Halogen-Free Flame-Retardant Polymers: Next-generation Fillers for Polymer Nanocomposite Applications

122 Pages·2020·3.849 MB·English

by  Suprakas Sinha Ray, Malkappa Kuruma

Springer Series in Materials Science 294
Suprakas Sinha Ray
Malkappa Kuruma
Halogen-Free
Flame-Retardant
Polymers
Next-generation Fillers for Polymer
Nanocomposite Applications
Springer Series in Materials Science
Volume 294
Series Editors
Robert Hull, Center for Materials, Devices, and Integrated Systems,
Rensselaer Polytechnic Institute, Troy, NY, USA
ChennupatiJagadish,ResearchSchoolofPhysical,AustralianNationalUniversity,
Canberra, ACT, Australia
Yoshiyuki Kawazoe, Center for Computational Materials, Tohoku University,
Sendai, Japan
Jamie Kruzic, School of Mechanical & Manufacturing Engineering,
UNSW Sydney, Sydney, NSW, Australia
Richard M. Osgood, Department of Electrical Engineering, Columbia University,
New York, USA
Jürgen Parisi, Universität Oldenburg, Oldenburg, Germany
Udo W. Pohl, Institute of Solid State Physics, Technical University of Berlin,
Berlin, Germany
Tae-Yeon Seong, Department of Materials Science & Engineering,
Korea University, Seoul, Korea (Republic of)
Shin-ichi Uchida, Electronics and Manufacturing, National Institute of Advanced
Industrial Science and Technology, Tsukuba, Ibaraki, Japan
Zhiming M. Wang, Institute of Fundamental and Frontier Sciences - Electronic,
University of Electronic Science and Technology of China, Chengdu, China
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Suprakas Sinha Ray Malkappa Kuruma
(cid:129)
Halogen-Free
Flame-Retardant Polymers
Next-generation Fillers for Polymer
Nanocomposite Applications
123
Suprakas SinhaRay MalkappaKuruma
Centrefor Nanostructures andAdvanced Centrefor Nanostructures andAdvanced
Materials, DSI-CSIR Nanotechnology Materials, DSI-CSIR Nanotechnology
Innovation Centre, Council for Scientific Innovation Centre
andIndustrial Research Council for Scientific
Brummeria, Pretoria, SouthAfrica andIndustrial Research
Brummeria, Pretoria, SouthAfrica
DepartmentofChemicalSciences
UniversityofJohannesburg
Johannesburg, SouthAfrica
ISSN 0933-033X ISSN 2196-2812 (electronic)
SpringerSeries inMaterials Science
ISBN978-3-030-35490-9 ISBN978-3-030-35491-6 (eBook)
https://doi.org/10.1007/978-3-030-35491-6
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Dedicated to our parents
Preface
This monograph presents an overview of recent academic and industrial research
efforts on halogen-free flame-retardant (FR) polymers and their nanocomposites.
The synthesis methods of various types of halogen-free FR polymers and their
nanocomposites are summarized and their flame-retardant behavior, toxic gas
evolution during combustion, and inhibition methods are critically reviewed.
The FR activities of different FR compounds containing polymers, their FR
mechanisms, and fire toxicant releasing and inhibition methods are covered in this
book, with special emphasis on polyurethanes (PUs). The significance of thermal
stabilityandmeltdrippingontheFRactivityofPUsisexplained.TheFRactivities
of various P-, N-, and P-N-based FRs-containing PUs are critically analyzed.
The synergetic effect between different FR compounds and their importance in FR
activity, char formation, and improving char strength are systematically summa-
rized. The importance of metal oxide nanoparticles, nanoclay, and graphene in
flame inhibition is discussed. In summary, the various fundamental concepts
described in this book are essential to understand the FR activity of various
polymers and their nanocomposites, and they would be of great aid in developing
efficientenvironmentallyfriendlyFRpolymersandtheirnanocompositesforawide
rangeofapplications.Wehopethatgraduatestudentsandresearchersatuniversities
and industry alike will find this monograph enjoyable and stimulating, as well as
helpful for their future work.
Pretoria/Johannesburg, South Africa Suprakas Sinha Ray
Pretoria, South Africa Malkappa Kuruma
vii
Acknowledgements
TheauthorswouldliketothanktheDepartmentofScienceandInnovationandthe
Council for Scientific and Industrial Research, South Africa, for financial support.
We express our sincerest appreciation to all colleagues, postdoctoral fellows, and
students for their valuable contributions as well as the reviewers for their critical
evaluation of the proposal and chapters. We also thank the authors and publishers
for their permission to reproduce their published works. Our special thanks go
to Zachary Evenson at Springer Nature for his encouragement, cooperation,
suggestions, and advice during various phases of preparation, organization, and
productionofthis book. Finally, we would like tothank our CEO, T. Dlamini,for
his continued support and encouragement.
Pretoria/Johannesburg, South Africa Suprakas Sinha Ray
Pretoria, South Africa Malkappa Kuruma
ix
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Polymer Combustion and Flame Retardancy . . . . . . . . . . . . . . . . . . 5
2.1 FR Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1.1 Gas-Phase FRs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.2 Endothermic FRs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.3 Solid-Phase FRs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.4 Intumescent FRs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3 Flame-Retardancy Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1 Cone Calorimeter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2 Limiting Oxygen Index (LOI) . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.3 Underwriters Laboratory-94 (UL-94 V) . . . . . . . . . . . . . . . . . . . . 13
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4 Types of Flame Retardants Used for the Synthesis
of Flame-Retardant Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1 Nitrogen-Based FRs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.2 Nitrogen and Phosphorus-Based Salts as FRs. . . . . . . . . . . . . . . . 18
4.3 Phosphorus-Based FRs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.3.1 DOPO-Based Phosphorus FRs . . . . . . . . . . . . . . . . . . . . . 23
4.3.2 Phosphorus-Based FRs with Different Oxidation
States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.3.3 Phosphazene-Based FRs. . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.3.4 Phosphorus-Based Spiro Cyclic FRs. . . . . . . . . . . . . . . . . 31
4.4 UV-Curable FRs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
xi
xii Contents
5 Flame-Retardant Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5.1 Thermal Degradation and Evolution of Components
During PU Combustion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.2 Importance of Polyols in Flame-Retardant PUs. . . . . . . . . . . . . . . 53
5.3 Phosphorus-Based Polyols for Flame-Retardant Polyurethanes. . . . 54
5.4 Importance and Reactivity of Diisocyanates in FR PUs. . . . . . . . . 55
5.5 Effect of Segmental Separation in PUs on Their FR Activity . . . . 56
5.6 Interactions Between P,N-Based FRs and PUs for FR Activity . . . 58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
6 Melt-Dripping and Char Formation . . . . . . . . . . . . . . . . . . . . . . . . . 69
6.1 Relationship Between the Melting Dripping Characteristics
of Polymer Films and Fire Properties. . . . . . . . . . . . . . . . . . . . . . 69
6.2 The Relationship Between Char Formation and Morphology
Development in Fire Retardant Activities. . . . . . . . . . . . . . . . . . . 73
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7 Polymer Nanocomposites for Fire Retardant Applications . . . . . . . . 83
7.1 FR Polymer Nanocomposites Based on Various
Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.2 Clay-Based Flame-Retardant Polymer Nanocomposites. . . . . . . . . 93
7.3 Graphene-Based FR PNCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
Index .... .... .... .... .... ..... .... .... .... .... .... ..... .... 111