Polyolefins, used widely in electrical applications, roofing, and automotive parts, have a high heat of combustion and tend to burn with substantial fuel evolution and little char. Since the polyolefins can usually accept high loadings of solid additives, aluminum hydroxide and magnesium hydroxide have found use. At lower loadings, vapor-phase-active flame retardants of the halogen-antimony oxide type have proved useful; older chlorinated types are still in use, and both old and new bromine compounds are widely employed in polyolefins. Much effort has been expended on intumescent phosphorus-based additives and there are some newer ones which show promise.
Levchik, S.V. and Weil, E.D. (2007). New Developments in Flame Retardancy of Styrene Thermoplastics and Foams, International Polymers, submitted.
2.
Levchik, S.V. and Weil, E.D. (2007). Flame Retardants for Polystyrenes in Commercial Use or Development, J. Fire Sciences , 25(3): 241—265.
3.
Glass, R.D. and Luther, D. (2002). Overview of Flame Retardant Technology and Associated Applications, presented at Polyolefins 2002: The International Conference on Polyolefins, Houston, TX, 24—27 February.
4.
Zhang, S. and Horrocks, A.R. (2003). A Review of Flame Retardant Polypropylene Fibers, Progress in Polymer Science, 28: 1517—1538.
5.
Lewin, M. and Weil, E.D. (2001). Mechanisms and Modes of Action in Flame Retardancy of Polymers, In: Horrocks, A.R. and Price, D. (eds.), Fire Retardant Materials, Woodhead Publishing Ltd., Cambridge, UK. pp. 31—68.
6.
Fire Retardancy of Polymeric Materials (2000). Grand, A.F. and Wilkie, C.A. (eds), Marcel Dekker Inc., NY.
7.
Cullis, C.F. and Hirschler, M.M. (1982). The Combustion of Organic Polymers, Oxford Univ. Press, Oxford, UK.
8.
Richardson, C.G. (2003). Evolution in the Needs for Compounding Flame Retardant Materials, In Proceedings of the 52nd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, 17—20 November.
9.
Troitzsch, J. (2004). Plastics Flammability Handbook, 3rd edn, Hanser Publishers, Munich/Hanser-Gardner, New York .
10.
Wickström, U. (2006). Reaction to Fire Testing under the CPD, Fire Resistance in Plastics 2006, Conference, Düsseldorf, Germany, 6—8 November.
11.
Cogen, J.M., Whaley, P.D., Lin, T.S. and Bolz, K. (2004). Assessment of Flame Retardancy in Polyolefin-Based Non-Halogen FR Compounds, in Proceedings of the 53rd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, November 14—17.
12.
Whaley, P.D., Cogen, J.M., Lin, T.S. and Bolz (2004 ). Nanocomposite Flame Retardant Performance: Laboratory Testing Methodology, In Proceedings of the 53rd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, 14—17 November.
13.
Lyon, R. (2000). Ignition Resistance of Plastics, International SAMPE Symposium and Exhibition (2003), 48 (Advancing Materials in the Global Economy — Applications, Emerging Markets and Evolving Technologies, Book 2), pp. 1441—1451.
14.
Johnson, P.R. (1974). A General Correlation of the Flammability of Natural and Synthetic Polymers, J. Appl. Polym. Sci., 18: 491—504.
15.
Hornsby, P. and Rothon, R. (2005), chapter 2, In: Le Bras, M., Wilkie, C. and Bourbigot, S. (eds), Fire Retardant Fillers for Polymers: New Applications of Mineral Fillers, Royal Society of Chemistry, Cambridge/ London, UK.
16.
Musselman, L.L. (1990). Production Processes, Properties and Applications for Aluminum-Containing Hydroxides, In: Handbook of Science and Technology of Alumina Chemicals, AmericanCeramic Society, Westerville, OH. pp. 75—91.
17.
Musselman, L.L. (1990). Alumina Chemicals as Additives for Paper, Dentifrices, Paints, Coatings, Rubbers and Plastics with Emphasis on Fire-Retardant Products, In: Handbook of Science and Technology of Alumina Chemicals, AmericanCeramic Society , Westerville, OH. pp. 195—239.
18.
Dando, N.R., Clever, T.R., Kolek, P.L., Pearson, A. and Martin, E.S., Aluminum Trihydroxide (ATH) as a Filler for Polymer Composites: Comparative Evaluation of Precipitation and Grinding on Thermal Stability and Dehydration Kinetics, paper at 51st Annual Conference and Expo '96, Proceedings of the SPI/CI 51st Annual Conference, Session 19A, pp. 1—9.
19.
Levendusky, T.L. and Musselman , L.L. (1983). Alumina Trihydrate as a Flame Retardant and Smoke Suppressant Additive for Polypropylene; Development of a Commercial Flame Retardant Polypropylene, paper at 38th SPE ANTEC, Chicago, IL , May 2—5.
20.
Rex, G. (2005). Rheological Study of Particle Packing in Unsaturated Polyester Resin Loaded With Alumina Trihydrate, paper at Composites 2005, American Composites Manufacturers Assn., Columbus, OH, 28—30 September.
21.
Herbiet, R., Luther, D.W. and Thomas Jr, S.G. (2001),Benefits of Brominated & Mineral Based Flame Retardants for Wire & Cable, In: Proceedings of the 50th International Wire & Cable Symposium, pp. 807—814.
22.
Herbiet, R. (2004). U.S. Pat. Appl. 2004/0063838.
23.
Chen, T. (2003). Comparison of Ground vs. Precipitated Fine Aluminum Trihydrate for Flame Retardant Wire and Cable Applications, paper at 52nd International Wire and Cable Symposium/Focus, Philadelphia, 16—20 November.
24.
Sauerwein, R. (2004). Optimized Mineral Flame Retardants and Synergisms - New Aspects Focused on the Balance of Fire Performance and Polymer Process Ability, In: Flame Retardants 2004, London, 27—28 January, Interscience Communications , Greenwich, UK, pp. 117—127.
25.
Imahashi, T., Okada, A. and Abe, T. (1996), U.S. Pat. 5,583,172.
26.
Shen, K. and Olson, E. (2004). Borates as Fire Retardants in Halogen-Free Polymers , paper presented at 15th Annual BCC Conference on Flame Retardancy, Stamford, CT, 7—9 June.
27.
Innes, J. (2006). Magnesium hydroxide - The other metal hydrate flame retardant, in Fire Resistance in Plastics, Düsseldorf, Germany, 6—8 November.
28.
Lin, T.S., Bunker, S.P., Whaley, P.D., Cogan, J.M., Bolz, K.A. and Alsina, M.F. (2005). Evaluation of Metal Hydroxides and Coupling Agents for Flame Resistant Industrial Cable Applications, In: 54th IWCS/Focus International Wire & Cable Symposium, Providence, RI, 13—16 November.
29.
Hornsby, P.R. (1994). The Application of Magnesium Hydroxide as a Fire Retardant and Smoke-suppressing Additive for Polymers , Fire and Materials,18(5): 269—276.
Chen, T. (2006). Novel Magnesium Hydroxide Products for Non-Halogen Performance Compound Applications, In: Fire Resistance in Plastics Conference, Düsseldorf, Germany, 6—8 November.
32.
Walter, M.D. and Wajer, M.T. (1995). Overview of Flame Retardants Including Magnesium Hydroxide, paper at Functional Filler Conference , Houston, TX, pp. 173—6.
33.
Chen, T. and Lynch, T.J. (2004). Surface Treated Magnesium Hydroxide for Flame Retardant Wire and Cable and TPO Roofing Compounds, paper at 15th Annual BCC Conference on Flame Retardancy, Stamford, CT, 7—9 June.
34.
Schultz, R.E. and Hendrix, A.C. (to J.M. Huber Corp.) (2001). U.S. Pat. 6,242,511.
35.
Chen, T. (2004). Effects of Morphological and Surface Characteristics of Magnesium Hydroxide on Performance of Flame Retardant Wire and Cable Compounds , In: Proceedings of the 53rd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, 14—17 November.
36.
Chen, T. (2005). Magnesium Hydroxide for Flame Retardant Polyolefin pPerformance Compounds, Society of Petroleum Engineers International Conference on Polyolefins 2005: The Challenge of Globalization, 2: 708—720.
37.
Artingstall, L., Preston, J., Sawyer , D. and Pender, A. (2005). A Fifth Generation of HFFR Compounds to Enhance the Performance of Wire and Cable Sheathing, In: 54th IWCS/Focus International Wire & Cable Symposium , Providence, RI, 13—16 November.
38.
Sawyer, D., Artingstall, L. and Preston, A. (1998). PCT Appl. WO 98/10432 (published 12 March).
39.
Chen, T. and Shen, K., Synergistic Benefits of Metal Hydroxides and Zinc Borate in Flame Retardant Wire and Cable Performance Compounds, In: 54th IWCS/Focus International Wire & Cable Symposium, Providence, RI, 13—16 November.
40.
Park, D.H., Ahn, M.J., Kim, S.C. and Lee, G.J. (2001). The Synergistic Effect of MDH and ATH on Flame Retardancy and Smoke Suppression, International Wire and Cable Symposium, 50: 409.
41.
Isarov, A., Chen, T. and Baker, B. (2006). Non-halogen Flame Retardant Polyolefins Containing Magnesium Hydroxide - Effect of Synergistic Fillers on Compound Performance , In: Functional Fillers for Plastics, Intertech-PIRA Conference, Atlanta, GA, Sept. 25—27.
42.
Weil, E.D. (1975). Additivity, Synergism and Antagonism in Flame Retardants, Chapter 3, In: Kuryla, W.C. and Papa, A.J. (eds), Flame Retardancy of Polymeric Materials, Vol. 3, Marcel Dekker, Inc., New York , pp. 186—243.
43.
Weil, E.D. (2000). Synergists, Adjuvants and Antagonists in Flame-Retardant Systems, In: Grand, A. and Wilkie, C. (eds), Fire Retardancy of Polymers , Marcel Dekker, Inc., New York, NY, pp. 116—145.
44.
Clerc, L., Ferry, L., Leroy, E. and Lopez-Cuesta, J.-M. (2005). Influence of Talc Physical Properties on the Fire Retarding Behaviour of (Ethylene-Vinyl Acetate Copolymer/Magnesium Hydroxide/Talc) Composites, Polymer Degradation and Stability , 88(3): 504—511.
45.
Trivedi, P.J. , Deanin, R., Orroth , S.A. and Dunn, R.F. (1999). Synergistic Flame Retardance of Polypropylene, SPE ANTEC, 45: 3682.
46.
Jouffret, F. and Meli, G. (2004). Talc as a Functional Additive in Flame Retardant Systems, In: Flame Retardants 2004 , London , 27—28 January, Interscience Communications , Greenwich, UK, pp. 129—132.
47.
Weil, E. and Zhu, W. (to Polytechnic University) (1995). U.S. Pat. 5,475,041.
48.
Gray, R.L. and Lee, R.E. (1997). The Influence of Flame Retardant Structure on UV Stabilization Approaches in Polypropylene, Angew. Makromol. Chem., 247: 61—72.
49.
Sinturel, C. , Lemaire, J. and Gardette, J.-L. (2000). Photooxidation of fire retardant polypropylene. III. Mechanism of HAS inactivation , Eur. Polym. J., 36: 1431—1443.
50.
Antos, K. and Sedlar, J. (2005). Influence of brominated flame retardant thermal decomposition products on HALS, Polymer Degradation and Stability , 90(1): 188—194.
51.
Bewart, D. and Freyer, W. (2000). U.S. Pat. 6,114,591.
52.
Stein, D. and Stevenson, D. (2003). Chlorinated Paraffins as Effective Low Cost Flame Retardants for Polyethylene, paper at the SPE International Conference on Polyolefins 2003, Houston, TX, 23—26 February.
53.
Chlorinated Paraffins Industry Assn., Regulatory Update, October 2006; www.regnet.com/cpia/;www.epa.gov/oppt/chemtest/pubs/chloropf.htm
Markezich, R. (2004). Low Smoke Formulations for FR Resins, paper presented at 15th Annual BCC Conference on Flame Retardancy, Stamford, CT, 7—9 June.
56.
Shen, K. and Ferm, D.J. (1999). Maximizing Fire Test Performance of Polyolefins with Zinc Borate, paper presented at 10th Annual BCC Conference on Flame Retardancy, Stamford, CT, 24—26 May.
57.
O'Brien, D. (to Belden) (1996). U.S. Pat. 5,525,757.
58.
Markezich, R. (1999). Bromine-chlorine Synergism, paper presented at 10th Annual BCC Conference on Flame Retardancy, Stamford, CT, 24—26 May.
59.
O'Brien, D. (to Belden) (1994), U.S. Pat. 5,358,991.
60.
Geran, T., Finberg, I., Resnick, G., Hini, S., Plewinsky, D. and Bar Yaakov, Y. (2003). Development of Fire Retarded Plastics with Reduced or No Presence of Antimony Trioxide, paper presented at 14th Annual BCC Conference on Flame Retardancy, Stamford, CT, 2—4 June.
61.
Bar-Yakov, Y. and Hini, S. (to Bromine Compounds, Ltd.) (2004). U.S. Pat. 6,737,456.
62.
Reyes, J., Georlette, P., Finberg, I. and Reznick, G. (1999). Flame Retardants for Enhanced Properties in Polyolefins , paper presented at 10th Annual BCC Conference on Flame Retardancy, Stamford, CT, 24—26 May.
63.
Utevskii, L. , Scheinker, M., Georlette, P. and Reyes, J.D. (1996). Development of flame retardant copolymers imparting high impact properties to polypropylene, paper at 7th Annual BCC Conference on Flame Retardancy, Stamford, CT, 20—22 May.
64.
Dvir, H. and Gottlieb, M. (2006). A Reactive Flame Retardant as a Polypropylene-Sized Glass Adhesion Promoter, Macromol. Mater., 291: 913—916.
65.
Web site of International Antimony Oxide Industry Association : www.iaoia.org/.
66.
Le Bras, M., Camino, G., Bourbigot, S. and Delobel, R. (eds) (1998). Fire Retardancy of Polymers: The Use of Intumescence, Royal Society of Chemistry Special Publication 224, Springer Verlag, Cambridge, UK.
67.
Bourbigot, S., Le Bras, M., Duquesne , S. and Rochery, M. (2004). Recent Advances for Intumescent Polymers, Macromol. Mater. Eng., 289: 490—511.
68.
Cogen, J.M., Jow, J., Lin, T.S. and Whaley, P.D. (2003). New Approaches to Halogen Free Polyolefin Flame Retardant Wire and Cable Compounds, In: Proceedings of the 52nd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, 17—20 November.
69.
Representative earlier patents are: Staendeke, H. and Scharf, D. (to Hoechst Celanese) (1988). Ger. Pat. Appl. 3,720,094; Bertelli, G. and Locatelli, R. (to Montedison SpA) (1986). U.S. Pat. 4,579,894; Landoni, G., Fontani, S. and Cicchetti, O. (to Montedison) (1982). U.S. Pat. 4,336,182; Fontanelli, R., Landoni, G. and Legnani, G. (to Montedison S.p.A.) (1985). U.S. Pat. 4,504,610.
70.
Nalepa, R. and Scharf, D. (to Hoechst Celanese) (1993). U.S. 5,204,392 and 5,204,393 .
71.
Staendeke, H. (to Hoechst) (1996). U.S. Pat. 5,484,830.
72.
Pernice, R., Checchin, M., Moro, A. and Pippa, R. (to Enichem) (1996). U.S. Pat. 5,514,743.
73.
Weil, E.D. and McSwigan, B. (1994). Melamine Phosphate Flame Retardants, Plastics Compounding, May—June 1994, 31—39.
74.
Imanishi, S. (to Daicel Chemical Industries) (2005). U.S. Pat. 6,921,783 .
75.
Goin, C.L. and Huggard, M.T. (1992). In: Lewin, M. and Kirshenbaum, G.S. (eds), Recent Advances in Flame Retardancy of Polymeric Materials, Vol. II, pp. 94-101, Business Communication Co., Inc., Norwalk, Conn.
76.
Rhodes, M.S., Israilev, L., Tuerack, J. and Rhodes, P.S. (2004). U.S. Pat. Appl. 2004/0012004 and 2004/0036061 .
77.
Amigouet, P. and Shen, K. (2006). Talc/Zinc Borate: Potential Synergisms in Flame Retardant Systems, In: Flame Retardants 2006, Interscience Commun., London, pp. 155—162.
78.
Kurumatani, H., Yamaki, A. and Kimura, R. (2005), (to Asahi Denka Co., Ltd.) U.S. Pat. Appl. 2005/0256234 (published November 17, 2005).
79.
Kamimoto, T., Murase, H., Yamaki, A., Nagahama, M., Kimura, R., Funamizu, T. and Zingde, G. (2004). A Highly Efficient Intumescent Flame Retardant for Polyolefins, International Conference on Polyolefins 2004, Houston, TX, 22—25 February 2004.
80.
Futterer, T., Nägerl, H.-D., Götzmann, K., Mans, V. and Tortosa, E. (2002). New Intumescent Flame Retardants Based on APP and Phosphate Esters, paper presented at 13th Annual BCC Conference on Flame Retardancy, Stamford, CT, 3—5 June.
81.
Liu, Y. and Wang, Q. (2006). Catalytic action of phospho-tungstic acid in the synthesis of melamine salts of pentaerythritol phosphate and their synergistic effects in flame retarded polypropylene, Polym. Degrad. Stab., 91: 2513—9.
82.
Chyall, L.J. , Hodgen, H.A., Vyverberg, F.J. and Chapman, R.W. (2003). U.S. Pat. Appl. 2003/0209699 .
83.
Chyall, L.J. , Hodgen, H.A., Vyverberg, F.J. and Chapman, R.W. (to PABU Services) (2003). U.S. Pat. 6,905,693 (2005), also U.S. Pat. 6,632,442.
84.
Costanzi, S. (to Italmatch) (2007). PCT Appl. WO 2007010318 published 25 January.
85.
Costanzi, S. and Leonardi, M. (to Italmatch) (2005). PCT Appl. WO 2005121232 published 22 December.
86.
Leite, L., Zanetto, J.-E., Ponnouradjou, A. and Lambert, A. (2006). U.S. Pat. Appl. 20060100325 (published 15 May 2006).
87.
Gatti, N. and Costanzi, S. (2003). Is red phosphorus an effective solution for flame proofing polyolefin articles, paper presented at 14th Annual BCC Conference on Flame Retardancy, Stamford, CT, 2—4 June; also in Flame Retardants 2004, London, pp. 27—28 January, Interscience Communications , Greenwich, UK, pp. 133—8.
88.
Okisaki, F. (1997). Flamecut® GREP Series - New Non-Halogenated Flame-Retardant Systems, Papers from the FRCA Spring Meeting, San Francisco, CA, March, pp. 11—24.
89.
Representative patent, citing others: Kaprinidis, N. and Lelli, N. (to Ciba Specialty Chemicals) (2006). U.S. Pat. 7,109,260 .
90.
Pirngadi, P. and Richter, S. (2005). New Developments in the Application of Nanoclays for HFFR Cable Compounds, In: 54th IWCS/Focus International Wire & Cable Symposium, Providence, RI, 13—16 November.
91.
Beyer, G. (2007). Flame Retardant Properties of Organoclays and Carbon Nanotubes and their Combinations with Alumina Trihydrate, Chapter 7 , In: Morgan, A. and Wilkie, C. (eds), Fire Retardant Polymer Nanocomposites , Wiley-Interscience, NY, pp. 163—190.
92.
Lan, T. (2006). Flame retardancy properties of nanocomposites materials, In: Fire Resistance in Plastics Conference , Düsseldorf, Germany, 6—8 November.
93.
Kenig, S., Shepelev, O. and Peled, M. (2005). Flame Retardant Polypropylene Containing Functionalized Nanoclays, papers from SPE ANTEC 2005, pp. 3318—3321.
94.
Chenouf, D. (2005). Glockner, R. and Moneke, M., Flame Retardant Polypropylenes, Papers at SPE ANTEC 2005, pp. 389—393.
95.
Cogen, J.M., Morgan, A.B. and Lin, T.S. (to Dow Chemical Co.) (2006). U.S. Pat. Appl. 2006/0142460 (published 29 June 2006).
96.
Beyer, G. (2003). Carbon Nanotubes as a New Class of Flame Retardants for Polyolefins, In: Proceedings of the 52nd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, 17—20 November.
97.
Beyer, G. (2006). Can PVC, TPU and PE be made flame retardant by nanostructured fillers? In: Fire Resistance in Plastics Conference, Düsseldorf, Germany, 6—8 November.
98.
Collins, P., Carbon Multiwall Nanotubes as a Conductive or Flame Retardant Additive for Wire and Cable, In: Proceedings of the 52nd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, 17—20 November.
99.
Du, Y.L. , Pees, B. and Perrinaud, R. (2003). The Use of Functionalized Polyolefins in Halogen Free Flame Retardant (HFFR) Compounds, In: Proceedings of the 52nd IWCS/Focus International Wire & Cable Symposium, Philadelphia, PA, 17—20 November.
100.
Kim, O.-Y. , Yoon, S.H., Nam , G.J. and Lim , H.J. (2003). The Effect of Compatibilizers on the Mechanical and Flame Retardant Properties in HFFR Compounds for Automotive Wire Insulation, In: Proceedings of the 52nd IWCS/Focus International Wire & Cable Symposium , Philadelphia, PA, 17—20 November.
101.
Adedji, A., Haylock, J.C., Hossan, R., Pecak, W.E. and Vendon, M.V. (to GE) (2004). U.S. Pat. Appl. 2004/0082719 (published 29 April 2004).
102.
Mhetar, V.R. , Rajamani, V., Rexius, K., Sato, S. and Tai, X. (to GE) (2006). U.S. Pat. 7,084,347 .
103.
Pape, P.G. and Romanesko, D.J. (1996). The Effect of Powdered Silicone Additives as Flame Retardant Synergists in Thermoplastic Fire Retarded Plastics, paper presented at 7th Annual BCC Conference on Flame Retardancy , Stamford, CT, 20—22 May.
104.
Hshieh, F.-U. (1998). Shielding Effects of Silica-ash Layer on the Combustion of Silicones and Their Possible Applications on the Fire Retardancy of Organic Polymers, Fire and Materials, 22: 69—76.
105.
Lundpren, A. , Hjertberg, T. and Sultan, B.-A., FlameRetardant Mechanism and Behavior of a Halogen-free Polyethylene Cable Material , In: Flame Retardants2006, pp. 77—88, Interscience Communications, London.
106.
Sultan, B., Hirvensalo, M. and Laurell, J. (to Borealis Tech. Oy) (2000). U.S. Pat. 6,166,120.
107.
Ahmadnia, A., Hornsby, P.R., Marosi, G. and Anna, P. (2003). paper at SPE ANTEC 2003, Nashville, TN, 4—8 May.
108.
Moneke, M. (Deutsches Kunststoff-Institut, Darmstadt , 2006). Polypropylene and magnesium hydroxides - an option for cable compounds In: Fire Resistance in Plastics Conference, Düsseldorf, Germany, 6—8 November.
109.
Kosaka, K., Li, X., Mhetar, V., Tenenbaum, J. and Yao, W. (2005). U.S. Pat. Appl. 20050154100 published 14 July .
110.
Davis, J.A., Barham Jr, W.F. and Brandt, G.A. (to BFS Diversified Products LLC) (2003). U.S. Pat. 6,632,509.
111.
Sharp, S.A. (2002). TPOs - commodity or specialty?, Professional Roofing Magazine, 2002 June, pp. 38—48 (on line as http://www.professionalroofing.net/article.aspx? A_ID=79).
112.
Weil, E.D. , Zhu, W., Patel , N. and Mukhopadhyay , S.M. (1996 ). A Systems Approach to Flame Retardancy and Comments on Modes of Action, Polymer Degradation and Stability, 54: 125—136.
