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Progress in Polymer Science 67 (2017) 77–125

Contents lists available at ScienceDirect

Progress in Polymer Science


journal homepage: www.elsevier.com/locate/ppolysci

Review

Polymer/polyhedral oligomeric silsesquioxane (POSS)


nanocomposites: An overview of fire retardance
Wenchao Zhang a , Giovanni Camino b,∗ , Rongjie Yang a,∗
a
National Engineering Technology Research Center of Flame Retardant Materials, School of Materials, Beijing Institute of Technology, 5 South
Zhongguancun Street, Haidian District, 100081 Beijing, PR China
b
Department of Applied Science and Technology, Politecnico di Torino, sede di Alessandria, Viale Teresa Michel 5, 15121 Alessandria, Italy

a r t i c l e i n f o a b s t r a c t

Article history: A review is presented of the recent developments concerning the use of polyhedral oligomeric
Received 9 September 2015 silsesquioxane (POSS) for designing polymer nanocomposites endowed with enhanced fire retardancy.
Received in revised form Emphasis is placed on the scientific and technological advances in the use of POSS as fire retardants, as
21 September 2016
well as on the achievements and challenges associated to the exploitation of POSS either alone or in com-
Accepted 30 September 2016
bination with conventional fire retardants to provide the required fire retardancy to polymer materials.
Available online 17 October 2016
Polymer/POSS nanocomposites show a great potential to provide materials characterized by improved
fire retardancy together with superior physical properties and environmental neutrality. Achievements
Keywords:
Polyhedral oligomeric silsesquioxane obtained with POSS in fire retardancy are presented for the different types of polymer materials and
Fire retardance critically discussed, especially in terms of the modes of fire retardant action, in the attempt to reveal
Nanocomposite attractive strategies for successful development of the next generation of polymer/POSS materials and
applications.
© 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2. Preparation methods and properties of POSS and polymer materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3. Fire retardance of polymer/POSS nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.1. Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.2. Polystyrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.2.1. Polystyrene with POSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.2.2. Polystyrene with POSS and halogen-containing compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.3. Poly(methyl methacrylate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.4. Polycarbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.4.1. Polycarbonate with POSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.4.2. Polycarbonate with POSS and Organophosphate compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.4.3. Polycarbonate with POSS and metallic compounds or organic salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.5. Poly(phenylene ether) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.6. Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.6.1. Poly(ethylene terephthalate) with POSS and inorganic phosphorus compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.6.2. Poly(ethylene terephthalate) with POSS and montmorillonite clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.6.3. Poly(1,4-butylene terephthalate) with POSS and phosphinate compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.6.4. Poly(butylene succinate) with POSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.7. Vinyl esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95

∗ Corresponding authors. Fax: +39 0131 229399/86 10 68912927.


E-mail addresses: zwc18@bit.edu.cn (W. Zhang), giovanni.camino@polito.it (G. Camino), yrj@bit.edu.cn (R. Yang).

http://dx.doi.org/10.1016/j.progpolymsci.2016.09.011
0079-6700/© 2016 Elsevier Ltd. All rights reserved.
78 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

3.7.1. Vinyl ester resins with POSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95


3.7.2. Vinyl ester resins with POSS and organophosphate compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.8. Acrylic fabrics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.9. Polyurethane and polyurea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.9.1. Polyurethane with POSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.9.2. Polyurea with POSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3.10. Polylactide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.11. Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.12. Polyvinyl alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.13. Epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.13.1. Epoxy resins with POSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.13.2. Epoxy resins with POSS and inorganic phosphate fire retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3.13.3. Epoxy resins with POSS and reactive organic phosphate fire retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.13.4. Epoxy resins with POSS and metallic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.13.5. Epoxy resins with POSS and Boron compound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.13.6. Epoxy resins with POSS and halogen-containing compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.14. Polyimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.15. Bismaleimide resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.16. Cyanate ester resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.17. POSS and nanoparticle for polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.17.1. POSS intercalated MMT for polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.17.2. POSS grafted carbon nanofibers for polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Appendix A. POSS structures, nomenclatures and application fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121

Nomenclature
FIGRA Fire growth rate
[Al] Aluminum triacetylacetonate FPI Fire performance index
ABS Acrylonitrile-butadiene-styrene FR Flame retardant
AIBN 2,2 -Azo-bis-isobutyronitrile FTIR Fourier transform infrared spectroscopy
APP Ammonium polyphosphate GF Glass fibers
ASEA Average specific extinction area HRC Heat release capacity
ASTM American society for testing and materials HRR Heat release rate
ATH Aluminium hydroxide IFR Intumescent flame retardant
BDP Bisphenol A bis(diphenyl phosphate) iPP Isotactic polypropylene
BMI Bismaleimide KSS Potassium diphenyl sulfonate
CaSiEMAA Polyethylene–calcium carbonate–silicone LbL Layer-by-layer
CE Cyanate ester resin LDH Layered double hydroxides
CNF Carbon nanofiber LHS Layered hydroxy salt
CNT Carbon nanotubes LOI Limiting oxygen index
CO2 Y Carbon dioxide yield MCC Microscale combustion calorimeter
COC Carbon monoxide concentration MDEA 4,4 -Methylene bis(2,6-diethylaniline)
CONE Cone calorimeter MFR Melt flow rate
CORR Carbon monoxide release rate MH Magnesium hydroxide
COY Carbon monoxide yield Micro-PCM Microencapsulated phase-change materials
DABP 4,4 -Diaminobenzophenone MLR Mass loss rate
DBSS Dodecyl benzene sulfonic acid sodium salt MP Melamine phosphate
DCP Dicumyl peroxide m-PDA m-Phenylenediamine
DGEBA Diglycidyl ether of bisphenol A MS Mass spectrometer
DMMP Dimethyl methyl phosphonate MWCNT Multiwalled carbon nanotube
DOPO 9,10-Dihydro-9-oxa-10-phosphaphenanthrene- NMR Nuclear magnetic resonance
10-oxide OMMT Organically modified montmorillonite
EA Epoxy acrylate OP1200 Combination of melamine cyanurate and of alu-
EG Expandable graphite minum diethylphosphinate
EHC Effective heat combustion OP1230 Aluminium phosphinate
EmiAc 1-Ethyl-3-methylimidazolium acetate OP1240 Aluminum diethylphosphinate
EP Epoxy resin OP950 Zinc phosphinate
ESCA Electron spectroscopy for chemical analysis
FAVE Fatty acid vinyl ester
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 79

1. Introduction

P(POSS-MMA-VBFC) Poly(octavinyl POSS-co-methyl Nowadays, polymers are used almost everywhere in our life,
methacrylate-co-4-vinylbenzyl fluoroether however, their flammability restricts their applications charac-
carboxylate) terized by fire risk and fire hazard. Thus, the reduction in their
PBS Poly(butylene succinate) propensity to ignite and/or burn is a very attractive subject for
PBT Poly(1,4-butylene terephthalate) research. Halogen-containing compounds are effective fire retar-
PC Polycarbonate dants for polymers [1], however, due to environmental concerns,
PCEP Phosphorus-containing epoxy resin some halogen-containing fire retardants have been gradually pro-
PCFC Pyrolysis combustion flow calorimeter hibited [2]. Non-toxic and environmentally sound, halogen-free
pCOC Peak of CO concentration fire retardant compounds, especially inorganic substances, require
pCORR The peak of CO release rate high add-on levels and impair polymer mechanical properties.
PE Polyethylene Phosphorous based fire retardants develop quickly as effective
PEPA 1-Oxo-4-hydroxymethyl-2,6,7-trioxa-l- halogen-free fire retardants, and are widely used to fire retard poly-
phosphabicyclo[2.2.2] octane mers. However, phosphorus based fire retardants could plasticize
PET Poly(ethylene terephthalate) the polymers, thereby reducing modulus, glass transition Tg , and
PFBS Potassium perfluorobutane sulfonate strength [3]. There are also environmental concerns associated with
pHRR Peak of heat release rate some phosphorous additives. The occurrence and environmental
PI Polyimide behavior of organophosphorus compounds (OPs) in diverse matri-
PLA Polylactide ces (e.g., dust, air, water, sediment, soil and biota) are reviewed
PMMA Poly(methyl methacrylate) by Wei et al. [4]. Inorganic oxides, including antimony trioxide, do
P-m-PMMA Phosphonated modified PMMA not improve fire retardance on their own. These additives act as
PNFC POSS-modified nanofibrillated cellulose synergists only, improving the fire retardance effects of bromine
POSS Polyhedral oligomeric silsesquioxane or intumescent fire retardants. Another way to effectively improve
PPE Poly(phenylene ether) the fire retardance of polymers is to reinforce them with nano-sized
PPgMA Maleic anhydride grafted polypropylene inorganic particles (defined herein as having at least one dimension
PPSQ Polyphenylsilsesquioxane in the range 1–100 nm). Using this approach, improvements in fire
PS Polystyrene retardance and maintaining or enhancement of their mechanical
PSPPP Poly(sulfonyl phenylene phosphonate) properties are often found even at relatively low filler content. The
PSS Polysilsesquioxanes field of polymer nanocomposites has attracted great attention from
PU Polyurethane polymer scientists and engineers in recent years.
PVDF Poly(vinylidenefluoride) Polyhedral oligomeric silsesquioxanes (POSS) are a kind of
Py-GC/MS Pyrolysis gas chromatography/mass spectrome- inorganic–organic hybrid materials which nanostructures have
try become attractive because of their environmental neutrality, good
RDP Resorcinol bis(diphenyl phosphate) heat resistance as well as excellent thermoxidative stability [5].
SEA Specific extinction area Many attentions were directed to the use of POSS, as a great
SEM Scanning electron microscopy potential for producing materials characterized by improved fire
SPR Smoke production rate retardance along with superior physical properties [6–8]. Research
sumHRC Sum heat release capacity results indicated that POSS exert astonishing effects on some fire
TBBPAER Tetrabromobisphenol A epoxy resin properties of polymers, because they can act as stand-alone fire
TCP Tricresylphosphate retardants or as synergistic fire retardant in important regulatory
TEM Transmission electron microscopy fire tests [9]. However, POSS used alone are not sufficient to meet
Tg Glass transition temperature commercial applications requirements, since they are more expen-
TGA Thermogravimetric analysis sive than other commercial halogen-free fire retardants. On the
TGA-FTIR Thermogravimetric analysis coupled with fourier other hand, the better fire retardant performance of POSS may open
transform infrared spectroscopy the door to highly fire safety demanding applications so far pre-
TGA-MS Thermogravimetric analysis coupled with mass cluded to current fire retardant polymers. In this respect, the aim
spectrometer of this work is to review the scientific and technological advances
TGDDM Tetraglycidy(diaminodiphenyl)methane in the use of POSS as fire retardants, and the advantage or inad-
TGIC Triglycidyl isocyanurate equacy of POSS used alone or in combination with conventional
THPB Tris (2-hydroxypropyl) borate fire retardants to provide the required fire retardancy to polymer
THR Total heat released materials.
TPP Triphenylphosphate Focus of this review was placed on fire performance of poly-
TPU Thermoplastic polyurethane mer/POSS nanocomposites and their thermal stability which is
TSP Total smoke production related with fire performance. Furthermore, important engineering
TSR Total smoke release properties of these materials are also addressed. Accordingly, in the
TTI Time to ignition first part, brief informations on the preparation methods of poly-
TTpHRR Time to peak of heat release rate mer/POSS nanocomposites are reported. The second part addresses
UPE Unsaturated polyester the fire retardance of different polymers with POSS alone or with
VE Vinly ester mixture of POSS and conventional fire retardants. The examples
VTES Vinyltriethoxysilane reported in this review are mostly drawn from the open literature.
XPS X-ray photoelectron spectroscopy Patent literature is not included since the reported claims regard-
XRD X-ray diffraction ing the fire retardant mechanism are more explicitly analyzed in
ZrP ␣-Zirconium phosphate nanoplatelets the authors’ research articles, found in the scientific literature. Basi-
cally, in this survey, some advanced discussions on the modes of fire
retardant action of Polymer/POSS nanocomposites are proposed, in
80 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 1. Structures of silsesquioxanes [10].


Copyright 2011. Reproduced with permission from Elsevier Ltd.

silsesquioxane (POSS) were isolated by Scott [18] along with other


volatile compounds through thermolysis of polymeric products
obtained from methyltrichlorosilane and dimethylchlorosilaneco-
hydrolysis. Around 1990s, Feher et al. made lots of important
improvements on exploring the synthesis method and improving
the yield of POSS [12,19,20]. In 1998, Lichtenhan and his team spun
this POSS® technology out of the Air Force Research Laboratory and
founded Hybrid Plastics® . Thus began the process of the converting
from a small R&D to a true commercialization of POSS. After decades
of development work, the preparation of POSS mainly divides into
four routes as shown in Fig. 3.
Fig. 2. POSS features.
Reaction (1) involves the direct complete condensation of tri-
alkoxysilanes or trichlorosilanes (RSiX3 precursors) leading to
the attempt to reveal attractive strategies for successful polymer
the formation of polyhedral oligomericsilsesquioxanes (RSiO1.5 )n
materials applications.
derivatives which have n values 4, 6, 8, 10, or 12 [16]. Typical R
groups include hydrogen, methyl, ethyl, n-proply, butyl, n-pentyl,
2. Preparation methods and properties of POSS and n-hexyl, ciclohexyl, benzyl, and some other substituted phenyl
polymer materials groups as shown in Fig. 3 [11,15,21,22]. Most of the R substituents
are small groups, because complete condensation in the presence
Silsesquioxanes are inorganic–organic hybrid materials synthe- of sterically hindered large and rigid organic groups is difficult to
sized from hydrolysis-condensation process of silanes with halogen achieve. Furthermore, the hydrolytic condensation performance
or alkoxy groups. They can be formed as random, ladder, cage, and from a mixture of different precursors to synthesize POSS cage bear-
partial cage structures as shown in Fig. 1 [10–12]. In recent years, ing different R and R groups, depends on molar ratio and chemical
the polyhedral oligomeric silsesquioxane (POSS) have become the reactivity [11].
most attractive silsesquioxane to be used as fire retardants in poly- Reaction (2) shows the incomplete condensation reaction
mer [13,14]. POSS have the general formula (RSiO1.5 )n , where R resulting in incompletely condensed POSS structures depending
may be a hydrogen atom or an organic functional group as shown on the synthetic conditions. In particular, a trisilanol POSS with
in Fig. 2. Moreover, these organic groups can be specially designed one missing corner is easily obtained with high steric hindrance
to be nonreactive or reactive. POSS are nanostructures with size substituents, such as cyclopentyl and cyclohexyl [23–25].
from 1 to 3 nm in diameter, which can be thought of as the smallest Reaction (3) is the corner capping reaction of incomplete POSS
possible particles of molecular silica. Unlike silica, POSS molecule structures. The incomplete cage can react with a functional R siY3
can carry organic substituents on its outer surface that make the to obtain a monofunctional complete POSS cage as shown in Fig. 3.
POSS nanostructure compatible with polymers, biological systems, This method could realize the precise control on the final POSS
and surfaces of organic nature [11,15]. Moreover, the incorpora- structure and offer a route for generation of hetero- and metal-
tion of POSS in polymers to obtain composites is responsible for the POSS, in which a hetero main group or a transition metal element
enhancement of mechanical properties, reduction in flammability is introduced into the POSS framework [26–28].
and also of heat release on burning [16]. Reaction (4) refers to the modification of the complete POSS
In early 1900s, Meads and Kipping [17] found that polycon- cage obtained from one of the three methods above by a second
densation of siliconic acids invariably leads to extremely complex reaction step involving the R groups depending on their chemical
mixtures of silsesquioxanes. Later in 1946, polyhedral oligomeric structures as shown in Fig. 3 [6]. For example, octaphenyl POSS has
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 81

Fig. 3. Preparation methods of POSS.

high thermal stability and can be used in the field of fire retardants
and high-temperature polymers, but it is very inert and insoluble,
which entails poor compatibility with a polymer matrix. However,
octaphenyl POSS functionalized by functions such as nitrate, amine,
sulfonic, etc. are robust and highly soluble compounds which are
easy to purify and process [29–31].
In relation to the neat polymer, POSS nanoparticles can decrease
viscosity in highly filled resins by forming strong bonds with the
surface of the fillers and breaking up particle–particle interactions,
resulting in enhanced mechanical properties and surface finish
[32]. Unlike most nanofillers (carbon nanotube or nanoclay), POSS
molecules contain organic constituents on their external surface,
which can make them compatible with many polymers [6]. It was
found that dispersing POSS nanoparticles into a polymer increases
the strength, modulus, rigidity and reduces the flammability, ther-
mal insulation and viscosity of the polymers, while retaining its Fig. 4. Synthesis of polystyrene-POSS nanocomposites [35].
lightweight and ductile features [33,34]. These enhanced proper- Copyright 2011. Reproduced with permission from the American Chemical Society.
ties allow for a wide range of applications of these polymer/POSS
nanocomposites [16]. ing methods. Compared to chemical reaction methods, physically
The preparation methods of polymer/POSS materials are mainly blending presents several advantages, being an inexpensive, fast
dependent on the chemical structures of POSS and polymer. The and versatile technology. Indeed, standard equipment used for
dispersion of POSS in the polymer matrix could strongly affect the polymer compounding, such as twin screw extruders, is gener-
properties of polymer/POSS composites [13]. Two approaches have ally suitable for the processing of nanostructured thermoplastic
been adopted to incorporate POSS particles into polymer matrices: polymers [23]. However, aggregation of POSS during the extrusion
chemical reaction and physical blending. process is difficult to control that will influence the final dispersion
In the chemical reaction approach, POSS nanoparticles are of POSS nanaparticles. For the thermosetting polymers, the POSS
bonded covalently with polymer through grafting reaction or poly- could be dispersed in the monomer by mechanical stirring with
merization. Indeed, monofunctional POSS could participate the or without solvent under heating [42]. During the curing period,
polymerization of polymer to form for example polystyrene-POSS without mechanical stirring and solvent, the settlement and aggre-
(Fig. 4), polyethylene-POSS or poly(methyl methacrylate)-POSS gation of POSS are important facts that influence the dispersion of
nanocomposites [7,35,36]. The monofunctional methacryl POSS POSS, especially when the content of POSS is high. Although POSS
g-ray radiation grafting on PP or PMMA was explored [37,38]. Mul- nanoparticles could be incorporated into almost all the polymers by
tifunctional POSS substituted with epoxy or amino groups could act chemical reaction or physical blending, the control of nanostructure
as curing agent or reactive monomer to create a polymer network and location of nanoparticles in polymer/POSS nanocomposites
(EP, PI, PU, etc.) [8,39,40]. More methods to prepare polymer/POSS remain open challenges.
nanocomposites by chemical reaction have been reviewed by Kuo
et al. and Fina et al. [10,23]. Some catalysts used for the reaction 3. Fire retardance of polymer/POSS nanocomposites
between polymers and POSS may have synergies with POSS to
improve the fire retardance of polymer/POSS nanocomposites [41]. The polyhedral oligomeric silsesquioxane (POSS) substituted
In the physical blending approach, POSS nanoparticles are with suitable organic groups makes it possible to incorporate
physically blended with polymer by melt mixing or solvent cast- them into almost every polymer. Its nanostructures and Si–O
82 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 5. (a) OME-POSS, (b) OIB-POSS, (c) OIC-POSS cage structures [43].
Copyright 2005. Reproduced with permission from Elsevier Ltd.

frameworks, provides some inherent fire retardent POSS structure


resulting in remarkable improvement in the fire retardancy of poly-
mer/POSS nanocomposites where polymer’s mechanical properties
are either preserved or enhanced. Nano-technology and nano-
materials occupy a relevant position in the fire retardancy materials
field. The nanoscopic size and structure of nano-materials with
their fine dispersion contribute to improve fire safety properties.
Using this approach, improvements in fire retardance and main-
taining or enhancement of their mechanical properties are often
found even at relatively low filler content. The field of polymer
nanocomposite has attracted great attention from polymer scien-
tists and engineers in recent years. POSS are considered as fire
retardants which main function involves the condensed phase with
reduction of the rate of supply of polymer degradation combustible
volatiles to the flame. They may be used in combination with gas
phase fire retardants which slow down combustion reactions in Fig. 6. Polysilsesquioxane approximate structure [45].
the flame, to improve retardance efficiency. Some representative Copyright 2009. Reproduced with permission from Elsevier Ltd.
systems are discussed below.

3.1. Polyolefins

POSS with different chain lengths [octamethyl POSS (OME-


POSS), octaisobutyl POSS (OIB-POSS), and octaisooctyl POSS
(OIC-POSS)] (Fig. 5) were introduced into polypropylene (PP) com-
posites by melt blending [43]. The thermoxidative behavior of the
PP matrix is improved when adding the POSSs as an increase in the
TGA weight loss peak temperature is found at high POSS loadings.
This effect is more evident at higher dispersion extents of POSSs.
However, a good dispersion is obtained particularly at low loading
of POSS functionalized with long organic chains.
The polysilsesquioxanes (PSS) that are characterised by a non-
crystalline cage/ladder structure reduce the interface interaction
strength of silsesquioxane, which is high for highly crystalline
POSS and represents an adverse contribution in the energy bal-
ance during mixing, thus limiting silsesquioxane dispersion into the
polymer [43,44]. At the same time, the PSS with methyl (Me-PSS),
vinyl (Vi-PSS) and phenyl (Ph-PSS) groups (Fig. 6) do not influ-
Fig. 7. TGA plots for PP/5 wt.% polysilsesquioxane in air [45].
ence PP degradation under nitrogen, whereas their presence clearly Copyright 2009. Reproduced with permission from Elsevier Ltd.
affects the polymer stability under air according to TGA [45]. With
increase of PSS’s content, the thermoxidative stability of PP/PSS
blends is much improved as shown by the delay in the weight loss HRR curves of PP/PSS blends. With increase of PSS’s content to
curves towards higher temperature, which depends on type of sub- 5 wt.%, significant pHRR reduction can be observed with Me-PSS
situent. As shown in Fig. 7, the stabilisation effect decreases going (−19%), Vi-PSS (−36%) and Ph-PSS (−10%) addition. The disper-
from the aromatic (Ph-PSS) to the reactive (Vi-PSS) and to the non- sion of PSSs and the nature of substituent play an important role
reactive alkyl (Me-PSS) substituent. Although the different types of on their flame retardancy. The lowest rate of combustion obtained
PSSs could improve the thermal stability of PP/PSS blends, the LOI with Vi-PSS is attributed to the homogeneous dispersion and the
values of PP/PSS composites were not improved by the presence of possibility to produce a crosslinked ceramic phase upon heating,
different PSS compared with pure PP. by the polymerization reaction of vinyl groups [46].
As far as forced combustion in cone calorimeter is concerned, at In another investigations, Barczewski et al. [47] reported an
1.5 wt.% silsesquioxane loading, limited effects are found on the increase in thermal stability of polypropylene modified with
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 83

Fig. 8. Structureal formula of tetrasilanolphenyl-polyhedral oligomeric silsesquiox-


ane (TO-ph-POSS) [48].
Copyright 2014. Reproduced with permission from Taylor & Francis.

0.5 wt.% tetrasilanolphenyl POSS (TO-ph-POSS as shown in Fig. 8). Fig. 10. Heat release rate of PP/POSS composites. [50].
Copyright 2006. Reproduced with permission from Elsevier Ltd.
In a further study of this system [48], they reported that TO-ph-
POSS addition to isotactic polypropylene (iPP) matrix resulted in a
significant lowering of nanocomposite flammability as determined isobutyl radicals. This improved behavior of Al-POSS as compared
by UL-94 horizontal burning test. The burning rate of composite to OI-POSS is caused by the catalytic effect induced by the metal
that contained 10 wt.% of TO-ph-POSS was two times lower than Al during the combustion process. The mechanism leading to com-
that of the neat iPP. This improvement was ascribed to the hybrid bustion rate reduction seems to be chemical rather than physical, as
nanofiller decomposition which led to a migration of inorganic in both cases, only a non-continuous thin ceramic layer from POSS
parts of TO-ph-POSS into the sample surface and caused a shielding degradation is formed on the specimen surface during combustion,
effect. which does not represent an effective physical barrier for combus-
Not only the organic type, but also special elements associated tion processes. Furthermore, the influence of Al-POSS and Zn-POSS
to the POSS cage could affect the thermal stability and combus- on PP thermo-oxidative degradation resulting in an improved ther-
tion properties of PP/POSS nanocomposites. The effect of metal mal stability are caused by a chemical action of the metals on PP
nanoparticles on polymer flammability was explored and shown degradation pathway [50].
that finely dispersed metals at low concentration (1 wt.%) strongly Similar conclusions were reported that metal isobutyl-
enhance PP char yield, by catalyzing dehydrogenation [49]. silsesquioxanes (M-POSS) with TiIV and VV metal centers (Fig. 11),
The effects of Al and Zn containing POSS, Al-POSS and Zn-POSS which have been used as additives (3 wt.%) in polypropylene by
respectively, on PP combustion are investigated by Fina et al. [50]. melt blending [51]. The neat polypropylene and metal-free PP/POSS
They take advantage from the possibility to disperse POSS cages on composites degrade rapidly at 250 ◦ C in air (leaving less than 10% of
a submicron scale into polymer matrix, coupling the POSS prece- residue after 50 min), in the presence of V- and Ti-POSS the degrada-
ramic effect with the catalytic action of a metal site on POSS cage. tion is significantly slower and leads to larger amounts of residues:
Fig. 9 shows the structures of the octaisobutyl POSS (OI-POSS), Al- 28% and 42% respectively after 250 min. This result was due to
POSS and Zn-POSS. Their effect on the fire behaviors of PP/POSS a chemical effect of metal-bearing POSS on the polymer matrix
composites are tested by cone calorimetry at 35 kW/m2 . As shown degradation pathway, thereby inducing significant modifications to
in Fig. 10, as compared with pure PP, PP/OI-POSS shows a higher the high temperature oxidative processes, in particular, oxidative
heat release rate. In the case of PP/Al-POSS, a significant reduction dehydrogenation reactions, which lead to thermally stable charring
(about 43%) of peak of heat release rate with respect to pure PP products.
can be observed. In contrast, PP/Zn-POSS does not show significant Wei et al. [52] prepared a hybrid phosphamide containing
differences on HRR curve as compared to PP. polysilsesquioxane and evaluated its effect on fire retardancy of
In fact, OI-POSS and Al-POSS differ mainly for the presence of polypropylene composites. They found that during the LOI test,
Al in the cage, being the groups linked to the Si atoms in any case the PP matrix burned continuously and the char originated from

Fig. 9. The OI-POSS, Al-POSS and Zn-POSS structures [50].


Copyright 2006. Reproduced with permission from Elsevier Ltd.
84 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

taisobutyl POSS (AM-POSS) during a one-step, high yield reactive


blending process is shown in Fig. 12 [56]. The chemical reactivity
between alkylamino POSS and PPgMA is the key factor for nanofiller
dispersion. The presence of POSS moieties grafted on PPgMA can
improve thermoxidative stability, in terms of delayed mass loss
during thermal degradation under air, as compared to both neat
POSS and PPgMA.
Similarly, the aminopropylisobutyl POSS (AIB-POSS) can be
introduced into PP hybrids by reaction with of PPgMA [57].
POSS nanoparticles dispersed evenly throughout the hybrids
with a spherical shape from several nanometers to a few hun-
dred nanometers. 2.5 wt.% POSS gave a reduction in pHRR (from
62 kW/m2 for reference PP hybrid to 55 kW/m2 ) and 33% decrease
in the total heat release (THR). Although consistent decrease of
pHRR and THR were found, smoke level was increased, which
reduces the interest of using aminopropylisobutyl POSS as a fire
Fig. 11. Structures of trisilanolisobutyl-POSS (1), V-isobutyl-POSS (V-POSS; 2) and retardant for PP. Furthermore, the aminopropylisobutyl POSS can
Ti-isobutyl-POSS (Ti-POSS; 3) [51].
improve fire retardancy of isotactic PP (iPP) as determined by LOI
Copyright 2007. Copyright 2012. Reproduced with permission from John Wiley &
test [58]. Bouza et al. [58] incorporated PPgMA as coupling agent to
Sons Inc.
improve POSS dispersion. The well dispersed POSS led to remark-
able increase in LOI values when 2 wt.% POSS and 10 wt.% MA-g-PP
polysilsesquioxane on the top of samples flowed with the melt-
were compounded with PP matrix. Furthermore, the presence of
ing drops. An effective continuous protective layer was not formed
aminopropylisobutyl POSS in iPP matrix gave a composite with
possibly due to the lower chemical interaction between PP matrix
higher thermal stability than neat matrix as measured by TGA.
and this phosphamide containing polysilsesquioxane.
Using POSS as a potential fire retardant for fibers has attracted
POSS containing hybrid polymers reported in most literature are
much attention. It is feasible to investigate the fire retardance of
made from one-pot copolymerization method or by melt blending,
knitted PP fabric and PP/polyvinylsilsesquioxane (Vi-PSS) multifil-
whereas some reports focused on graft copolymerization of POSS
ament yarns [59]. These were prepared via a melt spinning process
to polymer chains [53,54]. Reactive blending is proved to be key
after extruding virgin PP and PP/Vi-PSS. No significant differences
technology in the polymer industry and regarded as an efficient
can be observed between the PP fabrics and PP/Vi-PSS fabrics, but
method for the continuous polymerization of monomers and for
the touch of PP/Vi-PSS is softer. PP and PP/Vi-PSS show a similar
the chemical modification of existing polymers in the absence of
initial decomposition temperature at about 250 ◦ C, however, the
solvents.
degradation rate of PP/Vi-PSS is slower than that of PP. The residue
The octavinyl POSS (OV-POSS) was successfully grafted to iso-
of PP is close to zero (0.2 wt.%) at 500 ◦ C. while PP/Vi-PSS exhibits a
tactic PP chains by reactive blending of polypropylene (PP) and
stable residue (about 7 wt.%) between 450–800 ◦ C region while its
OV-POSS in the presence of dicumyl peroxide (DCP) [55]. Compared
final residue is 3 wt.%. The fire behaviors of PP and PP/Vi-PSS knit-
with the physical blending PP/OV-POSS composites, reactive blend-
ted fabrics were evaluated using cone calorimetry at a heat flux
ing hybrids had better mechanical and thermal properties. In the
of 35 kW/m2 . The heat release rate (HRR) curves of the two fab-
case of fire retardancy properties of the PP/OV-POSS hybrids, at an
rics show that the time to ignition of pure PP occurs at 21 s which
OV-POSS loading of 5 wt.%, the reduction in pHRR is around 18 and
is much shorter than that of PP/Vi-PSS (76 s) (Fig. 13). The bet-
22% for the reactive blending hybrid and physical blending compos-
ter thermal stability of PP/Vi-PSS yarns is the main reason for this
ite, respectively. The change of the TTI is small, whereas the time of
improvement. However, the peaks of HRR of the pure PP and PP/Vi-
flame out became longer for the PP/OV-POSS composites meaning
PSS fabrics are similar, furthermore, the total heat release (THR) is
that the composites combust longer time with smaller HRR, which
also not modified (about 200 kJ) for the two fabrics.
is profitable for the fire retardancy of PP. For the reactive blending
The effect of octamethyl POSS on the fire retardant properties of
hybrid, the HRR value is slightly higher than the physical blending
a polyethylene–calcium carbonate–silicone (CaSiEMAA) composite
composites, indicating it had worse fire retardancy properties than
system also performed poorly in the cone calorimeter (35 kW/m2 ),
physical blending composites due to DCP promoted PP degradation.
an earlier ignition and higher heat release rates were observed in
The maleic anhydride grafted polypropylene (PPgMA)/POSS
all these composites containing octamethyl POSS compared with
hybrid prepared by reaction with aminoethylaminopropyl hep-

Fig. 12. Reaction between PPgMA and alkylamino POSS during extrusion process [56].
Copyright 2009. Reproduced with permission from Elsevier Ltd.
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 85

Fig. 14. OctaTMA-POSS structure [70].


Copyright 2007. Reproduced with permission from Springer.

Fig. 13. Rate of heat release (RHR) curves of PP and PP/Vi-PSS knitted fabrics [59].
Copyright 2005. Reproduced with permission from the Royal Society of Chemistry.
an improvement of the resistance to thermal degradation in respect
to neat polystyrene, which was averagely higher than that found
with un-bridged POSSs and increasing as a function of aliphatic
Ref. [60]. The only improvement was their ability to increase the POSS bridge length.
combustion residue resulting in good performance in the drip- Besides reacting with PS backbone, some POSS molecular struc-
ping test. The addition of 1 wt.% octamethyl POSS reduced the ture also could form special architectures, which are helpful to
dripping of CaSiEMAA composite by 52%, and CaSiEMAA compos- reduce the flammability of polymer matrix. A flame retarded
ite with 2.5 wt.% octamethyl POSS showed no dripping at all. The PS/POSS nanocomposites containing octa(tetramethylammonium)
positive effect by adding octamethyl POSS is therefore likely an POSS (OctaTMA-POSS, Fig. 14) was prepared by melt-mixing [70].
effect of residue formation as suggested by electron spectroscopy In the TEM images of the hybrids, OctaTMA-POSS nanofiber (Fig. 15)
for chemical analysis (ESCA) of surface layer of materials after can be found in PS matrix. When the ratios of OctaTMA-POSS are
cone calorimeter test. The amount of oxygen and silicon increases raised from 5 wt.% to 30 wt.%, the pHRR and average HRR of the
whereas the carbon content decreases when octamethyl POSS is hybrids drops approximately linearly. There is 31.7% and 54.6%
added, which means that POSS is likely to promote ceramization of pHRR decrease for the composites 20 wt.% OctaTMA-POSS/80 wt.%
the silicon at the surface. PS and 30 wt.% OctaTMA-POSS/70 wt.% PS respectively, compared
Summarising: most of POSS in the polyolefin composites are to pure PS. The CO peak release rate (pCORR) and CO concentra-
added by means of melt blending. Although POSS with reactive tion (COC) in the combustion are also decreased: 1–3, and 5 wt.%
groups such as vinyl, silanol, or aminophenyl, could be grafted to OctaTMA-POSS in the hybrids make pCORR decrease by 51.2, 53.1,
polyolefins by melt blending in presence of maleated polymer. This 50.7, and 52.7% respectively. When the concentration rises to 20
process seems however not competitive with melt blending as far and 30 wt.%, pCORR can be decreased by 66.2 and 70.8% respec-
as fire retardance effectiveness and complexity is concerned. The tively. These fire retardant enhancements improve the fire safety
type of POSS substituent, such as the chain lengths, crystallinity, performance of PS hybrids, which are caused by the formation of
reactivity, play an important role on the flame retardancy, ther- organic–inorganic nanofiber, that can separate the PS matrix into
mal stability, and dispersion of polyolefin/POSS nanocomposites. small unities at nanometer scale [70,71].
But when some metal element (Zn, Al, Ti, or V) was included in Based on the OctaTMA-POSS, lamellar hybrids can be prepared
the POSS molecule, the influence of type of metal is more impor- via template-directed synthesis from OctaTMA-POSS and surfac-
tant than the type of the substituent organic groups. Aluminum tants, which were used to prepare novel PS nanocomposites via
showed the greatest catalytic effect on thermal behavior and fire melt-blending [72]. Compared to pure PS, the peak HRR of the
retardance of polyolefins/POSS nanocomposites. lamellar hybrid/PS composites with 1 wt.% load has been cut down
by 50.6%, and the CO release rate together with CO concentration is
also effectively decreased by more than 60.0%. These improvements
3.2. Polystyrene
in fire retardant properties resulted from homogenous disper-
sion of POSS-surfactant lamellar hybrid (Fig. 16) in the composites
3.2.1. Polystyrene with POSS
caused by its layered nanostructure, thus opening up new ways to
Linear thermoplastic hybrid materials containing polystyrene
prepare novel fire-retarded polymeric materials.
(PS) backbone and large inorganic silsesquioxane groups pendent
Flame retarded PS composites can also be prepared by adding
to the polymer backbone have been prepared by several methods,
lamellar hybrids made up of octa(chloroaminopropyl) POSS (OCAP-
such as: free radical copolymerization [61], Friedel–Crafts reaction
POSS) and dodecyl benzene sulfonic acid sodium salt (DBSS) [73].
[62], in situ polymerization [63,64], and grafting reaction [65]. The
All the chlorine ions in OCAP-POSS are replaced by surfactant
PS/POSS hybrids exhibited improved thermal stabilities with higher
organic chains and a two-dimensional multilayered structure is
degradation temperature and char yields than PS, revealing that
formed as shown in Fig. 17 [74]. The POSS are dispersed well in the
inclusion of the inorganic POSS made the organic polymer matrix
composites, and the value of pHRR of the composite with 1 wt.%
more thermally robust.
of POSS showed about 50.0% reduction compared to neat PS. Low
A series of PS/POSS hybrids were synthesized from styrene
addition of POSS could result in good fire retardancy of PS/POSS
and single styryl cyclopentyl POSS (SC-POSS) via copolymeriza-
nanocomposites, but further addition of POSS cannot improve the
tion using CpTiCl3 as a catalyst [66]. The char residue at 700 ◦ C
fire retardant action. The CORR and COC are also substantially
was increased from 0 to 21.8 wt.% in air when 3.2 mol% POSS
decreased.
was incorporated in the PS structure. Furthermore, the bridged
bis(triethoxysilyl)alkanes isobutyl POSS (HIB-POSS) can be pre-
pared by corner capping reaction of isobutyltrisilanol POSS with 3.2.2. Polystyrene with POSS and halogen-containing compounds
the suitable bis(triethoxysilyl)alkanes [67]. PS/POSS hybrids can be The POSS with heteroatom normally show two effects: the
easily prepared by in situ polymerization of 5% w/w POSS/styrene first one is that the fire retardant heteroatoms could improve
mixtures in toluene [68,69]. The hybrids thermal analysis showed the fire retardance of polymer by itself; the second one is that
86 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 15. TEM images of POSS/PS hybrids: (A) 20 wt.% OctaTMA-POSS/80 wt.%PS; (B) 30 wt.% OctaTMA-POSS/70wt.%PS [70].
Copyright 2007. Reproduced with permission from Springer.

Fig. 16. TEM images of PS composites containing (A) 1 wt.% (B) 5 wt.% lamellar hybrid [72].
Copyright 2011. Reproduced with permission from Taylor & Francis.

Br Br

Br
O
Si Si
O O
O
Si Si
O O Br
O O Br
Si Si
O O O
Si Si
O
Br Br
Fig. 18. Bromination of octaphenyl polydedral oligomeric silsesquioxane (Br.ph-
Fig. 17. Illustration of the lamellar OCAP-POSS/DBSS hybrid [74]. POSS).
Copyright 2007. Reproduced with permission from Elsevier Ltd.

the heteroatoms could bring some changes (reactivity, structures, Br.ph-POSS nanoparticles can be synthesized from the reaction
degradation process, etc.) for polymer composites which could between ph-POSS and Br2 catalyzed by Fe powder in CH2 Cl2 solu-
influence their fire retardance. tion (Fig. 18), and added them as fire retardants for polystyrene
Traditionally, halogenated compounds have been widely used [75]. The Br.ph-POSS was more effective in reducing the peak heat
as co-monomers or additives in polymers to obtain fire-retardant release rate (the largest relative decrease was 84.2%) compared
materials. It was however found that the polymers containing halo- with ph-POSS, while ph-POSS resulted in slower smoke produc-
gen elements can produce on burning poisonous and corrosive tion rate (SPR) and rather bigger drops in peak values of CO release
smoke and may produce highly toxic halogenated dibenzodiox- rate (pCORR) and CO concentration (pCOC) during the combustion
ins and dibenzofurans. POSS are used as typical halogen-free flame test (the largest relative decrease in pCORR and pCOC were 81.8
retardants therefore there is little work on polymers flame retarded and 84.3%, respectively) compared with Br.ph-POSS. These differ-
by combination of POSS with halogen-containing compounds. ences are due to the presence of Br in the Br.ph-POSS, which is an
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 87

effective fire retard element in the gaseous phase, but leads to more of T-POSS takes place within a temperature range much higher
smoke. than that of PMMA. The physical incorporation of both MAE-POSS
Furthermore, the (ph-POSS + Sb2 O3 ) and (Br.ph-POSS + Sb2 O3 ) and T-POSS into P-m-PMMA increases heat release capacity (HRC)
were used as flame retardants for polystyrene to reduce its from 200 J/gK to 207 J/gK and 249 J/gK respectively. Apparently,
flammability [75]. Both ph-POSS or Br.ph-POSS with Sb2 O3 syn- silicon–phosphorus interaction in PMMA either has no effect or it
ergist system can improve the fire-retardance performance of is antagonistic.
polystyrene. However, the (Br.ph-POSS + Sb2 O3 ) combination sys- The terpolymer P-m-PMMA-POSS was also prepared via copoly-
tem is more effective in reducing the HRR value. The improvements merization of MMA (MMA + P-m-MMA) and MAE-POSS via free
in HRR values were to be attributed to the decomposition of POSS radical polymerization technique as shown in Fig. 20 [82]. The
nanoparticles which absorbs a great deal of heat and slows the chemical incorporation of MAE-POSS into the PMMA chains
rising temperature rate in the base polymer and then delays its (Fig. 20A) led to a greater improvement of thermal stability, residue
further decomposition and combustion. After the exhaustion of amount as measured by TGA and fire retardant properties (HRC and
the organic parts of POSS nanoparticles, the residual material led total heat release) as measured by PCFC than the physical incorpo-
to the formation of compact ceramic layers made of silicon oxide ration of MAE-POSS in PMMA. Whereas the chemical incorporation
on the surface of nanocomposites which limit the oxidant dif- of MAE-POSS into the P-m-PMMA chains (Fig. 20B) led to an oppo-
fusion in the condensed phase and thereby delays the oxidation site result that is its thermal stability and flammability properties
and combustion processes. For the better performances of (Br.ph- were weakened compared to physical blend (P-m-PMMA/MAE-
POSS + Sb2 O3 ) system, these were mainly the results of high flame POSS).
retardant efficiency of Br-Sb synergistic effect, whose mechanism A fire retarded PMMA material was prepared by using
has been illustrated since many years ago. triphenylphosphate (TPP) and polyphenylsilsesquioxane (PPSQ)
nanospheres [83]. The total amount of fire-retardant TPP and PPSQ
3.3. Poly(methyl methacrylate) was 20 wt.%, and the amount of PPSQ was 0, 1, 3, 5 wt.% for different
samples. The thermal stability of PMMA composites measured by
Poly(methyl methacrylate) (PMMA) is a transparent poly- the temperature for 10% and 50% weight loss are all shifted to high
mer mainly used as coatings and glazings. Fire retarded PMMA temperature due to the addition of PPSQ. In cone calorimeter test,
nanocomposites have been prepared by the addition of nanoparti- the time to ignition (TTI) and time to peak heat release rate (tpHRR )
cles such as POSS, organically modified montmorillonite (OMMT), of the PMMA/TPP composites with PPSQ are higher than that of
layered double hydroxides (LDH), layered hydroxy salts (LHS), TiO2 , PMMA/TPP blend. Furthermore, the pHRR, total heat release (THR),
Fe2 O3 , and carbon nanotubes (CNT) [76–78]. The typical nanocom- and average mass loss rate (AMLR) of PMMA/TPP/PPSQ compos-
posites preparation methods, including in situ polymerization, ites decrease gradually with increase of PPSQ content. When PPSQ
solution blending, and melt blending were all successfully used to nanospheres were added, the reactions of pyrolytic products of TPP
obtain well-dispersed nanoparticles in the PMMA matrix. The ther- and PPSQ could form a ceramic-like silicon phosphate structure at
mal stability and fire retardancy of PMMA/POSS nanocomposites high temperature to promote the formation of a dense and compact
or hybrids were seriously influenced by the nanoparticles addition surface protective layer [83]. Furthermore, PPSQ can impede the
methods [79,80]. out-diffusion of the volatile decomposition products from matrix
The PMMA hybrids with trisilanolphenyl POSS (T-POSS) can or in-diffusion of oxygen into matrix due to the barrier structure of
be prepared by the bulk polymerization using azodiisobutyroni- the ceramic-like surface layer [84].
trile (AIBN) as the radical initiator [81]. The onset temperatures of It may be concluded that no matter whether the POSS were
PMMA/T-POSS hybrids are little higher than that of pure PMMA added by physical mixture or chemical reaction, the PMMA com-
and the temperature at which 50% degradation occurs is increased posites do not show improvement of fire retardancy due to the
by 30–60 ◦ C. However, the combustion behaviors such as time to addition of POSS. But when the POSS was added as a synergist with
ignition (TTI), peak of heat release rate (pHRR), total heat release some phosphorus containing fire retardants in low loading, there
(THR), and mass loss rate (MLR) of PMMA do not show significant is evidence that the fire retardancy of PMMA composites improves.
improvement upon the addition of T-POSS. On the contrary, a large
increase of specific extinction area (SEA) was detected which means
more smoke release due to addition of T-POSS. 3.4. Polycarbonate
The influence of trisilanolphenyl-POSS (T-POSS) and
methacrylateethyl-POSS (MAE-POSS) on thermal degradation 3.4.1. Polycarbonate with POSS
and flammability properties of both PMMA and a phosphonated Bisphenol A polycarbonate (PC) is one of the fastest growing
modified PMMA (P-m-PMMA) (Fig. 19) were investigated by engineering polymers, with excellent mechanical and electrical
Vahabi et al. [82]. The physical blends of PMMA or P-m-PMMA properties. The pure PC shows a V-2 rating in the UL-94 test because
with T-POSS and MAE-POSS were prepared by solution blending of flame dripping, but more strict fire retardant performance is
method using tetrahydrofuran as solvent. In the physical blends often required for electronic and electric applications [85]. Silicon
systems, the PMMA and P-m-PMMA filled with T-POSS showed containing compounds R3 SiO1/2 , R2 SiO, RSiO3/2 , and SiO2 in various
better thermal stability than the pure polymers, which was due to combinations, are commonly used as novel fire retardant additives
the high thermal stability of T-POSS. Whereas the thermal stability for polycarbonate [86]. Be one of them, POSS with different struc-
of PMMA and P-m-PMMA filled with MAE-POSS was reduced due tures can result in different dispersion morphology and different
to the fact that the first weight loss step of MAE-POSS (80% weight fire retardancy of PC/POSS nanocomposites.
loss) began at 165 ◦ C. Octaphenyl POSS (OPS) is one of the most simple non-reactive
According to pyrolysis combustion flow calorimeter (PCFC), POSS. The incorporation of OPS could improve thermal oxidative
MAE-POSS reduces the PMMA heat release capacity (HRC) by stability of PC composites and increase the residue upon thermal
about 21%, while T-POSS can only reduce it by about 5%. The degradation in air. Whereas OPS does not significantly affect the
higher decrease of HRC of PMMA/MAE-POSS can be explained PC thermal degradation in nitrogen, due to OPS sublimation [87].
by the interaction between the products formed from degrada- Furthermore, the tendency for OPS to aggregate and its poor dis-
tion of MAE-POSS and PMMA [82]. Whereas for PMMA/T-POSS persion in polymers restrict the use of it. So surface modification
sample, these interactions do not occur since the degradation of OPS or reduction of OPS particle size, which will improve the
88 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 19. Chemical structure of (a) pure PMMA, (b) phosphonated modified PMMA (P-m-PMMA), (c) trisilanolphenyl-POSS(T-POSS), (d) methacrylateethyl-POSS(MAE-POSS)
[82].
Copyright 2012. Reproduced with permission from Elsevier Ltd.

Fig. 20. The copolymerization of PMMA-POSS and P-m-PMMA-POSS [82].


Copyright 2012. Reproduced with permission from Elsevier Ltd.

compatibility and dispersion of OPS and help to improve the fire


retardancy of PC composite, should be the aspects to be adressed.
An ultrafine OPS with diameter of OPS cluster particles less than
400 nm were prepared and added to polycarbonate (PC) compos-
ites by melt blending [88]. The LOI values of PC composites increase
from 26% to 33.8% with 6 wt.% OPS loading, while the UL-94 rat-
ing of the PC/3 and 6 wt.% OPS composite could reach V-0 rating at
3.2 mm and 1.6 mm respectively. The peak heat release rate (pHRR)
of PC/6 wt.% OPS decreases from 570 kW/m2 of PC to 292 kW/m2 .
The ultrafine OPS can accelerate the char formation of PC compos-
ites (Fig. 21), which results in a lower heat release rate, average
carbon monoxide and dioxide production. The char layer of burnt
PC/OPS composites was studied by cone calorimetry under differ-
ent heat fluxes and the strength of their char residue was tested
[89]. It was found that the char formation of PC/OPS composites
takes a longer time than neat PC. The char layer of PC/OPS com-
posite combustion is compact and homogeneous, which is good for
preventing heat transfer. Fig. 21. Picture of char residue under cone calorimeter testing of PC/6 wt.% OPS
composite [88].
Song et al. prepared PC/POSS composites based on bisphenol A
Copyright 2012. Reproduced with permission from John Wiley & Sons Inc.
polycarbonate and trisilanolphenyl POSS (T-POSS) by melt blending
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 89

Fig. 24. Typical chemical structure of polyphenylsilsesquioxane (PPSQ) [92].


Copyright 2012. Reproduced with permission from John Wiley & Sons Inc.
Fig. 22. TEM image of the PC/3 wt.% TPOSS hybrid [90].
Copyright 2008. Reproduced with permission from Elsevier Ltd.
The use of silanol groups in trisilanolphenyl POSS (T-POSS) to
react with some polymers, is made difficult by the steric hindrance
of T-POSS and the low reactivity of its silanol groups, especially
[90]. Although the T-POSS cannot react with the PC matrix during during the melt blending. However, the T-POSS shows more com-
the melt blending process, the T-POSS could disperse in PC matrix as patibility compared with octaphenyl POSS (OPS) with completed
elliptical nanoscale particles as shown in Fig. 22. The T-POSS could T8 caged structure due to the existence of three silanol groups.
react with the alkyl and aromatic substituted phenols produced by The polyphenylsilsesquioxane (PPSQ), which is a ladder polymer
hydrolysis of PC (Fig. 23) and the high reactive free radicals derived with a double Si–O chain structure as shown in Fig. 24, was added
from the thermal oxidative degradation of PC which simultane- to PC composites by the melt blending method [92]. The spherical
ously interfere with the decomposing and crosslinking process of PPSQ particles of size 0.5–1.5 ␮m were homogeneously dispersed
PC matrix at lower temperature. The addition of 2 wt.% T-POSS sig- in PC. Thermal gravimetric analysis and Fourier transform infrared
nificantly decreased by about 45% pHRR of PC composites, while the spectroscopy revealed that PPSQ made the initial thermal decom-
presence of T-POSS shortened the ignition time. The incorporation position of PC occur fast. The early cleavages of C C and C O bonds
of T-POSS enhances the thermal oxidative stability of the char layer in the PC chains induced crosslinking reactions in the condensed
which is created on the surface of the burning polymer [90,91]. phase. 8 wt.% PPSQ reduced the peak heat release rate of PC com-

Fig. 23. The reactions between T-POSS and the alkyl substituted phenols derived from the hydrolysis/alcoholysis products of PC [90].
Copyright 2008. Reproduced with permission from Elsevier Ltd.
90 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 25. The structure of poly[(phenylsilsesquioxane)-co-(dimethylsiloxane)]


(PPSQDS) [93].
Copyright 2013. Reproduced with permission from Taylor & Francis.

Fig. 27. The structures of bisphenol A bis(diphenyl phosphate) (BDP) and resorcinol
bis(diphenyl phosphate) (RDP).

to dripping, showing that the cage structure performs better fire


retardancy than that of random structures.
Thus, literature data show that POSS either with caged or ladder
Fig. 26. Typical chemical structures of DOPO-POSS molecules [95].
structures, or POSSs with phosphorus elements, in the PC compos-
Copyright 2010. Reproduced with permission from Elsevier Ltd.
ites cannot make them reach UL-94 rating due to dripping. So an
anti-dripping agent must be used to improve the fire retardancy of
posites from 570 to 153 kW/m2 , and the total heat released by 60%. PC composites. However, due to the structure of POSS, especially for
Furthermore, the smoke release (SEA) was greatly reduced by PPSQ; the ladder structure, it has the potential to increase the fire retar-
and low average CO and CO2 emissions from PC/PPSQ composites dancy and address the dripping problems of PC composites at the
combustion was observed as well [92]. The chars obtained after same time.
cone calorimeter testing of PC/PPSQ composites showed continu-
ous, smooth, and flaky structure char and SiO2 ceramic layer on the 3.4.2. Polycarbonate with POSS and Organophosphate
top. Beside good performance of cone calorimeter test, PC/PPSQ compounds
composites also show remarkable results in the LOI and UL-94 Among the organophosphate flame retardants, bisphenol A
tests. LOI of PC was raised from 26.0% to 42.0% by the addition of bis(diphenyl phosphate) (BDP, Fig. 27) and resorcinol bis(diphenyl
8 wt.% PPSQ and 6 wt.% loadings of PPSQ made PC composites attain phosphate) (RDP, Fig. 27) are important compounds used in engi-
ratings of 1.6 mm V-0. neering plastics because of their excellent compatibility with the
Xia et al. [93] reported the thermal degradation and fire retar- matrix, and their relatively high thermal and hydrolytic stability
dancy of PC composites loaded with poly[(phenylsilsesquioxane)- [100,101].
co-(dimethylsiloxane)] (PPSQDS). The structure of PPSQDS is shown BDP in combination with trisilanolphenyl POSS (T-POSS) was
in Fig. 25, which is characterised by flexible polysiloxane chain seg- used to flame retard bisphenol A polycarbonate (PC) by melt blend-
ments and rigid POSS cage [85]. The addition of PPSQDS increased ing method [102]. The BDP enhances the thermo-oxidative stability
thermal stability of PC and the char residue yield. The LOI values of the PC composite, while the combination T-POSS with BDP can
and UL-94 burning rating of PC/PPSQDS composites are improved further enhance the thermo-oxidative stability of this composite,
with the increase of PPSQDS content. When PPSQDS content was especially with regard to increase of the onset degradation tem-
6 wt.%, the LOI value of PC was enhanced to 33% (26% for pure PC) perature and amount of char formation.The 2 wt.% T-POSS coupled
and the PC UL-94 rating improved to V-1 from no rating (3.2 mm). with 3 wt.% BDP significantly decreased the value of peak heat
Zhang et al. [94,95] synthesized a DOPO-containing polyhe- release rate (pHRR) of the PC composite more than 45%, while the
dral oligomeric silsesquioxane (DOPO-POSS) shown in Fig. 26. BDP could only reduce the pHRR by about 21%. The synergy between
SEM micrographs of PC/DOPO-POSS composites prepared by the T-POSS and BDP is caused by the fact that SiO2 residues from T-
melt blending method suggested that 100–250 nm DOPO-POSS POSS could react with phosphate groups of the char layer to yield
nanoparticles were dispersed but sharply separated from the PC silico-phosphate, which can stabilize phosphorus species and char
matrix. DOPO-POSS effect on fire retardancy of PC are positive and layer. The presence of SiO2 can further enhance the viscosity and
effective according to LOI, UL-94, and cone testing. When the DOPO- thermal-oxidative stability of the char layer containing phospho-
POSS content was 4 wt.%, the LOI value of PC was increased from rous which builds up on the surface of the burning polymer, and
24.1% to 30.5% and the UL-94 rating reached V-0 from V-2 rating. insulates it from heat and oxygen diffusion, as well the release of
During combustion processes of 4 wt.% PC/DOPO-POSS compos- volatile products of decomposing polymer matrix.
ite in cone calorimeter, the pHRR of the composite decreases, but Combination of RDP and T-POSS into PC can improve the flame
the THR remains the same as that of PC. Excellent fire retardancy retardancy of this composite without affecting its transparency
of DOPO-POSS in polycarbonate/acrylonitrile-butadiene-styrene [103]. TGA results have highlighted that PC/T-POSS/RDP sample
(PC/ABS) blends was also detected [96]. According to TGA, DOPO- exhibits a reduced rate of degradation and an increased residue
POSS significantly enhances the thermal stability of PC/ABS. When amount compared to PC, PC/T-POSS and PC/RDP. The cone calorime-
the DOPO-POSS content is 10 wt.%, the pHRR value of PC/ABS is ter test has shown that PC/T-POSS/RDP sample exhibits also the
reduced from 539 to 266 kW/m2 , and the UL-94 rating can reach best flame retardancy performance with a low HRR, THR, TSR and
V-0 (3.2 mm). A DOPO-POSS like random polymer structure named an important quantity of char residue. The presence of RDP can
P(DOPO-VTES) was prepared by Zhong et al. and Hu et al. [97–99], decrease the aggregation of T-POSS particles and thus improve their
which showed good fire retardancy for PC or PC/ABS. LOI values of dispersion in the matrix compared to PC/T-POSS blend as shown in
PC or PC/ABS is increased, but UL-94 rating is not reached owing Fig. 28. A better dispersion of T-POSS is helpful to form a cohe-
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 91

Fig. 29. The LOI of PC containging (a) KSS, (b) equivalent KSS and PAPSQ, (c) equiv-
alent KSS and PVDF, and (d) equivalent KSS and PAPSQ and PVDF as a function of
the complex additives [109].
Copyright 2006. Reproduced with permission from Elsevier Ltd.

As a general behavior, the adjuvant effect of organophosphate


flame retardants to POSS can work in two ways. One is that POSS
could react with phosphate groups of the char layer to yield silico-
phosphate, which can stabilize phosphorus species and char layer.
The other is that the presence of organophosphate flame retar-
dants can improve the dispersion and the compatibility of POSS. The
presence of synergistic effect between POSS and organophosphate
flame retardants could make the materials get good fire retar-
dancy performance at low loading of POSS and organophosphate
flame retardants, which is very useful to reduce negative impact to
materials brought by organic phosphorus flame retardants, such as
reducing modulus, glass transition Tg , and strength.

3.4.3. Polycarbonate with POSS and metallic compounds or


organic salts
Fig. 28. SEM images of (a) PC/T-POSS and (b) PC/T-POSS/RDP samples [103]. Sulfonate salts such as potassium perfluorobutane sulfonate
Copyright 2013. Reproduced with permission from Elsevier Ltd. (PFBS), potassium diphenyl sulfonate (KSS), and poly(sulfonyl
phenylene phosphonate) (PSPPP) are particularly effective in flame
retardancy of PC even at as low as 0.05–0.1 wt.% loading [106–108].
However, the use of these salts alone is not satisfactory especially
sive char layer and enhance the thermo-oxidative resistance of in thin walled articles, i.e. those with a wall thickness of less than
the protective layer. BDP combine with T-POSS shows better fire 2.5 mm, in which they are combined with additional additives. As
retardancy than that of combination of RDP and T-POSS, but RDP is a kind of burgeoning additive flame-retardant in high polymers
helpful to improve the dispersion of T-POSS. fire safety, POSS in combination with sulfonate salts significantly
Combination of dimethyl methyl phosphonate (DMMP) and reduce the generation of smoke, heat and toxic carbon monoxide
octavinyl POSS (OV-POSS) can flame retard ultraviolet-cured epoxy gas during PC combustion.
acrylate (EA) containing microencapsulated phase-change materi- A synergistic effect of poly[(phenylsilsesquioxane)-co-
als (Micro-PCM) [EA/Micro-PCM] [104]. The EA/Micro-PCM system (dimethylsiloxane)] (PPSQDS) and KSS on the thermal degradation
with 8 wt.% DMMP and 2 wt.% OV-POSS shows much lower heat and flame retardancy of polycarbonate (PC) was observed [93]. A
release capacity (HRC) and HRR than that of other EA/Micro-PCM 33.5% LOI value and V-0 rating for both sample bars, with thickness
system with DMMP or OV-POSS only. These facts are due to the of 3.2 mm and 1.6 mm, was obtained in the presence of 0.5 wt.%
synergistic effect of phosphorus and silicon: OV-POSS is oxidized at KSS and 4 wt.% PPSQDS. Whereas, when using PPSQDS alone, even
high temperature, and can react with DMMP in the EA/Micro-PCM at 6 wt.% loading, a V-0 rating could not be achieved for either
system to form branched and cross-linked structure. Combination the thick (3.2 mm) or thin (1.6 mm) samples, although a 32.5%
of Hexa-(phosphaphenanthrene-methyl-(p-hydrobenzal)-amino- LOI was obatined. The combination of PPSQDS and KSS could
phenoxyl)-cyclotriphosphazene (HPHAPC) and trisilanollsobutyl increase the PC degradation rate to promote a fast formation of a
POSS (TIB-POSS) were used to flame retard PLA/polycarbonate (PC) protective char layer on the surface, which inhibited the supply of
alloys by melt blending [105]. The flammability evaluation of this combustible gas and heat transfer [93].
composite has indicated that the LOI value can reach up to 31.5 and For PC added with equivalent weight KSS,
UL-94 grade can pass V-0 by the presence of only 3 wt.% HPHAPC poly(aminopropyl/phenylsilsesquioxane) (PAPSQ) and
and 3 wt.% TIB-POSS. It is demonstrated that HPHAPC can react with poly(vinylidenefluoride) (PVDF), the LOI was higher than the
POSS during processing to form an intumescent char structure. Fur- use of KSS alone whatever the KSS concentrations as shown in
thermore, the degradation products of HPHAPC/POSS can capture Fig. 29 [109]. The LOI amounted to the maximum value of 38.8%
free radicals in the gas phase and enhance char formation in the due to the synergistic retardancy of KSS, PAPSQ and PVDF when
condensed phase. the amounts each of the three additives went up to 0.2 wt.%.
92 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 30. The structures of additives and their effects on the melt flow rate (MFR) and the average flameout time of PPE [113].
Copyright 2007. Reproduced with permission from Elsevier Ltd.

Fig. 31. Cross-section photographs of burned test pieces of (1) PPE and (2) PPE/POSS nanocomposite. [113].
Copyright 2007. Reproduced with permission from Elsevier Ltd.

Furthermore, 1.6 mm thickness samples achieved successfully resistance of PPE. The PPE industry has long had the goal of devel-
UL94 V-0 rating when additives were present at 0.1–0.3 wt.% oping a PPE composite which shows both excellent processability
loading. The substantial synergy of KSS, PAPSQ and PVDF raised and fire retardancy while keeping the excellent thermal resistance
the PC degradation rate to promote the quick formation of a char of PPE.
layer on the surface and reduce the activation energy of thermal Ikeda and Saito [113] reported that addition of small amounts of
degradation of PC based on the Kissinger kinetic analysis. Thus a amino-POSS dramatically improves both the fire retardancy and the
highly cross-linking aromatic ester and ether char that inhibited melt processability of PPE at the same time, while maintaining the
the supply of flammable gas and heat transfer were formed. excellent thermal resistance of PPE. The structures of additives and
their effects on the MFR of PPE are shown in Fig. 30. The diamino-
silicone (A) and polyphenylsilsesquioxane (B) have no influence on
3.5. Poly(phenylene ether) the MFR of PPE. Whereas the amino-POSS (C or D) could dramat-
ically increase the MFR, which means easy processability of PPE
Poly(phenylene ether) (PPE) shows high glass transition tem- composites. Furthermore, in Fig. 30, the average flameout time of
perature, high heat distortion temperature, and also shows good PPE with amino-POSS (C or D) during the UL-94 tests is much lower
self-extinguishment. However, the melt flow rate (MFR) of PPE is than that of pure PPE, which means improved fire retardancy of
too low for melt processing [110], which could be increased by PPE. As shown by burned samples in Fig. 31, the control sample
blending PPE mainly with polystyrene (PS) [111,112]. However, this of PPE had many ruptured foam layers which allow the evolu-
improvement is at the expense of the fire retardancy and thermal
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 93

Fig. 32. HRR curves of PET/OP950/OMPOSS formulations containing 10 wt.% addi-


tives [115].
Copyright 2008. Reproduced with permission from Elsevier Ltd.

tion of flammable gas release during the combustion. Whereas the


PPE/amino-POSS showed an un-ruptured foam layer, which seems
Fig. 33. The Structure of DP-POSS (Dodecaphenyl POSS) [117].
act as a fire retardant barrier to heat and mass transfer. Copyright 2012. Reproduced with permission from Elsevier Ltd.

3.6. Polyesters
case of PET/OP950/OM-POSS or PET/OP950/Vi-PSS is comparable
3.6.1. Poly(ethylene terephthalate) with POSS and inorganic with that of PET/OP950. Whereas PET/OP950/DP-POSS shows a THR
phosphorus compounds reduction by more than 33%, reflecting its rapid extinction com-
Poly(ethylene terephthalate) (PET) use is in constant growth for pared to the sample containing OM-POSS or Vi-PSS. This is due
various applications, due to its easy processability, low cost and to the optimized intumescence of the material containing phenyl
good mechanical and chemical properties, Nevertheless, it may POSS (DP-POSS) where the char is expanded with cell structure,
constitute a potential high hazard as it poorly withstands elevated which is caused by the combination of the radicals groups released
temperatures and would feed fire by producing flammable volatile during the decomposition of DP-POSS into the polyaromatic char
thermal degradation products which play the role of fuel. That is structure.
why several works were carried out to enhance the fire resistance Substituting zinc phosphinate (OP950) by aluminium phosphi-
of this thermoplastic polymer [114]. nate (OP1230), the PET multifilaments containing 9 wt.% of OP1230
Recycled PET is fire retarded by the incorporation of octamethyl and 1 wt.% of POSS (OM-POSS or DP-POSS) has been successfully
POSS (OM-POSS) and zinc phosphinate (OP950) [115]. Addition of melt-spun [118]. A synergy trend was detected by incorpora-
OP950 to PET leads to intumescence explaining the improvement of tion of OP1230 and OM-POSS blends with decrease of the total
fire retardancy. Addition of OM-POSS, although poorly dispersed in heat evolved up to 38% and the peak of heat release rate up to
PET matrix, synergises with OP950 as shown by the increase in LOI 50%, conferring to the produced PET textile fire resistant prop-
values from 29% for PET + OP950 10 wt.% formulation to 36% when erties. Whereas incorporation of OP1230 and DP-POSS blends
1 wt.% of OP950 is substituted by OM-POSS. Cone calorimeter data which has no significant effect on the total heat evolved, and only
of Fig. 32 show that 9 wt.% OP950 and 1 wt.% OM-POSS burn with a could achieve a 20% reduction of peak heat release rate (pHRR)
pHRR lower than that of the composite containing 10 wt.% OP950. compared to that of pure PET. Summarising: PET textiles with OM-
Its HRR curve divides into two small peaks from one big peak of POSS/OP1230 showed the earliest ignition, allowed the production
composite containing only OP950, which indicates a different char of an effective physical barrier with early insulation of the material
formation process due to the addition of OM-POSS. However, time from the external heat, limiting the release of combustible gaseous
to ignition of PET which is increased from 75 s to 109 s by OP950, species. Contrarily, PET textiles with DP-POSS/OP1230 ignited later
decreases to 73 s in presence of 1 wt.% OM-POSS, while CO and total and produced a char under heat constraints but the carbonaceous
heat release is not modified [115]. Further investigation about the swollen protective layer was not highly effective against fire prob-
fire retardancy mechanism of OP950 and OM-POSS in PET compos- ably due to the large amount of combustible gases released on
ites showed that OM-POSS degrades to form mainly silica and other heating which may have broken the char layer giving way to the
silicone fragments, while OP950 degrades to form phosphine, phos- supply of flammable volatile.
phates, and polyphosphates without chemical interaction between Fire retarded PET multifilament fibers can be prepared also by
OM-POSS and OP950 [116]. The synergy observed between OM- loading with OP950 and OM-POSS via melt spinning method [119].
POSS and OP950 is therefore not due to chemical reactions but to In this knitted fabrics, incorporation of OM-POSS nanoparticles in
a physical effect that is sublimation and/or decomposition into gas PET/OP950 systems slightly damaged the fire properties showing
products of OM-POSS acting as a blowing agent inproving insula- a higher pHRR (312 kW/m2 ) than fabrics containing only OP950
tion by the intumescent system. (218 kW/m2 ). Fig. 34 shows the released smoke density of knitted
In order to investigate the influence of structure of POSS, three samples while burning. The PET/10 wt.%OP950 shows the fastest
different POSS: octamethyl POSS (OM-POSS), polyvinylsilsesquiox- smoke production rate, thus presenting a density peak of 339 u.a at
ane POSS (Vi-PSS), and dodecaphenyl POSS (DP-POSS) (Fig. 33) have 250 s while pure PET evolves smoke at a rate twice as slower but
been used to fire retard PET in combination with zinc phosphi- with a higher peak of 462 u.a at about 500 s. The addition of POSS
nate (OP950) [117]. The addition of 1 wt.% Vi-PSS or DP-POSS in completely changes the observed behavior as the smoke density
PET/OP950 blend could increase the onset temperature of decom- reached within the test period a plateau at optical density showing
position more than OM-POSS. Furthermore, substituting 1 wt.% of a reduction of 40% compared to pure PET.
OP950 by OM-POSS, DP-POSS or VI-PSS, the pHRR of PET reduces Carosio et al. [120] reported that ␣-zirconium phosphate
from 365 to 214–244 kW/m2 . The total heat evolved (THR), in the nanoplatelets (ZrP) combined with octa n-propylammonium
94 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 34. Released smoke density of kintted fabrics while burning under 25 kW/m2 heat flux [119].
Copyright 2012. Reproduced with permission from Elsevier Ltd.

chloride POSS (OCAP-POSS) in the layer-by-layer deposition


on poly(ethyleneterephthalate) fabrics evidenced a significant
improvement of their thermal and thermo-oxidative stability,
together with an increased time to ignition (15%), a lowering of heat
release rate (26%), as well as a significant decrease in smoke release
rate (17%) and production of carbon monoxide (35%). Thus, the
proposed approach may turn out to be very advantageous for con-
ferring flame retardancy to textiles. This is all due to the assembly
of nanoplatelets ZrP and nanocages POSS which form an inorganic
barrier that can physically protect PET fibers from heat and oxygen.
Fig. 35. Structure of aminoethyl-amino propyl-isobutyl POSS (AEAPI-POSS) [124].
The structure of such barrier depends on the assembly formula-
Copyright 2013. Reproduced with permission from Polimery.
tion since ZrP initially dehydrates (100 ◦ C), subsequently follows a
reversible phase transition (220 ◦ C) and then forms Zr pyrophos-
phate that is stable up to 900 ◦ C [121]. In addition, the further POSS (OM-POSS), and trisilanol phenyl POSS (T-POSS). As shown
presence of POSS leads to the formation of silica, which plays a in Table 2, a synergistic effect of the OM-POSS and phosphinate
key role in limiting the heat release and smoke production rate. salts can be detected in cone tests, which could lead to about 30%
decrease of the pHRR values. Whereas the LOI and UL-94 are not
3.6.2. Poly(ethylene terephthalate) with POSS and enhanced.
montmorillonite clay In contrast, an antagonistic effect of T-POSS with phosphinate
A series of nanofillers were used to flame retard poly(ethylene salts was detected in LOI and UL-94 tests, which decreases UL-94
terephthalate) (PET), including sodium montmorillonite (MMT) classification from V-0 to V-1 and reduces the LOI values, but a syn-
and trisilanolphenyl POSS (T-POSS) [122]. As shown in Table 1, it ergistic effect of the T-POSS and phosphinate salts in cone test was
is reported that incorporation of the MMT with or without adding observed. For the AEAPI-POSS, when it is coupled with phosphinate
T-POSS into PET only had modest effect upon flammability; the salts, an antagonistic effect can be detected in LOI test, but a syn-
MMT/T-POSS mixture could reduce the pHRR and mean HRR by ergistic effect was detected in the UL-94 test. Authors suggested
about 28% and 17%, respectively and strongly reduced TTI of PET that the synergistic or antagonistic effect when POSS is combined
composite. From these researches, it is implied that adding POSS to with phosphinate salts not only depends on the organic groups
the polymer/clay nanocomposites does not induce any synergistic of POSS, but also has relationship with the combustion condition
effect between POSS and nanoclay. which could influence the decomposition process of fire retardants
and polymer matrix.
3.6.3. Poly(1,4-butylene terephthalate) with POSS and
phosphinate compounds 3.6.4. Poly(butylene succinate) with POSS
Poly(1,4-butylene terephthalate) (PBT) is a very important engi- Poly(butylene succinate) (PBS) is one of the most promising and
neering thermoplastic polymer, which is very often reinforced by important biodegradable polymers with superior mechanical and
glass fibers (GF) to improve its mechanical properties (GF-PBT) thermal properties. However, being an aliphatic polyester, PBS is
[123]. Applications of GF-PBT could be limited due to its high highly combustible which limits its application for example in auto-
flammability. motive components and electronic/electrical industry [125,126]. It
Louisy et al. [124] reported the use of aluminum diethylphos- is therefore necessary to provide fire retardance to PBS materials.
phinate (OP1240) or a combination of melamine cyanurate and PBS composites were prepared by melt blending PBS with
of aluminum diethylphosphinate (OP1200) in combination with melamine phosphate (MP) and octaaminophenyl POSS (OAPS,
POSS in the GF-PBT composite. The POSS are the amino-ethyl- Fig. 36) [127]. A series of blends of MP and OAPS used to fire retard
amino-propyl-isobutyl POSS (AEAPI-POSS, Fig. 35), octamethyl PBS did not show significant improvement on the fire retardancy
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 95

Table 1
Cone calorimetry results of PET composites (35 kW/m2 ) [122].

Samples pHRR (kW/m2 ) Mean HRR (kW/m2 ) THR (MJ/m2 ) Char yield (%) TTI (s)

PET 1008 575 81.8 15.0 70.9


PET/5%MMT 869 524 82.9 18.4 58.5
PET/5%MMT/T-POSS 720 478 86.8 17.1 36.8

Copyright 2014. Reproduced with permission from Elsevier Ltd.

Table 2
LOI UL-94 results, and cone calorimeter data of FR GF-PBT with and without POSS [124].

FR formulations (wt.%) LOI (%) UL-94 (0.8 mm) Cone (50 kW/m2 )

Rating Total burning time (s) pHRR (kW/m2 ) TTI (s)

OP1200 (20) 42 ± 1 V-0 36 250 66


OP1200/AEAPI-POSS (18/2) 36 ± 1 V-0 25 / /
OP1200/OM-POSS (18/2) 43 ± 1 V-0 37 172 (31%) 70
OP1200/T-POSS (18/2) 38 ± 1 V-1 63 214 (−14%) 62

OP1240 (20) 40 ± 1 V-0 40 191 67


OP1240/API-POSS (18/2) 38 ± 1 V-0 29 / /
OP1240/OM-POSS (18/2) 42 ± 1 V-0 35 135 (−29%) 70
OP1240/T-POSS (18/2) 38 ± 1 V-1 82 134 (−30%) 64

Copyright 2013. Reproduced with permission from Polimery.

O
R O
Si Si 2
O
R O O
Si Si R R=i-butyl
O O

O R O
Si Si R
O O O
R Si Si R
O

Fig. 37. The structure of methacrylisobutyl-POSS (MI-POSS).

Fig. 36. Structure of octaaminophenyl POSS (OAPS). R O R


Si Si O
O R= H2C
(LOI, UL-94, and Cone) of PBS than that using MP only. Although R O O
Si Si R O
more char residue can be created by blends of MP and OAPS, the O O
central part of this char layer still burns owing to cracks due to poor
thermal-oxidative resistance. The OAPS shows a negligible effect on O R O
fire retarding PBS/MP composite. Si Si R
O O
By now, almost all POSS which were used to flame retard O
polyesters were mixed with phosphorus containing flame retar- R Si Si R
dants. When the content of POSS is very low, the mixture of POSS O
and phosphorus containing fire retardants could improve the fire
Fig. 38. The structure of octamethacryl POSS (OMA-POSS).
retardancy of polyester. The synergy between POSS and phospho-
rus containing fire retardants in polyester is effective. However,
reports about polyesters fire retarded by POSS only are very few. also highly flammable and can produce toxic gases during combus-
In the future, it would be worth carrying out more research work tion.
on novel phosphorous containing POSS molecular structures which A series of fire retarded vinyl ester resins was prepared by
should further improve polyesters fire retardance blending vinyl ester resins with three different POSSs including:
polyvinylsilsesquioxane (Vi-PSS), methacrylisobutyl-POSS (MI-
3.7. Vinyl esters POSS, Fig. 37), and octamethacryl-POSS (OMA-POSS, Fig. 38) [129].
After mechanical stirring at room temperature, only OMA-POSS
3.7.1. Vinyl ester resins with POSS was completely dissolved in all resins, remaining clear even after
Vinly ester (VE) resins are often preferred resin material because the addition of 30 wt.% OMA-POSS, which was caused by the reac-
they offer ease of processing and lower cost over epoxy resins, while tion between OMA-POSS and vinyl ester resins. Whereas both the
they exhibit superior properties relative to unsaturated polyester MI-POSS and Vi-PSS settled out of the resin over the mixing time,
(UPE) resins [3]. Glass fiber reinforced vinyl ester resins are also requiring additional mixing, and caused the resin to become cloudy
increasingly used for military and commercial applications due to as the concentration of POSS increased. In a commercial vinyl ester
good toughness, excellent chemical resistance and good mechan- resin (VE), 30 wt.% of MI-POSS or Vi-PSS cannot make this VE resin
ical properties [128]. However, vinly ester matrix composites are pass the UL-94 test due to the burning times lasting longer than 30s.
96 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 39. Schematic representation of layer-by-layer assemblies from APP and POSS [131].
Copyright 2016. Reproduced with permission from Elsevier Ltd.

Table 3 deposited on acrylic fabrics exploiting the LbL assembly (Fig. 39)
Cone calorimetric data for VE/POSS nanocomposites [130].
[131]. The coatings consisting of 4 or 6 bi-layers have been found
Samples tign (s) pHRR (kW/m2 ) THR (MJ/m2 ) to homogeneously cover each fiber, creating an intimate inter-
Pure VE 82 1197 80 connection between those adjacent. As a result, the melt dripping
VE + 3 wt.% vinyl-POSS 71 796 71 phenomenon has been completely suppressed and the combustion
VE + 5 wt.% vinyl-POSS 73 844 62 rate significantly reduced. The success of the proposed treatments
VE + 10 wt.% vinyl-POSS 69 849 69 has been ascribed to the char-former character of APP, the ceramic
VE + 5 wt.% vinyl-POSS + 10wt.%TCP 64 479 39
thermal insulating barrier created by POSS and the intimate contact
VE + 5 wt.% vinyl-POSS + 15wt.%TCP 63 483 41
VE + 5 wt.% vinyl-POSS + 30 wt.%TCP 36 384 32 between these two species. These three aspects have proven to be
responsible of a significant modification in the thermal degradation
Copyright 2005. Reproduced with permission from Elsevier Ltd.
mechanism and fire safety of acrylic fibers.

On the other hand, the OMA-POSS could reduce average burning


times and improved the flammability to V-2 class from no rating. 3.9. Polyurethane and polyurea
In the fatty acid vinyl ester (FAVE), OMA-POSS also showed sig-
nificant reduction in the average burning time, which is 16.8–96.9% 3.9.1. Polyurethane with POSS
lower than that of neat resin. However, the MI-POSS or Vi-PSS can- Thermoplastic polyurethanes (TPUs) are well known for their
not make it. Glodek [129] suggested that only OMA-POSS had any excellent abrasion resistance, high tensile, compressive and tear
real effectiveness in reducing flammability of VE or FAVE compos- strength, good flexibility over a wide range of temperatures, good
ites, which is a result of its good dispersion and insertion reaction hydrolytic stability, and selection of a wide range of hardness but
into the polymer network relative to MI-POSS or Vi-PSS. they exhibit as many thermoplastics poor fire retardancy [132,133].
Therefore, the search for an appropriate fire retardant or synthesiz-
3.7.2. Vinyl ester resins with POSS and organophosphate ing an inherently non-flammable TPU represents a major scientific
compounds challenge.
Chigwada et al. [130] reported the fire retardancy of VE/vinyl- Bourbigot et al. [134] prepared a thermoplastic polyurethane
POSS nanocomposite with or without tricresylphosphate (TCP). As (TPU) containing polyvinylsilsesquioxane (Vi-PSS) by melt-mixing,
shown in Table 3, there are significant reductions in pHRR for showing good dispersion of Vi-PSS particles with ellipsoidal shape
the VE/vinyl-POSS nanocomposites and this reduction is further between 200 and 400 nm. 10 wt.% Vi-PSS in TPU decreases about
enhanced by the presence of TCP. There is also a reduction in the 80% the peak of heat release rate (pHRR) compared to virgin TPU
total heat released of about 40–50% in the presence of both the TCP during calorimetry test as shown in Fig. 40, which is due to an
and vinyl-POSS, leading to reduced flammability for these materi- intumescent mechanism producing a ceramified char made of sil-
als. At the same time, substantial reduction in the time to ignition icon network in a polyaromatic structure. The expansion occurs
was observed, as it often happens in nanocomposites. because of the partial volatilization of the organic part of Vi-PSS and
because of the evolving degradation products of TPU. The intumes-
3.8. Acrylic fabrics cent structure makes an efficient insulation barrier at the surface
of the substrate, limiting heat and mass transfer and then decreas-
Nowadays, a new frontier of nanotechnology is its application ing heat release rate. However, time to ignition of the TPU/Vi-PSS
for the building up of smart flame retardancy coatings by the composite (60 s) is twice shorter than that of pure TPU (120 s). Fur-
layer-by-layer (LbL) assembly which is certainly one of the most thermore, there is no significant enhancement of LOI value and
interesting and promising among all the different techniques that UL-94 V-2 rating (3.2 mm) when incorporating Vi-PSS in TPU.
may be exploited for this purpose. Nanostructured LbL coatings Furthermore, the polyvinylsilsesquioxane (Vi-PSS) or dode-
based on ammonium polyphosphate (APP) and octapropyl ammo- caphenyl POSS (DP-POSS) was added at 10 wt.% during the
nium polyhedral oligomeric silsesquioxane (POSS) layer have been synthesis of thermoplastic polyurethane (TPU) which have no effect
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 97

40 kJ respectively that are significantly lower than 70 kJ for the pure


TPU. Bourbigot indicated that DP-POSS and Vi-PSS act as real fire
retardants in TPU that could reduce the HRR and THR of materials.
Devaux et al. [136] prepared polyurethane/POSS nanocompos-
ites as fire retarded coating for polyester (PET) using octamethyl
POSS (OM-POSS) and Vi-PSS. The performance of Vi-PSS in PU/Vi-
PSS composite is similar to the results reported by Bourbigot et al.
[59,135]. However, there were no many improvement of the fire
retardant properties using OM-POSS, only the THR maximum was
lower than that of virgin coating, but the THR plateau started simul-
taneously with that of the virgin coating. The chemical groups on
a POSS appreciably influence their fire retardant applications. The
suggested mechanism of these fire retardancy performances was
the char formation at the surface of the material which can act as
an insulation barrier for heat and mass transfer. The organic groups
Fig. 40. Heat release rate (HRR) as a function of time of virgin TPU compared to on POSS cages undergo Si C bond cleavage at about 300–350 ◦ C in
TPU/POSS composite (35 kW/m2 ) [134]. air. This process is immediately followed by fusion of POSS cages to
Copyright 2009. Reproduced with permission from Elsevier Ltd. form a thermally insulating and oxidatively stable silicon oxycar-
bide char layer [137,138].
A hydroxyl-terminated polybutadiene-based polyurethane
composites grafted by polyhedral oligomeric silsesquioxane
(HTPB-based PU-g-POSS) were prepared by a one-step PU reaction
using the HTPB prepolymer, two types of reactive POSS diol, and
isophorone diisocyanate [139]. POSS molecules in the HTPB-based
PU composites exhibited distinct microphase separation, aggregat-
ing into a spherical shape on the nanometer scale. This morphology
of the POSS domain in the HTPB-based PU matrix leads to the for-
mation of densely accumulated spherical silica (SiO2 ) droplets on
the top of the surface of materials under thermally oxidative con-
ditions during ablation, resulting in improved ablation resistance
compared with pristine HTPB-based PU. This unique SiO2 -forming
Fig. 41. Heat release rate (HRR) curves of TPU, TPU/DP-POSS and TPU/Vi-PSS(FQ- ability of POSS molecules can also enhance the flame-retardant
POSS) as coating of woven PET fabrics (35 kW/m2 ) [59].
behavior of the composites, as illustrated by the limiting oxygen
Copyright 2005. Reproduced with permission from the Royal Society of Chemistry.
index and cone calorimeter measurements.

on the temperature of initial decomposition of TPU, nor on the TPU


degradation residue [59,135]. As shown in Fig. 41, the heat release 3.9.2. Polyurea with POSS
rate (HRR) curves of POSS containing TPU coating on woven PET Ultrasonication was employed to achieve good dispersion of
fabric showed a significant reduction peak of HRR (pHRR) com- Vi-PSS nanoparticles in the polyurea matrix, obtaining a signifi-
pared with pure TPU. The pHRR of TPU/DP-POSS and TPU/Vi-PSS are cant reduction in pHRR (73%) (Fig. 42) [140]. This improvement
decreased by 31% and by 50% respectively. Furthermore, the total in fire retardant properties has been obtained at 3 wt.% Vi-PSS
heat releases (THR) of TPU/DP-POSS and TPU/Vi-PSS were 60 kJ and loading, but increasing the loading of Vi-PSS above this limit has

Fig. 42. Heat release rate curves of polyurea/POSS (Vi-PSS) nanocomposites [140].
Copyright 2009. Reproduced with permissio the American Chemical Society.
98 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

R CH3
OH
Si R= C CH3
OH
R O O
Si Si R CH3
O OH

O R O
Si Si R
O O O
R Si Si R
O

Fig. 43. Structure of trisilanolisobutyl-POSS (TIB-POSS).

little further effect on pHRR value. Furthermore, a reduction of Fig. 44. Reaction scheme among reactive groups of dimethyloldihydrox-
yethyleneurea, cellulose and POSS [154].
polyurea peak heat release rate well above 90% was obtained by
Copyright 2012. Reproduced with permission from John Wiley & Sons Inc.
combining the Vi-PSS with phosphorus-based fire retardants such
as ammonium polyphosphate (APP) and expandable graphite (EG),
which demonstrate synergistic effects of Vi-PSS with conventional products is lower than that of neat PLA, implying a significant
fire retardants. Awad et al. [141] investigated the fire behavior reduction of combustible gases release.
of polyurea after coating the samples with commercial intumes- A POSS-modified nanofibrillated cellulose was prepared by
cent paints, either solvent or water-based, added with Vi-PSS. The using glycidylphenyl POSS in an ionic liquid [148]. The use of POSS-
commercial intumescent paints can enhanced fire retardancy for modified nanofibrillated cellulose (PNFC) as a carbon source in
polyurea, but there is no further improvement in combining the intumescing fire retardants (IFR) was effective at reducing flamma-
commercial intumescent paints with Vi-PSS. bility of PLA. The addition of 15% by mass IFR resulted in a 45%
It is seen that extensive work has been carried out on reduction in peak heat release rate (pHRR) and a 18% reduction
polyurethane (PU) flame retarded by the POSS. However, the POSS in total heat released (THR) over pure PLA, while simultaneously
just show good performance to reduce the heat release rate of PU, the use of PNFC did result in a shorter ignition time, but reduced
but there is no significant enhancement of LOI value and UL-94 V- smoke emission [149]. The POSS moieties on PNFC acted as a slight
2 rating. Even when the POSS is combined with commercial fire plasticizer in melt rheology studies, but did not affect the glass tran-
retardants, there is no further improvement in fire retardancy for sition temperature. The PNFC formed a cross-linked network with
PU. APP when melt-blended with PLA, which reduced polymer degra-
dation, decreased PLA crystallinity, reduced the melt viscosity, and
3.10. Polylactide improved composite stiffness relative to the neat extruded PLA
[150]. The cross-linked network formed between cellulose, POSS,
Polylactide (PLA) is a linear aliphatic thermoplastic polyester, and PLA helps produce composites with superior fire retardant, rhe-
which possesses many advantages of eco-friendliness, biocom- ological, and mechanical properties relative to other intumescing
patibility, and processibility [142]. PLA is a good substitute for formulations.
petrochemical thermoplastics, but flammability and serious melt
dripping during burning tests are a major drawback that limits 3.11. Cellulose
its applications [143]. PLA flammiability and flaming melt drip-
ping which propagates fires, could be limited by compounding with Cellulose fabrics have received much attention due to their
POSS particles depending on POSS content and type [144]. structural reinforcing potential, light weight, biodegradability,
A relevant fire retardancy improvement by addition of trisi- renewability, and low cost [151]. To guarantee human safety, most
lanolisobutyl POSS (TIB-POSS, Fig. 43) to a PLA intumescent of the cellulose fabrics are properly treated to become fire retar-
formulation was detected [145]. 30 wt.% of intumescent fire retar- dant, according to their final use in different application fields [152].
dant additive (IFR, ammonium polyphosphate/melamine) could Fox et al. [148,153] reported a nanofibrillated cellulose
increase the LOI of PLA composite, but it could not pass the UL- modified with glycidyphenyl POSS in the ionic liquid, 1-ethyl-
94 V-0 rating test. Combined TIB-POSS and IFR in PLA, produce 3-methylimidazolium acetate (EmiAc). The onset of degradation
stable poly(phosphoricacid) and polysiloxane derivatives by ther- temperature decreased and the char yield increased as the POSS
mal degradation of the PLA/IFR/TIB-POSS composite. These stable content of the cellulose increased. The pyrolysis combustion flow
chemical structures created a protective compact and continuous calorimetry (PCFC) was used to provide some evidence of material
surface on burning PLA, while the interior had a porous structure, performance in combustion. It is found that modifying cellulose
which could act as a barrier to the heat and mass transfer. With with glycidyphenyl POSS resulted in a 25–30% decrease in heat
IFR (22.5 wt.%) and TIB-POSS (7.5 wt.%), PLA composites achieved release capacity (HRC) and a 3-fold increase in char yield.
the V-0 rating in UL-94 test and its LOI value was 40% compared Several cotton fabrics were fire retarded by a finishing process
to V-1 rating and 33% of PLA with only IFR [145]. Furthermore, this with octa n-propylammonium chloride POSS (OPCA-POSS), which
composite showed a 69% reduction in heat release capacity (HRC) could enhance the thermal stability and fire retardancy of cotton
and 33.8% reduction in the total heat release (THR) compared with fabrics [154]. Cotton fabrics were linked to POSS by the coupling
pure PLA in PCFC test [146]. Another report about the improve- agent dimethyloldihydroxyethyleneurea (Fig. 44) that has func-
ment of fire retardancy of PLA composites caused by TIB-POSS tional groups able to react with hydroxyl groups of cotton fabrics
found that the interactions between TIB-POSS and IFR (pentaery- and ammonium groups of POSS. So POSS nanoparticles are homo-
thritol phosphate/melamine phosphate) led to the formation of an geneously distributed on the surface of cotton fibers and finely
high protective intumescent char which could slow down poly- dispersed at nanometric level. POSS nanoparticles have turned out
mer degradation [147]. Thus the flux of PLA/IFR/TIB-POSS pyrolysis to play a protective role on the thermo-oxidation of the cotton. The
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 99

Fig. 45. Chemical structures of deposition materials and schematic of the LbL deposition process [155].
Copyright 2011. Reproduced with permission from the Royal Society of Chemistry.

kinetics of cotton fabrics combustion process has been modified by


POSS as compared with that of neat cotton fabrics. This finding is
due to the tendency of POSS nanoparticles to form a ceramic bar-
rier able to delay the cellulose ignition and reduce the heat release
more than 40% according to the cone calorimetry data.
Fully siliceous layer-by-layer assembled thin films, using dif-
ferent POSSs as building blocks, were successfully deposited on
cotton fabric [155]. Watersoluble octa(3-ammoniumpropyl)
octasilsesquioxane octachloride (OctaAmmonium
POSS, (+)POSS) and octakis(tetramethylammonium)
pentacyclo-[9.5.1.13,9 .15,15 .17,13 ] octasiloxane 1,3,5,7,9,11,13,15-
octakis(cyloxide)hydrate (OctaTMA POSS, (−)POSS) were used as
cationic and anionic components for thin film deposition from
water. Furthermore, aminopropyl silsesquioxane oligomer ((+)AP),
was also used to assemble films with OctaTMA POSS ((−)POSS).
Two different multilayer films were assembled on cotton fabrics
using the procedure shown in Fig. 45. After vertical fire test, there
Fig. 46. Preparation of P(POSS-MMA-VBFC) [156].
was no char left from the control fabric, but all coated fabrics
Copyright 2011. Reproduced with permission from John Wiley & Sons Inc.
left significant residue. In general, more bilayers on a fabric left
more residue and char was darker after fire test. Greater char yield
was accompanied by the lower THR and pHRR. The maximum
based nanocomposites heated or combusted, a stable ceramic-char
reduction in THR (23%) and pHRR (20%), as compared to the
surface can be detected as shown in Fig. 47. The fabric crisscross
control fabric, are observed for the fabric coated with 20 bilayers
networks of the uncoated one are broken, leaving slim and loose
of (+)AP/(−)POSS. For the (+)POSS/(−)POSS coated fabrics, the best
fiber residues (Fig. 47a), while the crisscross network structure of
performance is also the 20 bilayers coated fabric, which showed a
P(POSS-MMA-VBFC) coated fibers is still retained (Fig. 47b). This
17% reduction in THR and 11% in reduction in pHRR.
phenomenon implies that this kind of hybrid copolymers may have
Gao et al. [156] reported that the cotton fabrics coated
a potential for applications in fire retardant fabrics.
with the hybrid copolymers poly(octavinyl POSS & methyl
Literature state of the art shows that in most studies, cellulose
methacrylate & 4-vinylbenzyl fluoroether carboxylate) (P(POSS-
fabrics were fire retarded through the surface modification using
MMA-VBFC)) possessed improved fire retardancy. The hybrid
chemical reaction or layer-by-layer assembly. The POSS showed
copolymer (P(POSS-MMA-VBFC)) was prepared via radical poly-
good performance on reducing the heat release rate and improve
merization as shown in Fig. 46, and its thermal properties were
the LOI value and UL-94 rating. Whereas, studies on cellulose fab-
improved by the introduction of POSS cage [157]. The LOI of the cot-
rics fire retarded by POSS added during the solution spinning stage
ton fabric coated by P(POSS-MMA-VBFC) (content POSS is 7.1 wt.%)
is rare. If the fire retardants were added during the solution spin-
is 19.4%, while the LOI of the untreated cotton fabric is 18.1%.
ning stage, while the unreactive POSS particles need to be smaller
Although this improvement hardly meet expectations, after POSS-
than 1 ␮m, the reactive POSS should not affect the spinning pro-
100 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

dancy [158]. However, it is well known that pristine MoS2 is


unsuitable for intercalation by large species, such as polymer
chains, because MoS2 as a bulk material has a pronounced tendency
to agglomerate in polymer matrix which usually destroys the prop-
erties of the composites [159]. Therefore, there has been a great
interest in the improvement of the dispersion of MoS2 nanosheets
in polymer matrix.
The surface functionalization of molybdenum disulfide (POSS-
MoS2 ) was prepared by a simple reflux reaction between
dithioglycol-MoS2 (DIGT-MoS2 ) and octavinyl POSS (OV-POSS)
[160]. PVA/POSS-MoS2 nanocomposites were prepared by ultra-
sonic solvent blending and casting technique. The synthetic route
of the PVA/POSS-MoS2 nanocomposites is shown in Fig. 48. The
authors reported that after the surface functionalization of MoS2 ,
the diffraction peaks observed in the XRD patterns of MoS2 disap-
pear from that of PVA/POSS-MoS2 composites, which implied the
exfoliation of the MoS2 layered structure. In contrast, the strongest
diffraction peak of the MoS2 is still observed in the XRD patterns of
PVA/MoS2 composite, indicating the presence of stacked structure
of MoS2 . From TGA, DSC, PCFC and cone tests results, it seems that
the addition of POSS-MoS2 to PVA matrix can effectively improve
degradation temperature and glass transition temperature (Tg ),
decrease the pHRR and THR value.
As shown in Fig. 49, it can be observed that neat PVA burns
extremely rapidly after ignition and the pHRR value reaches to
375 kW/m2 , while incorporating MoS2 nanosheets into PVA makes
the pHRR decrease to 297 kW/m2 . For PVA/POSS-MoS2 , its HRR
is reduced by about 50% in the char protected combustion step
Fig. 47. SEM images of the residues of the burned uncoated cotton fabric (a) and (120–170 s, Fig. 49) of PVA/POSS-MoS2 before increasing when char
coated cotton fabric (b) [156]. breaks down at 170 s. This effect results in a THR of for PVA/POSS-
Copyright 2011. Reproduced with permission from John Wiley & Sons Inc. MoS2 decrease by 30% compared to PVA and PVA/MoS2 . The
total pyrolysis products of PVA/POSS-MoS2 , such as the aliphatic
cess. POSS added during the solution spinning stage may lead to hydrocarbons, aromatic compounds and carbon monoxide were
some good flame retardant effect. significantly reduced, compared to those of neat PVA. The improve-
ment of fire retardant properties and reduction of the fire hazards
of PVA/POSS-MoS2 were due to the formation of a compact and
3.12. Polyvinyl alcohol
insulating char layer protecting the polymer matrix from further
burning induced by the homogeneously dispersed POSS-MoS2 .
Like other nanofillers, single MoS2 nanosheets were used to
fabricate polymer based nanocomposites, which can effectively
enhance mechanical and thermal properties besides flame retar-

Fig. 48. Illustration for the functionalization of POSS-MoS2 nanosheets and PVA nanocomposites [160].
Copyright 2014. Reproduced with permission from the Royal Society of Chemistry.
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 101

HO R
R O R OH
Si Si Si
R O OH
O R O O
HO Si Si R Si Si R
O O O OH

O R O O R O
Si Si R Si Si R
O O O
O O O
R Si Si R Si Si R
R O
O R=
SDOH STOH

Fig. 50. Structures of disilanol cyclohexyl POSS (SDOH) and trisilanol cyclohexyl
POSS (STOH).

3.13. Epoxy resins

3.13.1. Epoxy resins with POSS


Epoxy resin (EP) is one of most important thermosetting mate-
rials and widely used as a matrix material for the fabrication
of advanced composites in the electrical/electronic and transport
industries, owing to its high tensile strength and modulus, good
adhesive properties, good chemical and corrosion resistance, low
shrinkage in curing, and excellent dimensional stability [161,162].
However, with most of the organic polymers, flammability is one
of the main drawbacks of the epoxy resins. In order to meet appli-
cation requirements, their fire retardant properties have to be
improved while maintaining the of other important characteris-
tics such as mechanical and thermal properties and respecting of
environmental issues [163,164].
Recently, many studies have shown that using the POSS
nanoparticles to fire retard epoxy resins can well satisfy
Fig. 49. HRR and THR curves of neat PVA and PVA composites obtained from cone these requirements. Silanol-containing POSS possess a three-
calorimeter tests (35 kW/m2 ) [160]. dimensional cage structure that contains from one to four silanol
Copyright 2014. Reproduced with permission from the Royal Society of Chemistry. (Si OH) groups. The terminal silanol Si OH could react with the

Fig. 51. Proposed mechanism of capture of free radical by POSS [168].


Copyright 2009. Reproduced with permission from Elsevier Ltd.
102 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

R O
Si Si O
O O
R O O
Si Si R
O O

O R O
Si Si R
O O O R=isobutyl or phenyl
R Si Si R
O

Fig. 52. The structures of glycidyloxypropyl heptaphenyl POSS (Gly-Ph POSS) and
glycidyloxypropyl heptaisobutyl POSS (Gly-iBu POSS).

Fig. 53. Heat release rate (HRR) curves of epoxy networks containing Gly-Ph POSS
and Gly-iBu POSS [172].
reactive groups in epoxy polymer through the following two ways,
Copyright 2009. Reproduced with permission from Elsevier Ltd.
one is reacting with mid-hydroxyl in the polymer chain forming
Si O C bond, the other is reacting with the oxirane ring through
ring opening reaction forming new hydroxyls which can react in
turn with silanol groups [165,166].
Fire retarded epoxy resins (EP) could be prepared by reaction
with two kinds of silanol-containing POSS: disilanol cyclohexyl
POSS (SDOH) and trisilanol cyclohexyl POSS (STOH) shown in Fig. 50
[166,167]. The SDOH and STOH were successfully introduced into
epoxy resin forming EP1-SDOH and EP2-STOH hybrid resins. With
SDOH contents increasing from 0 to 25 wt.%, the LOI values of EP1-
SDOH hybrid resins were raised from 26 to 32% [166]. In addition,
with the STOH contents increasing from 0 to 5 wt.%, the LOI val-
ues of EP2-STOH hybrid resins increased from 22.6 to 32.8% [167].
The POSS decompose producing silica which interfered with the
combustion process during heating, pyrolysis, ignition, or spread
of flames. The different fire retardant efficiency between SDOH and Fig. 54. Heat release rate (HRR) curves of epoxy networks containing Gly-Ph POSS
and octaphenyl POSS [172].
STOH was attributed to their different silanol number.
Copyright 2009. Reproduced with permission from Elsevier Ltd.
Wu et al. [168] synthesized a functional polyhedral oligomeric
silsesquioxane (NPOSS) via the reaction of trisilanol isobutyl
POSS (TIB-POSS) with triglycidyl isocyanurate (TGIC) and stud- of POSS nanoclusters leads to a different reduction of the pHRR
ied its effect on the flammability of an epoxy resin (diglycidyl as shown in Fig. 53. For the Gly-Ph POSS with phenyl groups, its
ether of biphenol A and m-phenylenediamine). The PCFC results pHRR is decreased by 40% in this case as compared to 25% for
indicated that 10 wt.% NPOSS in epoxy resin could reduce peak isobutyl-based POSS (Gly-iBu POSS) network. This tendency was
heat release rate (pHRR) by about 30%. Furthermore, their confirmed by the UL-94 results: while the epoxy containing Gly-
extended study to observe the effectiveness of TIB-POSS and TGIC iBu POSS burnt entirely, showing no improvement as compared to
on an aerospace grade EP (1,4-butanediol diglycidylether and the neat matrix, the Gly-Ph POSS caused the epoxy net work to self-
cycloaliphatic amines) [169]. However, instead of synthesizing extinguish, leaving a mass residue of 96%. The phenyl groups in the
NPOSS, TIB-POSS with or without TGIC have been added to the POSS were the cause of a larger improvement, as compared with
aerospace grade EP to observe whether TGIC and TIB-POSS can react isobutyl groups.
and work as efficiently as NPOSS. When 10 wt.% TIB-POSS present Furthermore, Franchini et al. [172] studied the effect of phenyl
alone in the aerospace grade EP, more than 53% reduction of pHRR POSS linkage with the epoxy network as a parameter influencing
and 28% reduction of THR can be detected. However, there is no its fire behavior. The POSS were octaphenyl POSS surrounded by
beneficial effect of further addition of TGIC. eight phenyl groups and Gly-Ph POSS with seven phenyl groups
The NPOSS cage structure can retard the movement and scission and a reactive glycidyl group. As concerns the fire performance,
of the chains of EP during thermal degradation process [168,169]. both epoxy networks with POSS showed better results in UL94 tests
EP/NPOSS released on degradation mainly methyl-substituted, car- with self extinguishment fires and product large residue (about
bonyl and aromatic ring compounds with higher molecular weight 96%). From the cone calorimeter experiment, a remarkable reduc-
compared with that of EP control. Furthermore, NPOSS can inter- tion in the pHRR was exhibited for both POSS-epoxy networks,
fere with the free radical oxidative degradation process of EP. The with a decrease equal to 34% and 40% for octaphenyl POSS and Gly-
isobutyl radical can capture the hydrogen radical and the silicon Ph POSS respectively as shown in Fig. 54. Thus a slightly superior
radical of NPOSS can capture the hydroxy radical (Fig. 51). It is pro- improvement was obtained in the case of the reactive monofunc-
posed that this would be help to form a stable charred layer in the tional POSS as compared with the inert POSS, but the difference
condensed phase which would prevent the underlying materials between both epoxy networks was not remarkable.
from further decomposition during combustion [168]. The effect of DodecaPhenyl POSS, Epoxycyclohexyl POSS,
Glycidyl POSS functional groups which can react with the Glycidyl POSS and TriglycidylCyclohexyl POSS to act as flame retar-
curing agent amino groups were often used for fire retardants dants of the epoxy resin for aeronautic applications was evaluated
of epoxy resin [170,171]. Two reactive POSSs: glycidyloxypropyl [173]. The Glycidyl POSS has meaningful effects on the flame retar-
heptaphenyl POSS (Gly-Ph POSS, Fig. 52) and glycidyloxypropyl dancy of the epoxy mixture tested by the limiting oxygen index
heptaisobutyl POSS (Gly-iBu POSS, Fig. 52) contain one glycidy- (LOI) and calorimetry measurements.
loxypropyl tether, and bear either phenyl or isobutyl groups on the A comparison of DGEBA/m-phenylenediamine (m-PDA)
seven other silicon atoms were investigated [172]. The presence networks containging octaphenyl POSS (OPS, 4.1 wt.%) or
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 103

Fig. 55. Photographs of chars from EP composites after the cone calorimeter test [174].
Copyright 2012. Reproduced with permission from Elsevier Ltd.

Table 4
Cone results for cast epoxy resins [175,177].

Samples TTI (s) pHRR (kW/m2 ) THR (MJ/m2 )

Pure DGEBA/DETA 49 813 33


DGEBA/DETA/5 wt.% octamethyl POSS 50 731 36
Pure DGEBA/m-PDA 45 855 112
DGEBA/m-PDA/5 wt.% octaphenyl POSS 60 712 103
DGEBA/m-PDA/5 wt.% DOPO-POSS 58 588 92
Pure DGEBA/DDS 64 821 94
DGEBA/DDS/5 wt.% OD-POSS 59 417 74

Copyright 2013 and 2012. Reproduced with permission from Elsevier Ltd.

ied the combustion of DGEBA/m-PDA networks containing 5 wt.%


octaphenyl POSS (OPS), and Gérard et al. [177] investigated epoxy
systems based on DGEBA/DETA with 5 wt.% of octamethyl POSS. The
Fig. 56. Heat release rate (HRR) curves of epoxy networks containing ladder-type morphology was assessed in both cases [175,177], and better dis-
PPSQ and cage-type OPS [175].
persion was achieved in the case of octamethyl POSS where rod-like
Copyright 2013. Reproduced with permission from Elsevier Ltd.
clusters of about 0.5–1 ␮m were observed, while the octaphenyl
POSS constituted rough, crystalline phases. As shown in Table 4,
octaaminophenyl POSS (OAPS, 4.6 wt.%) has been done [174]. the results of cone calorimeter showed that addition of octamethyl
The OAPS could potentially act as a crosslinking point by reaction POSS to epoxy network brought unremarkable reduction of pHRR
of amino groups with the oxirane ring of the epoxy prepolymer. that lay within the error margin of the cone experiment, and
An increase of time to ignition (TTI) and the reduction of peak heat a 9% increase of THR that actually is unexpected. Whereas the
release rate (pHRR) can be detected after the EP networks were octaphenyl POSS proved more efficient in decreasing the pHRR
loaded with OPS or OAPS. No relevant improvement was obtained (about 17% reduction) and reducing the THR (about 10% reduc-
in the case of the pre-reacted OAPS as compared with the inert tion). Furthermore, a significant improvement of time to ignition
OPS, but a more continuous and integrated SiO2 surface layer can (TTI) caused by octaphenyl POSS can be observed.
be observed in the EP/OAPS composites combustion residue as An octadiphenylsulfonyl POSS (OD-POSS, Fig. 57) which was
shown in Fig. 55. prepared from octaphenyl POSS and benzenesulfonyl chloride via a
The use of ladder-type polyphenyl silsesquioxane (PPSQ) in Friedel–Crafts reaction exhibited high thermal stability according
DGEBA/m-PDA networks was also reported by Zhang et al. [175]. to thermogravimetric analysis, whose initial thermal decomposi-
When 4.1 wt.% PPSQ was introduced in DGEBA/m-PDA networks, tion temperature (5% weight lost) was at 491 ◦ C in air and 515 ◦ C
the LOI value was increased from 25% to 27.1%, but the UL-94 sam- in nitrogen [30]. Li and Yang [178] studied the combustion of
ples failed to pass the minimum requirements for classification. DGEBA/DDS networks containing OD-POSS which possesses eight
The pHRR of EP/PPSQ was actually similar to that of the neat epoxy inert groups. When 5 wt.% OD-POSS was introduced in DGEBA/DDS
network within experimental error (Fig. 56), showing the absence networks, the LOI value was increased from 23.2% to 24.3%, and
of a fire-retardant behavior from the ladder-type PPSQ, which was the UL-94 samples failed to pass the minimum requirements for
unexpected, especially given the good thermal stability and char classification. However, addition of OD-POSS to epoxy networks
yield of ladder-type PPSQ via TGA analysis. It was worth noting that brought a significant improvement by about 50% reduction of pHRR
the use of the cage-type OPS obtained similar results of LOI and UL- and about 22% reduction of THR can be detected. Compared with
94 as ladder-type PPSQ did, but showed a relative enhancement of octamethyl POSS [177], octaphenyl POSS [176], and ladder-type
the cone calorimeter results through a significant decrease of the PPSQ [175], the higher concentration of phenyl groups in OD-POSS
pHRR (Fig. 56). The reason for the poor fire behavior of EP/PPSQ net- is one reason that could explain its best performance in the cone
work is that the ladder structure of PPSQ reacts too slowly to cause calorimeter test. Furthermore, the sulfur element in the OD-POSS
cross-linking and charring in the condensed phase to match the should be another important reason that should arise our attention
intumescent and charring process of the EPs during combustion. in the future.
The solid chars cannot develop stable structure, and are damaged Three phosphorus containing polyhedral oligomeric
before they can protect the bulk EP. On the contrary, cross-linking silsesquioxanes (P-POSS) T8 caged structures were synthesized by
in the condensed phase caused by OPS seems to have the desired the addition reaction of octa vinyl POSS with diphenylphosphine
retarding effect. (DPP), diphenylphosphine oxide (DPOP), and 9,10-dihydro-9-
The influence of the non reactive organic groups surrounding the oxa-10-phosphaphenanthrene-10-oxide (DOPO), respectively
POSS cage can be an important parameter for the fire retardancy [179,180]. Furthermore, DOPO-POSS can also be synthesized via
of the POSS-containing epoxy networks. Zhang et al. [176] stud- hydrolytic condensation of a DOPO modified vinyltriethoxysilane
104 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Other interesting results were that the LOI value and UL-94 rat-
ing of EP/2.5 wt.%DOPO-POSS composites reached 30.2% and V-1
rating. These improvements were never seen in the epoxy networks
with octamethyl POSS [177], octaphenyl POSS [176], ladder-type
PPSQ [175] or OD-POSS [30]. This dramatic improvement of LOI
and UL-94 rating was caused by a mechanism named blowing-
out effect [183]. As shown in Fig. 59, the blowing-out effect had
been described as that: “after the sample was ignited, it showed
an unstable fire for several seconds; with the pyrolytic gaseous
products jetting outward from the condensed-phase surface, the
flame was extinguished, it appears as though the gas blew out the
flame” [184]. However, with increase of DOPO-POSS content, the
blowing-out in the EP composites was weakened. Their LOI val-
ues and UL-94 rating was gradually reduced with the weakened
blowing-out effect.
Furthermore, DOPO-POSS was introduced into DGEBA cured by
an aliphatic oligomeric polyamide 650 (PA650) or the aromatic 4,4-
diaminodiphenylsulphone (DDS) by Zhang et al. [184]. The results
of UL-94 tests show that the DEGBA/DDS with DOPO-POSS exhibits
a blowing-out effect through vigorous emission of pyrolytic gases,
but the DEGBA/PA650 does not. The HRR curves of EP composites
based on the two different curing agents are shown in Fig. 60. The
DOPO-POSS in EP cured by aromatic DDS leads to an evident pHRR
Fig. 57. Schematic illustration for the preparation of OD-POSS [30].
reduction with increasing of DOPO-POSS content. However, in the
Copyright 2014. Reproduced with permission from John Wiley & Sons Inc.
EP cured by aliphatic polyamide 650, the reduction of pHRR only
can be detected in EP with 10 wt.% DOPO-POSS. In the PA650 epoxy
(VTES) [181]. P-POSS have good compatibility and showed nan- based network, the residues with crosslinking structures could
odispersion in the epoxy networks in Fig. 58. The fire and pyrolysis not be created in the condensed phase until addition of 10 wt.%
behaviors of DGEBA/m-PDA epoxy networks (EP) loaded with DOPO-POSS during the combustion. Whereas in DDS based net-
DOPO-POSS were investigated in detail [182]. The pHRR of EP com- work, the proportion of aromatic segments is high, so when as little
posites with 5 wt.% DOPO-POSS showed about 32% reduction from as 2.5 wt.% DOPO-POSS is added to the epoxy resin, the charring
855 kW/m2 to 588 kW/m2 . As shown in Table 4, this improvement crosslinking structures are created and easily survive.
caused by DOPO-POSS is better than the effects of octamethyl The internal temperature profile of DGEBA/DDS networks with
POSS and octaphenyl POSS in epoxy networks, but weaker than different DOPO-POSS loading during the UL-94 tests have been
the work of OD-POSS. The phosphorus in the DOPO-POSS seemly studied [185]. The temperature profiles showed that blowing-out
played an important role. effect in DGEBA/DDS/2.5 wt.%DOPO-POSS slows down the heat

Fig. 58. SEM micrographs of EP/DPP, EP/DPOP, and EP/DOPO composites [179].
Copyright 2016. Reproduced with permission from Elsevier Ltd.
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 105

Fig. 59. The model of the blowing-out effect mechanism [184].


Copyright 2012. Reproduced with permission from Elsevier Ltd.

1200
DGEBA/PA650
DGEBA/PA650/2.5wt.% DOPO-POSS
1000 DGEBA/PA650/5wt.% DOPO-POSS
DGEBA/PA650/10wt.% DOPO-POSS

800
HRR (kW/m )
2

600

400

200

0
0 100 200 300 400 500
Fig. 61. Synthetic route of POSS-bisDOPO (a) and schematicillustration of the prepa-
Time (s) ration process of POSS-bisDOPO-modifiedepoxy resin (b) [186].
Copyright 2016. Reproduced with permission from the Royal Society of Chemistry.
DGEBA/DDS
1000 DGEBA/DDS/2.5wt.% DOPO-POSS
DGEBA/DDS/5wt.% DOPO-POSS
DGEBA/DDS/10wt.% DOPO-POSS mechanical strength of POSS-bisDOPO/EP was higher than those of
800 pure EP and POSS–NH2 /EP due to the outstanding reinforcement
HRR (kW/m )
2

effect of the unique nanostructure of POSS-bisDOPO assembled in


600 the EP matrix. The surfactant-like structure of this flame-retardant
endows it with excellent self-assembly capability, thus significantly
400 improving its dispersion uniformity in the epoxy resin. The self-
assembly of POSS-bisDOPO in epoxy resin not only enhanced the
200 flame retardancy, but also improved the mechanical properties.
From the vast literature on fire retardancy of epoxy resins-POSS
0 materials it can be concluded that good dispersion of reactive POSS
0 100 200 300 400 500 in epoxy resins is generally obtained. However, neither reactive
Time (s) nor inert POSS lead to satisfactory ranking of epoxy resins in LOI
or UL-94 tests although they can reduce heat release rate in cone
Fig. 60. Heat release rate curves of fire retarded DGEBA/PA650 composites and calorimeter. The adjuvant action of phosphorous either as a fire
DGEBA/DDS composites [184].
retardant compound or as an atomic constituent of the POSS struc-
Copyright 2012. Reproduced with permission from Elsevier Ltd.
ture, was found to be helpful in increasing the fire retardant action
transfer from the flame to the unburned matrix; furthermore, this of POSS in epoxy resins, in some cases even at very low overall
blowing-out effect can even take away some heat from the surface loadings. Good fire retardant behaviors were found in LOI, UL-
zone by the spurting gases. The thermogravimety and Fourier trans- 94 and cone calorimeter test. These results are related to a novel
form infrared spectrometer result show that the spurting gases fire retardant mechanism found to be active in the P containing
during the blowing-out effect have a high content of CO2 , which POSS which encourages further research on this type of P-POSS
could reduce the flammability of the jetting gases. structures which could bring interesting solutions also for other
In order to develop a multi-element, synergistic, flame- polymers besides epoxy resins.
retardant system, the combination of DOPO, POM (polyoxymethy-
lene) and aminopropylisobutyl POSS (POSS-bisDOPO, Fig. 61) 3.13.2. Epoxy resins with POSS and inorganic phosphate fire
was achieved using the classical Kabachnik–Fields reaction [186]. retardants
POSS-bisDOPO was introduced into epoxy resins to obtain flame- The use of POSS in synergy with other compounds and/or
retardant materials. The LOI value increased from 25.4% to 34.5% nanofillers to improve the fire retardancy of epoxy resin has been
when the content of POSS-bisDOPO is 20 wt.%. Furthermore, the widely investigated. Amongst the many studies on the subject, par-
106 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 62. Char residue pictures: (a) virgin EP; (b) 5% OM-POSS-EP; (c) 5% APP-EP; (d) 4% APP + 1% OM-POSS-EP [188].
Copyright 2011. Reproduced with permission from John Wiley & Sons Inc.

ticular interest has been focused on the synergy between POSS and
phosphorus-containing compounds, such as intumescent flame
retardants (IFRs) which are considered as environmentally friendly
flame retardant systems. They consist of three fundamental ingre-
dients, namely acid source, carbonization agent, and blowing agent.
Its flame retardant mechanism is mainly due to the barrier effect
of swollen carbonaceous char created by the interactions during
combustion of the three components mentioned above [187].
Ammonium polyphosphate (APP) in combination with
octamethyl POSS (OM-POSS) can improve the flame retar-
dancy of DGEBA-diethylenetriamine network [177,188]. A clear
synergistic effect of both OM-POSS and APP was observed via cone
calorimetry, the epoxy network containing both APP and OM-POSS
displayed a large reduction of pHRR, and also a quasi-constant
HRR after the HRR peak, corresponding to a low and constant
burning rate. The reasons of synergistic effect of APP and OM-POSS
are detected in the morphology of the residues after burning. As
shown in Fig. 62, the virgin epoxy leaves almost no residue and
Fig. 63. Synthesis of amine-functionalized POSS (POSS-NH2 ) [194].
incorporation of 5 wt.% OM-POSS produces a fragile residue made Copyright 2011. Reproduced with permission from Elsevier Ltd.
of very thin gray–white layers. The sample containing 5 wt.% APP
creates an intumescent char layer with important voids inside
and the cracks at different locations are formed caused by the thesized from DOPO and 4,4 -diaminobenzophenone (DABP). It is
evolving gas flow. When APP is partly substituted by OM-POSS, found that the phosphorus-containing epoxy resins gave a better
only small cracks can be distinguished in the middle of small performance in flame test with the incorporation of POSS-NH2 . This
bubbles distribution, which is considered to be more resistant to result is due to the low surface energy of Si–O–Si present in POSS,
the heat and mass transfer. which migrates to the surface. The high thermal stability of Si–O–Si
linkage in the phosphorus-containing char layer could enhance the
char formation and the thermal stability of this char layer [194,195].
3.13.3. Epoxy resins with POSS and reactive organic phosphate A series of flame-retarded DGEBA/m-PDA networks con-
fire retardants taining DOPO in combination with octaphenyl POSS (OPS) or
In recent years, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- octaaminophenyl POSS (OAPS) were prepared [174,176]. The mix-
10-oxide (DOPO) and its derivatives have received outstanding ture of DOPO and POSS revealed a positive effect similar to the
attention because of their high reactivity and applicability in flame DOPO-POSS which is DOPO being grafted on the POSS structure
retardancy. Using DOPO or its derivatives as flame retardants for [183]. According to the cone calorimeter data in Table 5, the pHRR
epoxy resins has been extensiving reported [189–193]. of the ternary mixture EP/DOPO/POSS was much lower than the
A phosphorus-containing epoxy resin (PCEP) was synthesized expected value calculated by averaging data from binary EP/DOPO
via the reaction between bisphenol A epoxy resin (DGEBA) and and EP/POSS mixtures. Furthermore, other important parameters
DOPO. When using the OV-POSS in combination with PCEP, the like THR, TSR, and mean SEA of EP/DOPO/POSS were also lower than
peaks of heat release rate of PCEP/OV-POSS hybrids reduces sub- the calculated values. These results indicated a synergistic effect
stantially [8]. As the amount of OV-POSS rises from 1 to 3 wt.%, between POSS and DOPO that could enhance flame retardancy of
the peak of HRR and THR decrease to more than 40% and 14%, EP composites.
respectively. The synergy mechanism in the PCEP/OV-POSS hybrids Furthermore, DOPO mixed with OPS or OAPS could make the
was investigated by real time Fourier transform infrared spectra LOI of EP composites reach 31.1% and 33.8, and the UL-94 rat-
and pyrolysis/gas chromatogram/mass spectrometry (Py–GC/MS). ing V-0 and V-1, respectively. These results are much higher than
It was found that OV-POSS migrated to the surface of the matrix those of EP resins with only one flame retardant. The improvement
and then sublimed from the surface in nitrogen; whereas, the vinyl in the LOI and UL-94 tests were mainly caused by the formation
groups of OV-POSS were oxidised to form a radical trap which could of P( O) O Si linkages, which connect the three dimensional
react with pyrolysis radicals derived from PCEP to form branched network of Si( O)4 and polyaromatic carbon structures (Fig. 64),
and crosslinked structures in air. according to the FTIR and XPS analysis [174]. Zhang et al. suggested
Shree Meenakshi et al. [194] prepared another epoxy resin that the retention of polyaromatic carbon structures in the Si( O)4
(EP)/POSS hybrid based on aminopropyl POSS (POSS-NH2 ) (Fig. 63) net would enhances the quantity of the char [174]. Furthermore, the
and phosphorus-containing diamine (DOPO-NH2 ) which was syn- Si( O)4 structure around the polyaromatic carbon structures could
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 107

Table 5
Cone calorimeter data for the EP composites [174].

Samples EP EP/OPS EP/OAPS EP/DOPO EP/DOPO/OPS EP/DOPO/OAPS

TTI (s) 45 55 57 54 51 53
p-HRR (kW/m2 ) 855 626 635 686 557(656) 645(661)
THR (MJ/m2 ) 112 112 110 96 95(104) 102(103)
TSR (m2 /m2 ) 4182 3729 3753 4675 3671(4202) 3961(4214)
mean SEA (m2 /kg) 897 899 893 1111 902(1005) 944(1002)

Copyright 2012. Reproduced with permission from Elsevier Ltd.


The vaulues in the brackets are calculated values.

O
O
R P
R R
Si O O
R O
R O Si C
O O
Si O
A O O Si B
Si O
O O Si O O
Si C
Si
O O O
R O
Si P R
O R
O

O O Si
O
R P O
R Si
O O
O
O Si
C
O

C
Si
O
O O Si C
Si O O O
O
O Si P R
O R
O

R = H or (CH2)n or Aromatic structures

Fig. 64. The illustration of the bridging effect of P( O) O Si structure in the condensed phase [174].
Copyright 2012. Reproduced with permission from Elsevier Ltd.

protect them from decomposing under flame conditions. Thus the produce Si O C or Si O P( O) C cross-linked structures
formation of P( O) O Si linkages could increase both the quan- in the condensed phase under the action of heat, leading to forma-
tity and the thermal stability of the char. Li and Yang [178] reported tion of solid carbonaceous char containing little Si and P. Therefore,
a flame retarded EP composite loaded with octadiphenylsulfonyl such a solid char may be very brittle, and may crack very easily.
POSS (OD-POSS) and DOPO. It is found that the mixture of OD- Cracking of the solid char uncovered fresh bulk EP, causing further
POSS and DOPO had a similar remarkable synergistic effect on flame combustion with ensuing high heat release and productions of CO
retarding EP resins. and CO2 .
Zhang et al. [175] prepared an EP resin loaded with DOPO In addition, among the organophosphorus flame retardants,
and ladder-type polyphenyl silsesquioxane (PPSQ). Unexpectedly, caged bicyclic phosphates have attracted much interest, and many
when PPSQ was added to the EP/DOPO composite, PPSQ apparently investigations have been reported [196]. It is found that caged
increases the p-HRR of EP/DOPO. The antagonism between PPSQ bicyclic phosphates and their derivatives can serve as effective
and DOPO in the EP composite seems to be anomalous, consider- intumescent flame retardants or charring agent in some polymers
ing that the thermal stability of ladder-type PPSQ was much larger [196,197].
than that of caged OPS, which showed good synergistic effect with One caged bicyclic phosphate PEPA (1-oxo-4-hydroxymethyl-
DOPO to fire retard EP resins. The authors concluded that due to 2,6,7-trioxa-l-phosphabicyclo[2.2.2] octane), which also is a
the higher thermal stability, the PPSQ in EP/DOPO can very slowly reactive phosphorus-containing flame retardant was loaded into
108 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 65. Synthesis route of branched phosphonate acrylate monomer (BPA) via thiol Michael addition of tri(acryloyloxyethyl) phosphate (TAEP) with octamercaptopropyl
POSS (OMP-POSS) [199].
Copyright 2015. Reproduced with permission from the Royal Society of Chemistry.

Table 6
The LOI values and microscale combustion calorimeter data of EP composites [200].
OH
OH Samples LOI (%) pHRR (W/g) THR (kJ/g)
Si
O O Pure EP 22.0 478.0 21.7
Si Si EP/2.0 wt.%Silicon 24.5 175.1 15.6
O OH
EP/1.5 wt.%Silicon/0.5 wt.%Boron 27.0 208.7 13.5
O O EP/1.0 wt.%Silicon/1.0 wt.%Boron 28.5 164.7 12.6
Si Si EP/0.5 wt.%Silicon/1.5 wt.%Boron 30.5 148.0 11.8
O O O EP/2.0 wt.%Boron 28.0 172.7 12.7
Si Si
O Copyright 2012. Reproduced with permission from Elsevier Ltd.

Fig. 66. The structure of trisilanolphenyl POSS (T-POSS). silanol and diglycidyl ether of bisphenol A (DGEBA). The metal-
lic catalyst would allow the reaction between silanols and epoxies
to occur [161,166]. The presence of [Al] latent catalyst leads to a
epoxy resins combined with octaphenyl POSS (OPS) to obtain halo- decrease in combustion rate with respect to epoxy and epoxy/POSS
gen free flame retardant systems [198]. According to the cone composites as well as reduction in smoke, CO and CO2 production
calorimeter test, the p-HRR of flame-retarded EP/PEPA (about rate. The effect of [Al] is to reduce the size of spherical POSS parti-
0.9 wt.% phosphorus) shows a 38% reduction from 860 kW/m2 to cles from 3–5 ␮m in epoxy/POSS to 0.5 ␮m in epoxy/POSS/[Al], then
538 kW/m2 . When PEPA in the EP/PEPA/OPS composite is partially the possible mechanism of this improvement could be attributed to
replaced by OPS (about 0.45 wt.% phosphorus and 0.45 wt.% silicon), the large area of the smaller POSS particles, which led to the higher
its pHRR is 524 kW/m2 that is almost the same as the pHRR of the efficiency in forming insulating char on the surface of composites
EP/PEPA composite (about 0.9 wt.% phosphorus). Furthermore, the during combustion.
THR, TSR and mean SEA of EP/PEPA/OPS composite are all higher The addition of aluminum triacetylacetonate ([Al]) catalyst in
than that of EP/PEPA. combination with trisilanolphenyl POSS greatly improved the fire
A novel branched phosphonate acrylate monomer (BPA, Fig. 65) retardant behaviors in the types of epoxy resins including: DGEBA,
containing phosphorus and polyhedral oligomeric silsesquioxanes TGDDM (tetraglycidy(diaminodiphenyl)methane), and commer-
(POSS) was successfully synthesized via thiol Michael addition of cial products MVR444R supplied by Cytek, UK [42]. The finer
tri(acryloyloxyethyl) phosphate with octamercaptopropyl POSS, dispersion of POSS in the cured epoxy resins network could account
and then incorporated into epoxy acrylate (EA) resins in different for the improvement of the fire retardant behavior. Furthermore, a
ratios using ultraviolet curing technology [199]. The flame retar- possible chemical effect of aluminium even at a low concentration
dant EA resins exhibited significantly improved LOI values, as high should be taken into account.
as 29%, while the PHRR and THR values were reduced by 50.8% and
29.8%, respectively. The improved flame retardancy of EA is due to 3.13.5. Epoxy resins with POSS and Boron compound
a condensed phase flame retardant mechanism, including the cat- The flame retarded epoxy resins were obtained through a
alyzing charring effect of phosphorus flame retardants and the char crosslinking reaction, using tris (2-hydroxypropyl) borate (THPB)
strengthening effect of silicon flame retardants, thereby forming a together with octaaminophenyl POSS (OAPS) as curing agents
more effective protective barrier. [200]. As shown in Table 6, THPB (boron) and OAPS (silicon) exhibit
a synergistic flame retardant effect on EP and the optimum result
3.13.4. Epoxy resins with POSS and metallic compounds both as LOI and PCFC data occur at Boron/Silicon = 3/1 ratio. There
Wu et al. [41] prepared an epoxy nanocomposite with trisi- are two possible synergistic flame retardancy mechanisms between
lanolphenyl POSS (T-POSS, Fig. 66) in the presence of aluminum THPB (boron) and OAPS (silicon). On the one hand, combination of
triacetylacetonate ([Al]) latent catalyst for the reaction between THPB and OAPS can be considered as a preceramic flame retardancy
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 109

Table 7 NH2
LOI of cured systems with different OAPS content [202], O O O
NH2
H2N O
Ns 0.25 0.5 0.75 1.0 Si
O O O Si O O
LOI (%) 45 46 48 49 Si Si
O O NH2
Copyright 2012. Reproduced with permission from Taylor & Francis. O BTDA O
O O
H2N OSi O Si
O NH2
Si Si
O
additive for EP which has an excellent heat and flame resistance H2N H2N O NH2
NH2
greater than traditional carbonaceous char [201]. On the other
hand, the THPB could catalyze the degradation of EP and accelerate OAPS ODA

the formation of a high temperature resistant char layer. Further-


more, the silica network from thermal degradation of OAPS besides Polyamidc Acid (PAA)
covering the surface of char layer, it also strengthens the char to
Δ/-H2O
make it more impermeable to both oxygen and pyrolytic volatile
products.

3.13.6. Epoxy resins with POSS and halogen-containing


compounds
Tetrabromobisphenol A is widely used as reactive fire retar-
dant for epoxy resin and polycarbonate, and as an additive fire
retardant for plastics, rubber, textiles, fibers, and paper. Gao et al.
prepared a tetrabromobisphenol A epoxy resin (TBBPAER) cured by O
O O O O O
the octaaminophenyl POSS (OAPS) [202]. Table 7 shows that the LOI
=* N N O n N
value of cured samples increases with Ns , which was defined as the
O O O O
molar ratio of amino group NH2 - in OAPS to the epoxy group in the
TBBPAER. The authors indicated that Si O bonds can form on heat- Fig. 67. Preparation of PI/OAPS composite [29].
ing an insulating glass coating which excludes oxygen and prevents Copyright 2013. Reproduced with permission from the American Chemical Society.
further propagation of combustion. No comment was made in this
work about possible positive effect of Si and Br during combustion. shine black char surface for the PI control, a white char layer of
PI/5.43 wt.%OAPS was generated at the surface of the char residues.
3.14. Polyimides The cross-linking reactions in the condensed phase, the formation
of compact char residues, and the out-migration effect of POSS
Polyimides (PI) are one of the most successful thermally sta- derived silicon moieties were the main reasons for the improved
ble commercial polymers, which has been widely used as coatings flame retardancy.
for microelectronic devices, gas-separation membranes, and high-
temperature materials due to their excellent thermal stability, high 3.15. Bismaleimide resins
glass transition temperatures, and remarkable mechanical prop-
erties [203]. Many researches showed that the thermal stability, Bismaleimide (BMI) resins are widely used as matrices of high
mechanical properties and flame retardancy of PI composites were performance composites in the fields of aerospace, transportation,
improved by the incorporation of POSS [204–206]. machinery, and electronics. This kind of resin has excellent prop-
Several polyimide/octaaminophenyl POSS (PI/OAPS) nanocom- erties, including good thermal stability, good processability, high
posites were prepared through thermally curing process with a mechanical strength, excellent dielectric properties [209,210].
controlled temperature program [207]. The PI/OAPS composites Devaraju et al. [211] reported a series of POSS incorporating
exhibited a considerably higher Tg value than that of the neat PI. BMI hybrids, which were developed by Michael addition reaction
Moreover, these composites showed an improved thermal stability of aliphatic ether linked aromatic bismaleimides (AEBMIs) with
and enhanced degradation temperature with increasing percent- octaaminophenyl POSS (OAPS) as shown in Fig. 68. The thermal
age concentration of OAPS. The residual char yields after the properties of neat AEBMI, and 1, 3 and 5 wt.% OAPS incorporated
incorporation of 5, 10 and 15 wt.% OAPS into the PI composites AEBMI systems, were studied using TGA. From the TGA data, it is
increase from 43.4 to 47.6, 48.8, and 50.4% respectively at 900 ◦ C. inferred that the increasing percentages incorporation of OAPS into
The authors expect that the increased char yield would lead to LOI the AEBMI systems increased the thermal stability and values of
increase as predicted by van Krevelen [208]. The high char yield char yield from 15 to 30% depending on structure. The authors pro-
leads to high flame retardancy, which can be calculated by van posed that the incresed char yield would increase LOI as predicted
Krevelen’s equation [LOI = 0.40() + 17.5] where  is the char yield by van Krevelen’s equation.
at 900 ◦ C. But actually, in van Krevelen’s equation the char yield is BMI/DOPO-POSS nanocomposites were obtained by thermal
that at 850 ◦ C. curing of 4,4 -bismaleimidophenyl methane (BDM) and 2,2 -dially
Fan and Yang [29] also prepared a series of PI/OAPS nanocom- bisphenol A (DBA) with DOPO containing POSS (DOPO-POSS) [212].
posites with different OAPS content through thermal curing
reaction as shown in Fig. 67. The thermal analysis results of PI/OAPS
composites show that, the OAPS loading did not change the degra- Table 8
Results of the LOI and UL-94 tests of the BMI and BMI/DOPO-POSS nanoposites [212],
dation process of PI composites, but could increase their residues
with increase of OAPS content. When 2.74 wt.% OAPS is incorpo- Samples LOI (%) UL-94 rating Dripping t1 /t2 (s)
rated, the LOI value of the PI/OAPS composite increased from 46.5% Neat BMI 25.3 ± 0.5 V-1 No 5.0/13.4
to 55.5%, which is much higher than the calculated value according BMI/5 wt.%DOPO-POSS 34.5 ± 0.5 V-1 No 3.0/13.1
to the van Krevelen’s equation used in the Devaraju et al. research BMI/10 wt.%DOPO-POSS 35.9 ± 0.5 V-0 No 2.6/5.3
BMI/15 wt.%DOPO-POSS 38.5 ± 0.5 V-0 No 2.2/2.5
[207]. The higher LOI values indicated that the flame retardancy of
PI composite was actually improved by OAPS. Compared with the Copyright 2015. Reproduced with permission from John Wiley & Sons Inc.
110 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 68. Schematic representation of OAPS-AEBMI nanocomposites [211].


Copyright 2014. Reproduced with permission from Springer.

Fig. 69. SEM micrographs of the char layer for (a) neat BMI and (b) BMI/15wt.%DOPO-POSS resins [212].
Copyright 2015. Reproduced with permission from John Wiley & Sons Inc.

In Table 8, the results show that DOPO-POSS increased the LOI of make the char layer become more integrated and dense (Fig. 69).
the resins from 25.3 to 38.5%. The neat BMI resins were evaluated This improvement was attributed to the synergistic effect of phos-
to have a UL-94 V-1 rating, but BMI resin containing DOPO-POSS phorous and silicon, which indicated that phosphorous accelerated
achieved a UL-94 V-0 rating. The presence of DOPO-POSS could the formation of char, whereas silicon kept the char from undergo-
enhance the charring degree of BMI resins during combustion and ing thermal degradation.
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 111

Fig. 70. Formation of the CE/OG-POSS hybrid composites [217].


Copyright 2006. Reproduced with permission from John Wiley & Sons Inc.

3.16. Cyanate ester resins composites had a higher char formation tendency with higher OG-
POSS contents; in particular, a weight loss was almost not observed
Cyanate ester resins (CE) are one of the most important ther- for the char from 800 to 900 ◦ C. This performance was based on
mosetting resins developed in the last few decades. These are the fact that OG-POSS produces a lot of silica (SiO2 ) residue and
currently in widespread use because of their low water absorp- interferes with the combustion process during heating, pyrolysis,
tion, good mechanical properties, low shrinkage on cure, excellent ignition, and flame propagation. With the OG-POSS concentration
dielectric properties along with good chemical resistance, and increasing from 0 to 50 mol %, the LOI values of the composites were
radiation resistant properties [213,214]. Modification of cyanate raised from 32 to 61% which demonstrated a significant improve-
ester properties with POSS has been attempted by several groups ment in the flame retardancy of the composites. All these results
[215,216]. indicated that OG-POSS not only improved the thermal stability of
The octa functional silsesquioxanes (octaaminophenyl POSS char but also provided the hybrid cyanate resin composites with
(OAPS) and octaglycidyl POSS (OG-POSS)) reinforced epoxy can good flame retardancy.
modify cyanate ester nanocomposites, in which crosslinking takes
place between cyanate ester and POSS [213]. The thermal stability
3.17. POSS and nanoparticle for polymers
of the CE/POSS nanocomposites increases with increasing percent-
age of both types of POSS macromer. Lu et al. [217] prepared several
3.17.1. POSS intercalated MMT for polymers
CE composites based on octaglycidyl POSS (OG-POSS) and cyanate
Nanocomposites may be produced using several different mate-
ester resin through the reaction of cyanate with epoxy groups in
rials, including clay, graphite, carbon nanotube, POSS, and so on.
the corner of cubic OG-POSS as shown in Fig. 70. The OG-POSS unit
Most work to data has been done with clays, particularly with
into the cyanate resin successfully modified the local structure of
montmorillonite clay, an alumina-silicate material [218]. Nanoclay
the molecule, made the chain more rigid, restricted the chain mobil-
even at a low loading with no additional flame retardants could
ity and improved the thermal stability and flame retardancy of the
greatly reduce heat release rate and mass loss rate (HRR and MLR)
cyanate resin. The TGA analysis showed that the cyanate/OG-POSS
compared to corresponding neat polymers. This was attributed to
112 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 71. TEM micrographs of polyamide 6 showing the dispersion quality of (a) organoclay layers; (b) organoclay layers and POSS particles [221].
Copyright 2009. Reproduced with permission from Elsevier Ltd.

Fig. 72. Bilayer structure of POSS-imidazolium exchanged montmorillonite [225].


Copyright 2007. Reproduced with permission from the American Chemical Society.

the structural collapse of the nanocomposite during combustion Besides adding POSS and nanoclay in the polymer separately,
and formation of a multi-layered carbonaceous-silicate barrier on POSS has been used as an organic surfactant to modify montmo-
the polymer surface. Nevertheless, the main disadvantage of poly- rillonite in recent years [222]. To investigate synergistic effects of
mer/clay nanocomposites is that most often they do not extinguish both layered silicates and POSS compounds, a dual nanocompos-
the flame and slowly burn. Time exceeding that required for safe ite approach consisting in exchanging montmorillonite clays with
use in fire risk application, as for example that stated by ignition POSS based surfactants was concurrently developed by Zhao et al.
resistance tests (such as vertical burning UL94 test) [219,220]. [223] and Fox et al. [224,225] (Fig. 72). Their studies indicated a
The trisilanolphenyl-POSS (T-POSS) was coupled with nanoclay mixed intercalated/exfoliated polymer (polyamide-6, polystyrene,
to flame retard polyamide 6 to pass fire testing standards [221]. poly(ethylene-co-vinyl acetate)) nanocomposite structure with
It is hoping that the POSS would transform on heating into glassy improved thermal properties over the pristine polymers. Since
material which by coupling with clay silicate layers could improve then, there has been a surge in the use of POSS surfactant exchanged
polymer fire protection. Additional incorporation of 15% POSS, in clays, all utilizing layered silicate structures which produced
polyamide 6/clay nanocompsite gave a finely dispersed nanocom- expanded interlayer spacings and improved polymer properties
posite (Fig. 71), which showed fire retardant improvement in the [226]. Both layered silicates and POSS have been shown to pro-
cone test as compared to the nanocomposte without POSS. The duce synergistic flame retardant enhancements when combined
nanoscopic size and structure of POSS and clay together with their with traditional flame retardants. Therefore, it is believed that some
fine dispersion contribute to these improved fire safety properties. POSS modified layered silicates will be potential flame retardants
Heat release rate together with other combustion parameters (such for polymers in the future.
as the release rates of CO and CO2 , the concentration of CO and CO2
and the smoke production rate) of composites is reduced effec- 3.17.2. POSS grafted carbon nanofibers for polymers
tively. More importantly, 5% replacement of POSS by organic clay Carbon nanofiber (CNF) and carbon nanotube (CNT), due to their
is very helpful to the further improvements in most of parameters unique reinforcing, mechanical, electronic, and thermal properties,
and cut down the cost effectively. have attracted tremendous research interests ranging from nano-
devices to composites [227–229].
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 113

Table 9
Cone calorimeter data for laminate composites samples [230].

Samples Average SEA (m2 /kg) Average HRR (kW/m2 ) THR (MJ/m2 )

Control sample (GF laminates without paper) 1194 ± 57 246 ± 12 91 ± 5


GF laminates + hybrid CNF paper (CNF/T-POSS = 5/10) 1011 ± 77 166 ± 17 70 ± 8
GF laminates + hybrid CNF paper (CNF/T-POSS/APP = 5/5/5) 1085 ± 60 204 ± 23 70 ± 4
GF laminates + hybrid CNF paper (CNF/T-POSS/APP = 5/3/7) 1132 ± 23 192 ± 16 75 ± 3
GF laminates + hybrid CNF paper (CNF/clay/T-POSS = 5/2/8) 1111 ± 45 197 ± 13 88 ± 2

Copyright 2011. Reproduced with permission from Elsevier Ltd.

Table 10
Cone calorimeter data for the nanocomposites coated with hybrid nanopaper [231].

Samples pHRR (kW/m2 ) Average SEA (m2 /kg) THR (MJ/m2 )

Control sample (GF laminates without paper) 375.9 ± 34.6 1044.1 ± 60.0 134.0 ± 8.2
GF laminates + CNF/T-POSS (9/1) paper 557.4 ± 25.0 898.6 ± 10.5 135.3 ± 5.2
GF laminates + CNF/T-POSS (1/1) paper 755.9 ± 64.2 926.2 ± 46.3 143.5 ± 10.4
GF laminates + CNF/T-POSS (3/7) paper 608.5 ± 5.4 889.5 ± 53.5 162.5 ± 22.5
GF laminates + CNF/T-POSS (1/9) paper 367.2 ± 2.1 775.2 ± 1.5 145.1 ± 2.2

Copyright 2011 Reproduced with permission from John Wiley & Sons Inc.

the composite laminates with CNF/T-POSS hybrid paper possessed


the lowest average specific extinction area (SEA), average heat
release rate (HRR), and total heat release (THR) as shown in Table 9.
According to these results, the synergy of carbon nanofiber and
trisilanolphenyl POSS performs a good action on flame retarding
the composite laminates.
Tang et al. [231] reported another hybrid nanopaper consist-
ing of carbon nanofiber (CNF) and octavinyl POSS (CNF/OV-POSS
nanopaper). The hybrid nanopaper was then coated on the surface
of glass fiber (GF) reinforced polyester resin composites through
resin transfer molding (RTM) process. The cone calorimeter results
for the control sample and various composite laminates coated
with hybrid CNF/OV-POSS nanopapers are shown in Table 10. The
peak heat release rate (pHRR) of the control sample is 375.9 kW/m2 .
For composite laminates coated with the CNF-POSS nanopaper, the
pHRR increases dramatically up to 755.93 kW/m2 when the weight
fraction of POSS in the nanopaper is 50 wt.%. Thereafter the pHRR
decreases with the increase in the weight fraction of OV-POSS. The
Fig. 73. HRRs of laminate composites incorporated with hybrid nanopapers [230]. pHRR drops to 367.2 kW/m2 with 90 wt.% of OV-POSS particles in
Copyright 2011. Reproduced with permission from Elsevier Ltd. the nanopaper, which is almost the same pHRR of control sam-
ple. Different POSS coupled with CNF show a totally different fire
behavior. The POSS particles were observed to migrate rapidly to
A nanopaper reinforced by carbon nanofiber (CNF) using the surface of polymer nanocomposites and sublime [232]. The evo-
trisilanolphenyl POSS (T-POSS) and ammonium polyphosphate lution of POSS particles from the surface to flame could increase the
(APP) as flame retardants was prepared [230]. The fire retar- HRR or even quickly ignite the polymer resin [231].
dant performance of composite laminates incorporating nanopaper Beside physical mixture of POSS and carbon nanofibers, Tang
was evaluated by cone calorimeter testing using a heat flux of et al. [233] reported on multiwalled carbon nanotubes (MWCNTs)
50 kW/m2 . As shown in Fig. 73, CNF/T-POSS hybrid paper on the covalently functionalized with aminopropylisooctyl POSS (AIO-
laminates reduces the pHRR by 5%, from 486 kW/m2 to 461 kW/m2 . POSS) (MWCNT-g-POSS, Fig. 74). The Fourier transform infrared
Furthermore, the addition of APP in CNF/T-POSS further decreases spectroscopy, Raman spectroscopy and transmission electron
the pHRR of the laminates. The reduction of 18 and 22% was microscopy (TEM) indicated that POSS particles were grafted onto
observed using 50 and 70 wt.% of APP to replace the same weight MWCNTs as shown in Fig. 75. The POSS content in MWCNT-g-
fraction of T-POSS in the hybrid paper respectively. As to the reduc- POSS was estimated to be about 25 wt.%. Two buckypapers were
tion of pHRR, the synergy between CNF and T-POSS was negligible, prepared using pristine MWCNTs or MWCNT-g-POSS. TGA and
whereas the synergy among the CNF, T-POSS and APP was remark- PCFC were used to evaluate the flame-retardant performance of
able. the buckypaper-based composites. The sample of pristine MWCNT
But as shown in Fig. 73, it was found that the HRR of nanocom- paper infused with unsaturated polyester resin shows that the
posites increased rapidly to high values after ignition (first peak) pHRR is significantly suppressed by 49%, from 249.1 W/g of the neat
and decreases slightly. Then there is a gradual increase followed by resin to 126.7 W/g. Further reduction of pHRR from 249.1 W/g to
a gradual decrease, resulting in a second broad peak at approx- 69.8 W/g (72%) is observed for MWCNT-g-POSS paper with resin.
imately 80–200 s. If the value of the second peaks is taken into Compared with the neat resin, the THR value of MWCNT and
account, the laminates coated with CNF/POSS hybrid paper has MWCNT-g-POSS buckypaper with resin is decreased by 43.6% and
the biggest reduction from 486 kW/m2 to about 350 kW/m2 . This 67.6%, respectively. The decrease of HRR and THR indicates that the
indicated that synergy between CNF and T-POSS could create good incorporation of the MWCNT and POSS showed a remarkable effect
barrier to prevent the composites from quick combustion. Since the that could restrict the fire development of polymer composites. The
second broad peak concerns the main combustion step of samples,
114 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

Fig. 74. Synthesis of MWCNT-g-POSS [233].


Copyright 2013. Reproduced with permission from John Wiley & Sons Inc.

Fig. 75. TEM images of (a) MWCNT and (b) MWCNT-g-POSS [233].
Copyright 2013. Reproduced with permission from John Wiley & Sons Inc.

remarkable fire retardant effect was due to the smaller median pore accelerate the degradation of polymers, which will result in a
size of MWCNT-g-POSS hybrid buckypaper and the char formation reduction of TTI. However, this kind of early decomposition helps
during combustion, which could effectively limit the heat and mass to create a timely char barrier to retard the further combustion of
transfer and the diffusion of the flammable gases and therefore slow polymer/POSS nanocomposites. Another catalytic action of POSS is
down the combustion and degradation of the resin [231,233]. caused by the metal element which may be carried in its structure.
This action could change the decomposition process of polymer
4. Conclusions matrix, increase the char yield and improve the morphology of
char layer.
Flame retardancy of polymer/polyhedral oligomeric POSS show a remarkable synergistic effect with traditional flame
silsesquioxane (POSS) nanocomposites, reported in this review, retardants even at a very low additive amount. Addition of POSS
involves several mechanisms. Each one of them influences mate- could improve the flame retardnacy of polymers with traditional
rial’s fire behaviors in a manner which is highly associated with the flame retardants or reduce the amount of traditional flame retar-
structure and properties of POSS. The construction of a superficial dants necessary to meet the requirements of fire prevention thus
char layer is generally considered as the principal mode of poly- reducing environmental impact. Due to the strong advantages of
mer/POSS nanocomposites’ flame retardant action in developing tailor-made specific atoms containing POSS structure, some syn-
fires. During burning in air, the organic groups on POSS cages can ergistic effects from the POSS are detected. Many kinds of flame
undergo homolytic Si C bond cleavage, resulting in the fusion of retarding elements such as P, N, S, B, and catalytic metal elements
the POSS cages and the formation of a thermally- and oxidatively- can be incorporated in the POSS structures via chemical synthe-
stable silicon-oxycarbide “ceramic” surface. The catalyst actions sis. Fine dispersion of these elements within the polymer matrix is
of POSS could influence fire behaviors of polymer. Free-radicals obtained due to the good compatibility of POSS.
from the organic groups of POSS during thermal degradation can
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 115

The main challenge restricting the commercial POSS applica- by nanocomposites tempts industries and research institutions to
tions is its cost. However, POSS have obtained practical application invest on further research.
in the military field, aviation and aerospace fields, and some high
performance materials where cost is not relevant. On the other Acknowledgements
hand, cost of POSS is not the right issue to consider, because high
efficiency of POSS based fire retardant may make its cost lower The authors are grateful to Prof. Alberto Fina at Politecnico di
than that issued by the use of current fire retardant additives. Torino for discussion and support during the preparation of this
Furthremore, POSS-based additives may confer to polymers high work.
fire retardant performances required by high demanding applica- This project was funded by International Science & Technology
tion so far precluded to polymers by using cheap fire retardants. Cooperation Program of China (No. S2014ZR0465), National Natural
Thus POSS-based additives may open new high tech, high value Science Foundation of China (No. 51273023) and China Postdoc-
applications for polymer materials. Finally, the commercializa- toral Science Foundation (No. 2014M550023).
tion of nanocomposites in the flame retardant market is still at
the beginning. The vast potential for product innovation offered Appendix A. POSS structures, nomenclatures and
application fields

Name Structure Relative polymers

(AIB-POSS) aminopropylisobutyl POSS PP [57] and iPP [58]

(AIBS-POSS) aminopropyl isobutyl PPE [113]


silanol POSS

(AIO-POSS) aminopropylisooctyl POSS EP [194,195] and Buckypaper


[233]

(Al-POSS) aluminium isobutyl POSS PP [50]

(AM-POSS or AEAPI-POSS) PP [56], PPE [113] and PBT


aminoethylaminopropyl [124]
heptaisobutyl POSS
116 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

(Br.ph-POSS) brominating octaphenyl PS [75]


POSS

(DOPO-POSS) dopo containing POSS PC [94,95], PC/ABS [96], EP


[181,182,184,185] and BMI
[212]

(DP-POSS) dodecaphenyl POSS PET [117,118] and PU [59,135]

(Gly-iBu POSS) glycidyloxypropyl EP [172]


heptaisobutyl POSS

(Gly-Ph POSS) glycidyloxypropyl Cellulose [81,148,153], EP


heptaphenyl POSS [172] and PLA [148]

(HIB-POSS) bis(triethoxysilyl)alkanes PS [67–69]


isobutyl POSS

(IC-POSS) isocyanate heptacyclopentyl PS [35]


POSS
W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 117

(MAE-POSS) methacrylateethyl POSS PMMA [82]

(MI-POSS) methacrylisobutyl POSS PLA [36], VE [129] and FAVE


[129]

(Me-PSS) methyl polysilsesquioxanes PP [45]

(NC-POSS) norbornenyl PE [7]


heptacyclopentyl POSS

(OAPS) octaaminophenyl POSS PBS [127], EP


[174,198,200,202], PI [29,207],
CE [234] and BMI [211]

(OCAP-POSS or OPCA-POSS) PS [73], Cotton fabrics


octa(chloroaminopropyl) POSS [152,154,155] and PET [120]
118 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

(OctaTMA-POSS) octasiloxane Cotton fabric [152,155] and PS


1,3,5,7,9,11,13,15- [70]
octakis(cyloxide)hydrate

(OD-POSS) octadiphenylsulfonyl POSS EP [30,178]

(OG-POSS) octa glycidyl POSS CE [217,234]

(OIB-POSS) octaisobutyl POSS PP [43,50,56]

(OIC-POSS) octaisooctyl POSS PP [43]

(OMA-POSS) octamethacryl POSS VE [129] and FAVE [129]

(OM-POSS) octamethyl POSS PP [43], PE [60], PET [115–119],


PBT [124], PU [136] and EP
[177,188]

(OMP-POSS) octamercaptopropyl POSS EA [199]


W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125 119

(OPS) octaphenyl POSS PC [88,89], EP [172,174–176]


and PS [75]

(OV-POSS) octavinyl POSS PP [55], P(POSS-MMA-VBFC)


[156], Hybrid nanopaper [231],
PVA [160], EP [8] and EA [104]

(TO-ph-POSS) PP [47] and iPP [48]


tetrasilanolphenyl-silsesquioxane

(Ph-PSS) phenyl polysilsesquioxanes PP [45]

(PPSQ) polyphenylsilsesquioxane PMMA [83], PC [92] and EP


[174,175]

(PPSQDS) poly[(phenylsilsesquioxane)- PC [85]


co-(dimethylsiloxane)]

(SC-POSS) styryl heptacyclopentyl PS [66]


POSS

(SDOH) disilanol cyclohexyl POSS EP [166]


120 W. Zhang et al. / Progress in Polymer Science 67 (2017) 77–125

(STOH) trisilanol cyclohexyl POSS EP [167]

(TIB-POSS) trisilanolisobutyl POSS PLA[145,147], EP[168,169] and


PS[67]

(TiIV -POSS) vanadium isobutyl POSS PP [51]

(T-POSS) trisilanolphenyl POSS PMMA [81,82], PC [90,103], EP


[41,42], Hybrid paper [230],
PET [122], PA6 [221] and PBT
[124]

(Vi-PSS or FQ-POSS) vinyl PP [45,59], PET [117], VE [129],


polysilsesquioxanes FAVE [129], PU [59,134] and
Polyurea [140]

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