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Review
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
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
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
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.
3.1. Polyolefins
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. 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. 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. 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. 27. The structures of bisphenol A bis(diphenyl phosphate) (BDP) and resorcinol
bis(diphenyl phosphate) (RDP).
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.
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
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.
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)
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 )
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. 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.
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
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.
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).
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].
Copyright 2013 and 2012. Reproduced with permission from Elsevier Ltd.
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
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
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].
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)
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
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
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
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.
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 )
Table 10
Cone calorimeter data for the nanocomposites coated with hybrid nanopaper [231].
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.
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
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