire performance , 2003 .

[75]  Smoke Development and Suppression , 2004 .

[76]  B. Qu,et al.  Synergistic flame retardant mechanism of fumed silica in ethylene-vinyl acetate/magnesium hydroxide blends ☆ , 2004 .

[77]  Takashi Kashiwagi,et al.  Flame retardant mechanism of polyamide 6–clay nanocomposites ☆ , 2004 .

[78]  Sophie Duquesne,et al.  Intumescent paints: fire protective coatings for metallic substrates , 2004 .

[79]  Serge Bourbigot,et al.  Kinetic analysis of the thermal degradation of polystyrene–montmorillonite nanocomposite , 2004 .

[80]  S. Bourbigot,et al.  Solid State NMR Characterization and Flammability of Styrene-Acrylonitrile Copolymer Montmorillonite Nanocomposite , 2004 .

[81]  Yuan Hu,et al.  Polypropylene/montmorillonite nanocomposites and intumescent, flame‐retardant montmorillonite synergism in polypropylene nanocomposites , 2004 .

[82]  S. Bourbigot,et al.  Recent Advances for Intumescent Polymers , 2004 .

[83]  P. Joseph,et al.  Thermal degradation and flammability characteristics of some polystyrenes and poly(methyl methacrylate)s chemically modified with silicon-containing groups , 2004 .

[84]  Bernhard Schartel,et al.  Layered silicate polymer nanocomposites: new approach or illusion for fire retardancy? Investigations of the potentials and the tasks using a model system , 2004 .

[85]  R. Delobel,et al.  Elaboration of a fire retardant coating for polyamide-6 using cold plasma polymerization of a fluorinated acrylate , 2004 .

[86]  Kathryn M. Butler,et al.  Thermal and flammability properties of polypropylene/carbon nanotube nanocomposites , 2004 .

[87]  B. Mutel,et al.  Characterization of organosilicon films synthesized by N2-PACVD. Application to fire retardant properties of coated polymers , 2004 .

[88]  Joseph G. Smith,et al.  Flame retardant aircraft epoxy resins containing phosphorus , 2005 .

[89]  S. Duquesne,et al.  Thermoplastic resins for thin film intumescent coatings – towards a better understanding of their effect on intumescence efficiency , 2005 .

[90]  E. Leroy,et al.  Use of oxide nanoparticles and organoclays to improve thermal stability and fire retardancy of poly(methyl methacrylate) , 2005 .

[91]  Richard H. Harris,et al.  Nanoparticle networks reduce the flammability of polymer nanocomposites , 2005, Nature materials.

[92]  Yuan Hu,et al.  Study on the properties of flame retardant polyurethane/organoclay nanocomposite , 2005 .

[93]  C. A. Wilkie,et al.  The Relationship Between Thermal Degradation Behavior of Polymer and the Fire Retardancy of Polymer/Clay Nanocomposites , 2005 .

[94]  T. Kashiwagi,et al.  Flammability properties of polymer nanocomposites with single-walled carbon nanotubes: effects of nanotube dispersion and concentration * , 2005 .

[95]  Serge Bourbigot,et al.  Flame retarded polyurea with microencapsulated ammonium phosphate for textile coating , 2005 .

[96]  M. Döring,et al.  Novel phosphorous-containing aromatic polyethers : synthesis and characterization , 2005 .

[97]  S. Bourbigot,et al.  Preparation of Homogeneously Dispersed Multiwalled Carbon Nanotube/Polystyrene Nanocomposites via Melt Extrusion Using Trialkyl Imidazolium Compatibilizer , 2005 .

[98]  Yu-Zhong Wang,et al.  Flame-retardant and anti-dripping effects of a novel char-forming flame retardant for the treatment of poly(ethylene terephthalate) fabrics , 2005 .

[99]  C. A. Wilkie,et al.  Effects of Surfactants on the Thermal and Fire Properties of Poly(Methyl Methacrylate)/Clay Nanocomposites , 2005 .

[100]  G. Camino,et al.  New nanocomposites constituted of polyethylene and organically modified ZnAl-hydrotalcites , 2005 .

[101]  Paul H. Maupin,et al.  Synthesis of imidazolium salts and their application in epoxy montmorillonite nanocomposites , 2006 .

[102]  M. Tsafack,et al.  Plasma-induced graft-polymerization of flame retardant monomers onto PAN fabrics , 2006 .

[103]  M. Lewin Reflections on migration of clay and structural changes in nanocomposites , 2006 .

[104]  G. Marosi,et al.  Flame retardancy of epoxy resin with phosphorus‐containing reactive amine and clay minerals , 2006 .

[105]  Thermal stability and fire behavior of intumescent systems in presence of layered inorganic fillers and silica , 2006 .

[106]  S. Bourbigot,et al.  Polymer Nanocomposites: How to Reach Low Flammability? , 2006 .

[107]  Synthesis, crosslinking and flame retardance of polymers of boron-containing difunctional styrenic monomers , 2006 .

[108]  B. Guo,et al.  Thermal stability and flame retardant effects of halloysite nanotubes on poly(propylene) , 2006 .

[109]  G. Beyer Flame retardancy of nanocomposites based on organoclays and carbon nanotubes with aluminium trihydrate , 2006 .

[110]  Qi Wang,et al.  Catalytic action of phospho-tungstic acid in the synthesis of melamine salts of pentaerythritol phosphate and their synergistic effects in flame retarded polypropylene , 2006 .

[111]  S. Bourbigot,et al.  Intumescent fire protective coating: Toward a better understanding of their mechanism of action , 2006 .

[112]  Sophie Duquesne,et al.  Characterization of the performance of an intumescent fire protective coating , 2006 .

[113]  Fire retardancy of polypropylene- metal hydroxide nanocomposites , 2006 .

[114]  M. Tsafack,et al.  Flame retardancy of cotton textiles by plasma-induced graft-polymerization (PIGP) , 2006 .

[115]  A. I. Balabanovich,et al.  Novel phosphorus-modified polysulfone as a combined flame retardant and toughness modifier for epoxy resins , 2007 .

[116]  J. Nagy,et al.  How Carbon Nanotube Crushing can Improve Flame Retardant Behaviour in Polymer Nanocomposites , 2007 .