polymers

Review
Recent Advances for Flame Retardancy of Textiles
Based on Phosphorus Chemistry
Khalifah A. Salmeia 1, *, Sabyasachi Gaan 1 and Giulio Malucelli 2, *
1 Additives and Chemistry, Advanced Fibers, Empa, Swiss Federal Laboratories for Materials Science and
Technology, St. Gallen CH-9014, Switzerland; sabyasachi.gaan@empa.ch
2 Department of Applied Science and Technology, Local INSTM Unit, Politecnico di Torino, Viale T. Michel 5,
15121 Alessandria, Italy
* Correspondence: khalifah.salmeia@empa.ch (K.A.S.); giulio.malucelli@polito.it (G.M.);
Tel.: +41-5-8765-7038 (K.A.S.); +39-0131-229369 (G.M.);
Fax: +41-5-8765-7499 (K.A.S.); +39-0131-229399 (G.M.)

Academic Editors: Baljinder Kandola, Abderrahim Boudenne and Paul Kiekens

Received: 30 June 2016; Accepted: 19 August 2016; Published: 25 August 2016

Abstract: This paper aims at updating the progress on the phosphorus-based flame retardants
specifically designed and developed for fibers and fabrics (particularly referring to cotton, polyester
and their blends) over the last five years. Indeed, as clearly depicted by Horrocks in a recent review,
the world of flame retardants for textiles is still experiencing some changes that are focused on
topics like the improvement of its effectiveness and the replacement of toxic chemical products
with counterparts that have low environmental impact and, hence, are more sustainable. In this
context, phosphorus-based compounds play a key role and may lead, possibly in combination with
silicon- or nitrogen-containing structures, to the design of new, efficient flame retardants for fibers
and fabrics. Therefore, this review thoroughly describes the advances and the potentialities offered by
the phosphorus-based products recently developed at a lab-scale, highlighting the current limitations,
open challenges and some perspectives toward their possible exploitation at a larger scale.

Keywords: flame retardants; fibers and fabrics; phosphorus-based products; biomacromolecules;

cotton; polyester; cotton-polyester blends; polyamide

1. Introduction
Textiles play an important role in everyday life: one of their main drawbacks refers to
their structure, as they are mainly made of organic polymers, which conversely, if not inherently
flame-retarded (such as polyaramides and polyphosphonate fibers), are flammable and potentially
dangerous species. Specifically referring to fibers and fabrics, the annual UK fire statistics have clearly
demonstrated that most of fire incidents occur in houses, involving upholstering furniture, bedding
and nightwear [1].
In this context, the ease of flammability of textiles has been faced by designing and synthesizing
suitable flame retardants (FRs), i.e., additives that are able to suppress or delay the appearance of a
flame and/or reducing the flame-spread rate (flame retardants) or delaying ignition or reducing the
rate of combustion when needed (fire retardants) [2].
From an overall point of view, combustion in the presence of flames is a gas-phase process
exploiting the oxygen taken from the surroundings. As a consequence, before the occurrence of
the combustion process, the textile undergoes degradation: some of the so-obtained degradation
products turn into combustible volatile species that, in combination with oxygen, fuel the flame. If the
heat generated in the combustion is sufficient, it can be easily transferred to the textile substrate,

Polymers 2016, 8, 319; doi:10.3390/polym8090319 www.mdpi.com/journal/polymers

Polymers 2016, 8, 319 2 of 36
Polymers 2016, 8, 319 2 of 36

hencehence
giving riserise
giving to further degradation
to further degradationphenomena andsupporting
phenomena and supporting a self-sustaining
a self-sustaining combustion
combustion
cyclecycle
(Figure 1).
(Figure 1).

Air
(oxygen supply)

GAS PHASE

Products
Volatile species Flame
(CO, CO2, ...)

Heat
to the atmosphere

Textile substrate Char

CONDENSED PHASE

Figure
Figure 1.1.Scheme
Schemeof
of the
the textile
textilecombustion
combustioncycle.
cycle.

On the basis of the chemical composition and their thermal and fire characteristics, if they are
On the basis of the chemical composition and their thermal and fire characteristics, if they
not inherently flame retarded, fibers and fabrics have to be treated with additives that may contain
are not inherently
halogen, flame
nitrogen, retarded,sulphur,
phosphorus, fibers and fabrics
boron, metals,have
etc., to be treated
hence becomingwith flameadditives
retarded.that
The may
contain halogen, nitrogen,
aforementioned additivesphosphorus,
can be addedsulphur, boron, metals,
during spinning processesetc., hence becoming
performed on syntheticflame retarded.
fibers, or
The aforementioned
deposited on the additives
synthetic or can be added
natural duringsurface,
fiber/fabric spinning processes
hence creatingperformed
a protectiveon synthetic fibers,
layer/coating.
or deposited on theand
Both finishing synthetic
coatingormethods
natural fiber/fabric surface,
can be exploited: hence creating
concerning a protective
the former, layer/coating.
the fiber/fabric is
impregnated with a solution or a stable suspension that contains the FR additive.
Both finishing and coating methods can be exploited: concerning the former, the fiber/fabric is Conversely, the
coating method
impregnated with ainvolves
solutiontheorapplication of a continuous
a stable suspension that or discontinuous
contains the FR layer/film
additive. on both
Conversely,
surfaces of the textile.
the coating method involves the application of a continuous or discontinuous layer/film on both
From an overall point of view, the self-sustaining combustion cycle of Figure 1 can be broken in
surfaces of the textile.
the presence of FR additives, thus achieving the extinction of the flame or reducing the burn rate. In
From an overall point of view, the self-sustaining combustion cycle of Figure 1 can be broken
particular, they can:
in the presence
• of FR
Lower additives,
the developedthus
heat achieving thenecessary
to below that extinction of theonflame
to carry or reducing
the combustion the burn rate.
process.
In particular,
• they can:
Modify the pyrolysis process to lower the quantity of flammable volatiles developed,
favoring, at the same time, the creation the char, i.e. a carbonaceous residue that also limits the heat
• Lower
and mass thetransfer
developed heat
between totextile
the belowmaterial
that necessary to carry on the combustion process.
and the flame.
• Modify• the
Isolate the flame from the oxygen/air supply. of flammable volatiles developed, favoring,
pyrolysis process to lower the quantity
at the• same time,flame
Release the creation
inhibitorsthe char,
(like i.e., a carbonaceous
chlorinated residue
and brominated that alsowhen
compounds) limitsthe
the heat and
textile
approaches
mass thebetween
transfer ignition temperature.
the textile material and the flame.
• • the
Isolate Lower
flame the heatthe
from flowoxygen/air
back to the fabric,
supply. hence limiting or preventing further pyrolysis.
• Favor the formation of a char or an intumescent protective layer when the textile interacts
• Release flame inhibitors (like chlorinated and brominated compounds) when the textile
with a flame or a heat source.
approaches the ignition temperature.
A review published in 2011 succeeded in summarizing the state of the art for the different
• Lower the heat
commercially availableflow back
flametoretardants
the fabric, forhence
textilelimiting orwhich
materials, preventing further pyrolysis.
were classified according to the
• Favor
followingthe periods
formation [3]: of a char or an intumescent protective layer when the textile interacts with a
flame• or 1950–1980:
a heat source. The ”golden period” of flame retardant research, involving the appearance of
the first patents on FRs based on organophosphorus compounds for cellulosic textiles (i.e. cotton).
A review
During thispublished in 2011
period, inherently FRsucceeded in summarizing
synthetic fibers thestructures
bearing aromatic state of were
the art
alsofor the different
developed.
•
commercially 1980–late
available1990s:
flameVery limited for
retardants advances
textileofmaterials,
the research in FRs
which were
were achievedaccording
classified during thisto the
period.
following periods [3]:

• 1950–1980: The “golden period” of flame retardant research, involving the appearance of the first
patents on FRs based on organophosphorus compounds for cellulosic textiles (i.e., cotton). During
this period, inherently FR synthetic fibers bearing aromatic structures were also developed.
• 1980–late 1990s: Very limited advances of the research in FRs were achieved during this period.
Polymers 2016, 8, 319 3 of 36

• 2000 onward: Several efforts were carried out in the design of char-former flame retardant
additives, possibly containing phosphorus-based products. Another goal was the investigation
into the possibility of replacing bromine derivatives with other less toxic and efficient products.
Furthermore, during this period, nanotechnology was demonstrated to show outstanding
potential for conferring flame retardant features to fibers and fabrics, through the use of
nanoparticles having different aspect ratios. In particular, the exploitation of both top-down
(using preformed nanoparticle suspensions) and bottom-up (exploiting the generation of
single nanoparticles or nanoparticle assemblies—even hybrid organic-inorganic structures) was
successfully considered [4,5].

Specifically referring to the textile field, FRs can also be classified according to their “laundry
durability”: indeed, a non-durable FR is washed off immediately when soaked in water, but may resist
dry cleaning. Conversely, semi-durable FRs are able to resist water-soaking and possibly a few washes,
while durable FRs endure some 50 or 100 washing cycles.
However, according to the very stringent directives recently promoted by the EU community
and USA, some of the halogenated compounds (such as brominated diphenyl derivatives) have been
banned, as they have clearly shown a high toxicity for both animals and humans [6].
The aforementioned disadvantages stimulated the scientific community toward the design and
development of phosphorus-based compounds, which seem less toxic and may represent a suitable
alternative to their halogen-based counterparts. Though it is not a general case that all phosphorus
compounds are non-toxic, the development of new flame retardants based on phosphorus compounds
has shown that they have lower toxicity profiles as compared to halogen-based counterparts [7,8].
In general, the development of any new flame retardant should involve a complete assessment of its
performance in material as well as its toxicity.
In this context, some new products have been designed and nowadays are commercially available.
®
In particular, Trevira CS , which is based on the use of a phosphorus-containing comonomer (in the
form of propionylmethylphosphinate), has been exploited for conferring flame retardant properties to
polyester fibers and fabrics [9,10]. Regarding cotton and cellulosic-rich substrates, the present focus is
either on the synthesis of effective non-halogenated additives for coatings and back-coated fabrics or on
the utilization of hydroxymethylphosphonium salts (Proban® ) or N-methylol phosphonopropionamide
derivatives (Pyrovatex® ).
The chemistry of the Proban® process exploits a tetrakis(hydroxymethyl) phosphonium–urea
condensate, which, after padding, is crosslinked by ammonia gas in a dedicated plant and then
subjected to peroxide oxidation for stabilizing the resulting polymeric matrix [11]. The washing
fastness of this treatment is due to the deposition of the chemical within the fibers by a construction of
a polymer network during the heating process: as a consequence, Proban® is not linked to the fibers
but is mechanically retained within the fiber interstices. One of its major disadvantages refers to the
possible release of formaldehyde during the fabric use [12].
Conversely, the chemistry behind Pyrovatex® is based on a conventional pad-dry-cure process in
the presence of a methylolated crosslinking agent, which is responsible for the formation of covalent
bonds with the hydroxyl groups of the cellulosic substrate. Nonetheless, about 50% of Pyrovatex® FR
treatment has been reported to be lost during the first laundry occurrence, because of the extraction of
unreacted products, though it remains stably linked thereafter.
Despite the efficiency of such commercially available treatments, both academic and industrial
researchers are still seeking worthy alternatives, also taking into account the requirements that have to
be fulfilled by the new products. In particular, with respect to the already existing FRs:

• Any new flame retardant should show equivalent or superior ease of application.
• Any new flame retardant should not emit formaldehyde during application or service.
• Any new flame retardant should provide comparable textile service-life features, specifically
referring to durability, comfort, tensile properties, outward appearance and aesthetics.
Polymers 2016, 8, 319 4 of 36

• Any new flame retardant should possess an overall comparable cost-effectiveness to the already
existing chemicals and preferably be less costly.
• Any new flame retardant should possess equivalent or even lower toxicity and environmental impact.
• Air permeability of the treated textiles should be maintained, irrespective of the possible high
amounts of chemicals needed to provide flame retardant features.
• Any new flame retardant should not cause any alteration in the hue of the dye and/or dyeability
of the fibers/fabrics.

Nowadays, the approach adopted by the scientific community is being slightly changed:
indeed, the durability of any new flame retardant is still needed, but the novel processes and
methods developed in last five years seem to be more addressed to the design of low impact and
eco-friendly systems.
In this context, the present paper aims at providing an overview of the recent advances in the
design of phosphorus-based FRs, also in combination with nitrogen- or silicon-containing structures,
for different fibers and fabrics: in particular, the evolution from chemical to low environmental impact
products will be thoroughly described, highlighting the current achievements and limitations, as well
as the open challenges and perspectives.

2. Assessment of the Fire Behavior of Textiles

This section summarizes the current methods that allow assessing the reaction of a textile toward
the exposure to a flame or a heat flux. All the developed methods take into account that, for textiles,
the high fiber surface to mass ratio favors their easy ignition; in fact, these materials burn faster than
other bulk polymers.
Generally speaking, ignition occurs when a small flame is applied to flammable fabrics for no
more than 12 s and the textile continues to burn after the removal of the flame. Therefore, most of the
work on flammable fabrics focuses on the evaluation of the facility of ignition, the rate and extent of
flame spread, the duration of flame propagation, the heat release and heat of combustion. All these
parameters are merged with a quantitative portrayal of burning wreckages, such as melt dripping.
It is very difficult to find a single test method able to measure all the aforementioned parameters.
Concerning the fabrics that show self-extinction, such as flame-retarded fabrics, tests comprise the
evaluation of time of afterflame and afterglow and extent of fire damage (specifically referring to char
length, dimension of holes, or damaged sample length).
The measurement of textile flammability involves either scientific (i.e., research) test or the
standard test methods. The former provide information suitable for assessing the burning behavior
and are exploited for the design of new FRs or fire-retardant treatments.
Limiting oxygen index (LOI), also called oxygen index (OI), is one of the most popular scientific
methods, used in many standards, such as ISO 4589 and ASTM D2863. LOI denotes the minimum
concentration (vol %) of O2 in a mixture of O2 and N2 that will just sustain flaming combustion of a
material in a candle-like manner. Textile materials burn rapidly when they exhibit LOI values up to
21 vol %, while they burn slowly when LOI is in between 21 vol % and 25 vol %. LOI values beyond
26 vol % indicate some flame retardant features [13].
The obtained LOI values may be affected by several fabric structural parameters, when measured
for the same fiber type: this makes LOI values relative and not absolute data. In addition, the textile
material is ignited at the top and thus it burns vertically downward (i.e., in candle-like manner) which
is opposite to the burning of any material freely suspended.
Simple ignition tests (used in many standards, such as BS 5438 and EN ISO 6941) represent another
usual approach for assessing the flammability of a textile material: more specifically, a standard gas
flame is applied to the face or lower edge of a vertically oriented fabric sample; ignition is examined by
visual observations and the time needed to ignite the specimen is recorded. The textile does not pass
the test when, after the removal of ignition source, the flame achieves any end of the sample. If the
Polymers 2016, 8, 319 5 of 36

flame reaches extinction, the char length, dimension of holes, afterglow, and type of any wreckage
(molten drops, etc.) are thoroughly evaluated.
Flame spread (UL-94, which contains EN 60695 11-10, ASTM D 635-03 and D 3801-00) is a
Polymers 2016,
bench-scale test 8,which
319 measures the rate of flame spread usually calculated as the ratio of the 5 of 36
distance
to the time taken of the advancing flame front to reach defined distances marked on the fabric specimen.
Flame spread (UL-94, which contains EN 60695 11-10, ASTM D 635-03 and D 3801-00) is a
The upward fire spread is far faster than downward and horizontal flame spread and, hence, adopted
bench-scale test which measures the rate of flame spread usually calculated as the ratio of the
as a better
distance to theoftime
means assessing the
taken of thefire hazard of
advancing a fabric.
flame front to reach defined distances marked on the
Although not specifically
fabric specimen. The upwarddesigned
fire spreadfor fabrics,
is far faster cone calorimetry
than downward andtests (according
horizontal flametospread
ISO 5660)
have and,
become
hence,a standard
adopted as bench scale
a better means model of early the
of assessing flaming [14,15].
fire hazard of aInfabric.
particular, the cone calorimeter
mimics the Although
penetrativenot specifically
burning seendesigned
as firefor fabrics,into
burning conea calorimetry
specimen. It tests (according
evaluates theto ISOrelease
heat 5660) rate
have become a standard bench scale model of early flaming [14,15].
and the effective heat of combustion from a burning material exposed to a controlled radiant In particular, the cone heat
source (ISO 5660 part 1). Usually, such parameters as Time To Ignition (TTI), Total Heat Releasethe
calorimeter mimics the penetrative burning seen as fire burning into a specimen. It evaluates (THR),
Heat heat release rate and the effective heat of combustion from a burning material exposed to a
Release Rate and corresponding peak (pkHRR), Effective Heat of Combustion (EHC), Mass Loss
controlled radiant heat source (ISO 5660 part 1). Usually, such parameters as Time To Ignition (TTI),
(ML) and Mass Loss rate (MLR) can be evaluated. The cone calorimeter can also be utilized to evaluate
Total Heat Release (THR), Heat Release Rate and corresponding peak (pkHRR), Effective Heat of
smoke generation (ISO 5660 part 2): in this case, the measured parameters include the determination of
Combustion (EHC), Mass Loss (ML) and Mass Loss rate (MLR) can be evaluated. The cone
CO and CO2 concentrations,
calorimeter as welltoasevaluate
can also be utilized the assessment of smoke density
smoke generation (ISO 5660 (Specific
part 2):Extinction
in this case,Area–SEA,
the
Totalmeasured
Smoke Production–TSP,
parameters include etc.).the determination of CO and CO2 concentrations, as well as the
The micro-combustion
assessment of smoke density calorimeter (MCC) has
(Specific Extinction Arearecently been
– SEA, Total standardized
Smoke Production(ASTM D7309-13)
– TSP, etc.).
The micro-combustion
and exploited for evaluating the calorimeter
flammability (MCC) of has recently[16,17].
polymers been standardized (ASTM
In this process, D7309-13)
a small specimen
and
(about exploited
2–10 for evaluating
mg) undergoes the flammability
pyrolysis through of polymers
a fast heating [16,17].
up inIninert
this process, a small
atmosphere specimen
(with a heating
(about 2–10
◦ mg) undergoes pyrolysis through a fast heating up in inert atmosphere
rate below 1 C/s). The obtained pyrolysed products are then mixed with O2 /N2 mixture to expedite (with a heating
rate below 1 °C/s). The obtained pyrolysed products are then mixed with O2/N2 mixture to expedite
combustion. The oxygen concentration and flow rates of the combustion gases are evaluated, and the
combustion. The oxygen concentration and flow rates of the combustion gases are evaluated, and
amount of generated heat is calculated on the basis of oxygen consumption calorimetry.
the amount of generated heat is calculated on the basis of oxygen consumption calorimetry.
3. Phosphorus Chemistry in FRs: An Overview
3. Phosphorus Chemistry in FRs: An Overview
Phosphorus-based
Phosphorus-based flame retardants
flame are quite
retardants versatile
are quite in their
versatile inflame
their retardant action. Phosphorus
flame retardant action.
compounds
Phosphorus compounds often exhibit both condensed and gas phase activity [18].scheme
often exhibit both condensed and gas phase activity [18]. A simplified of various
A simplified
flamescheme
retardant actions
of various of phosphorus
flame is presented
retardant actions in Figure
of phosphorus 2.
is presented in Figure 2.

Figure 2. Mode of action of phosphorus-based flame retardants.

Figure 2. Mode of action of phosphorus-based flame retardants.
Polymers 2016, 8, 319 6 of 36

An additive is considered to be active in condensed phase if it alters the thermal decomposition

characteristics of the polymer by a chemical reaction. Hydrolysis, dehydration, chain scission or
de-polymerization are some of the main chemical reactions occurring in condensed phase activity.
This activity is usually characterized by a reduction in the decomposition temperature of the polymer
and increased formation of char residue at elevated temperatures [19].
In some cases, the de-polymerization of thermoplastic polymer chains in the presence of a heat
source reduces the viscosity of the system and enables it to retreat from the fire without producing
any residue.
The efficiency of phosphorus compounds to change the decomposition and combustion
characteristics of polymers makes their fire suppressant use imperative. Depending on the substrate
and their chemistry, there could be chemical interactions in the condensed phase at elevated
temperatures, which lead to changes in the decomposition pathway of the polymer and possible
formation of carbonaceous char residues on the surface of decomposing polymer, hence preventing
its further oxidation. In other instances, the phosphorus compounds and some of their decomposed
products preferably volatilize from the polymer substrate when heated. These phosphorus species
further decompose to release reactive phosphorus species, which then interact with the combustion
intermediates in the gas phase as inhibitors. In most cases, such interactions lead to recombination of
the H and OH radicals and prevent their oxidation.
The condensed or gas phase activity of phosphorus compounds significantly depends on their
structure, as well as on the polymer substrate. For example, in case of natural polymers like cellulose
and wool, the phosphorus compounds primarily exhibit condensed phase activity where dehydration
of the polymer, leading to the formation of a thermally stable char, is the predominant mechanism.
Referring to synthetic polymers containing oxygen and nitrogen atoms in their structure, catalytic
hydrolysis of the ester or amide groups by phosphorus acids promotes an enhanced melt dripping
and fast shrinkage from flame. As far as olefin-based polymers are considered, the phosphorus
compounds mainly act in the gas phase by recombining the key fuel species such as H and OH radicals
and preventing their oxidation. Some minor physical effects due to volatilization of phosphorus
compounds and dilution of the fuel can also occur.

4. Chemical Phosphorus-Based FRs for Textiles

The following paragraphs will describe the recent advances concerning the use of
phosphorus-based chemical products, suitable for conferring flame retardant properties to different
fibers and fabrics. In general, Table 1 summarizes the recent findings of P-based flame retardants and
their performance on textile fabrics.
Polymers 2016, 8, 319 7 of 36

Table 1. Main results achieved by treating fabrics with phosphorus-based flame retardants.

Durability
Type of P-based FR Textile material Highlights Ref.
(washing fastness)
New oligomers were synthesized and their burning behavior was compared to Antiblaze 19® .
The new oligomers showed higher thermal stability and more char residue comparing to
Dioxaphosphorinane Antiblaze 19® .
PET ND * [20]
derivatives The thermal stability and flame retardant properties were studied only on the oligomeric
derivatives.
Treated PETs with these oligomers were not investigated.
Cotton fabric was treated with UV-curable flame retardants and cured under UV-lamp in
presence of photoinitiator.
LOI values increased with increasing the FR content.
Cotton MCC showed a decrease in HRC and HRR and THC with increasing the FR content. Yes [21–23]
As increasing the monomer concentration and UV exposure time, the coating yield increased.
Relatively small monomers were not suitable for UV-curing as they might evaporate during
curing process.
UV-curable flame Allyl-functionalized polyphosphazene additive was investigated, avoiding the disadvantage of
retardants Cotton and Cotton/ small molecules.
Yes [24]
polyester blend The treated fabrics showed good flame retardancy with char formation.
The additive acts in the condensed phase mode of action
UV-curable epoxy based oligomer formulation.
Vinyl phosphonic acid (VPA) was incorporated in the formula.
Polyester/
The thermal stability, char formation and LOI values of the treated fabrics increased with ND [25]
Polyamide blend
increasing the concentration of the VPA acid
The peel strength values increased gradually up to 50.8 N/cm with increasing VPA.
The triazine-based flame retardants are derivatives of cyanuric chloride.
These additives are considered as active flame retardants, forming ether bond by replacement
the chlorine atoms with the hydroxyl groups pf cellulose.
Triazine-based flame The fabrics were treated with flame retardants by impregnation.
Cotton Yes [26–33]
retardants Thermal analysis showed a char formation which proves the condensed phase mode of action.
LOI values increased with increasing the add-on of flame retardants.
With increasing the flame retardant concentration, the treated fabrics did not show any
afterglow, which can be considered as self-extinction.
Polymers 2016, 8, 319 8 of 36

Table 1. Cont.

Durability
Type of P-based FR Textile material Highlights Ref.
(washing fastness)
The fabrics were treated with flame retardants using the sol-gel technique.
Increasing the sol-gel precursors on treated fabrics, showed a decrease of the HRC, PHRR and
Cotton TGA onset and an increase of the char residue. Yes [34–41]
Increasing the solid dry add-on increased relatively the after flame with no afterglow.
Hybrid
Increasing the solid dry add-on increased the LOI value and decrease of the THR and HRC.
organic-inorganic flame
retardants The PA6 samples were treated with different concentrations of equimolar mixtures of the flame
retardant and TEOS.
PA6 Combination of P- and Si-based additives improved the thermos-oxidative stability and ND [38]
combustion behavior by increasing the char residue and reducing the HRC and PHRR of
treated samples, respectively.
The cotton fabrics were treated by dipping/soaking in a solution of the polymeric flame
retardants.
Binders or crosslinkers were used when needed to bind the polymer permanently onto fabrics.
LOI values of the treated fabrics showed an increase with increasing the add-on.
Cotton Partially studied [42–49]
Polymeric flame The vertical burning test of the treated fabrics showed a reduction of the afterglow time and
retardant additives char length.
Cone calorimetry showed a decrease of HRR THR and CO2 /CO ratio with increasing
the add-on.
The nylon fabrics were dip-treated in a solution containing FR and crosslinker.
Nylon fabrics Yes [49]
MCC analyses showed a decrease of HRR, THR and HRC.
LOI values of the treated fabrics increased with increasing the phosphorus content.
The treated fabrics with add-on beyond 5 wt % were found self-extinction.
Phosphoramidate Cotton Partially studied [50–57]
The thermal stability and the flame retardancy performance of phosphoramidates are
derivatives
influenced by the nature of chemical substituents and type of cotton fabrics.
Nylon and polyester The vertical flame test showed better flame retardancy of treated nylon fibers. ND [56]
* Not determined.
Polymers 2016, 8, 319 9 of 36
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Polymers 2016, 8, x FOR PEER 9 of 36

4.1. DioxaphosphorinaneDerivatives
4.1 Dioxaphosphorinane
Dioxaphosphorinane Derivativesfor
forPET
PET Fibers
Fibers
4.1 Derivatives for PET Fibers
These newflame
These new
new flame retardants
retardants werewere designed
designed to exhibit
to exhibit
exhibit similar performances
similar performances
performances in their in their
their activity
activity to
These flame retardants
® , i.e., were designed to similar in to
activity
Antiblaze to Antiblaze
19®, i.e. a 19
trimethylolpropanea trimethylolpropane
methylphosphonate methylphosphonate
oligomer obtained oligomer
from the obtained
reaction of
Antiblaze 19®, i.e. a trimethylolpropane methylphosphonate oligomer obtained from the reaction of
from the reaction ofphosphite
trimethylolpropane trimethylolpropane
with phosphite
dimethyl with dimethyl methylphosphonate
methylphosphonate [54], employed [54],
for
trimethylolpropane phosphite with dimethyl methylphosphonate [54], employed for
employed for poly(ethyleneterephtalate)
poly(ethyleneterephtalate) (PET) fibers. In (PET)
fibers. In fibers.Negrell-Guirao
particular, In particular, andNegrell-Guirao
co-workers and [20]
poly(ethyleneterephtalate) (PET) particular, Negrell-Guirao and co-workers [20]
co-workers
synthesized [20] synthesized 2,5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane
2,5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (1), 2-butyl-
(1),
synthesized 2,5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (1),
5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane
2-butyl-5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (2) and 2-benzyl-5-ethyl-5(allyloxymethyl)-
(2) and
2-butyl-5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (2) and
2-oxo-1,3,2-dioxaphosphorinane (3) (Figure 3).
2-benzyl-5-ethyl-5(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (3) (Figure 3).
2-benzyl-5-ethyl-5(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (3) (Figure 3).

Figure 3.
Figure 3. Representative
Representative synthesis
synthesis of
of monomers
monomers (1),
(1), (2)
(2) and
and (3).
(3).

Due to
Due to the
the two
two pseudo-asymmetric
pseudo-asymmetric centers
centers for
for dioxaphosphorinane
dioxaphosphorinane monomers,
monomers, compounds
monomers, compounds
compounds (1), (1),
(1),
(2) and (3) exist
(3) exist
(2) and (3) as
exist as diasterioisomers.
as diasterioisomers. However, the
diasterioisomers. However, the radicalradical polymerization
radical polymerization
polymerization ofof dioxaphosphorinane
of dioxaphosphorinane
dioxaphosphorinane
monomers shows
monomers shows the
the influence
influence ofof the
the presence
presence of
of aa chain
chain transfer
transfer agent
agent (CTA)
(CTA) onon the
the efficiency
efficiency ofof
the radical
the radical polymerization
radical polymerization reaction.
polymerizationreaction. Moreover,
reaction.Moreover, dimethyl
Moreover,dimethyl
dimethyl phosphite
phosphite
phosphitecan play
cancan
play a role
a role
play by enhancing
by enhancing
a role by enhancing the
the
fire
the retardant
fire fire
retardant efficacy
efficacy
retardant of dioxaphosphorinane
of dioxaphosphorinane
efficacy of dioxaphosphorinane derivatives.
derivatives. As the
As the
derivatives. CTA
As CTA concentration
concentration
the CTA increases,
increases,
concentration the
the
increases,
monomer
monomer
the monomer conversion
conversion increases
increases
conversion as well
as well
increases and the
andand
as well degree
the the
degree of polymerization
of polymerization
degree decreases
decreases
of polymerization (Figure
(Figure
decreases 4).
4). 4).
(Figure

Figure 4.
Figure 4. Radical
Radical polymerization
polymerization of dioxaphosphorinane
dioxaphosphorinane monomers,
monomers, using
using dimethyl
dimethyl phosphite
phosphite as
as
Figure 4. Radical polymerization ofof
dioxaphosphorinane monomers, using dimethyl phosphite as CTA.
CTA.
CTA.
The products of the polymerization reaction were isolated as mono- and di-adduct, rather than
The products
The products of of the
the polymerization
polymerization reaction
reaction were
were isolated
isolated asas mono-
mono- and
and di-adduct,
di-adduct, rather
rather than
high
high M
M W polymers. Furthermore, the flame retardancy of these dioxaphosphorinane
W polymers. Furthermore, the flame retardancy of these dioxaphosphorinane derivatives was
derivativesthan
was
highassessed:
not MW polymers. Furthermore,
therefore, it was not the flameto
possible retardancy
make a of comparison
real these dioxaphosphorinane
with Antiblaze derivatives
19 ®. was
not assessed:
not assessed: therefore,
therefore, itit was
was not
not possible
possible toto make
make aa real
real comparison
comparison withwith Antiblaze
Antiblaze 19®.
19®.
4.2. UV-Curable Flame Retardants Coatings
4.2 UV-Curable
4.2 UV-Curable Flame
Flame Retardants
Retardants Coatings
Coatings
Xing and co-workers designed and applied UV-curable flame retardants coatings able to protect
Xing and
Xing and co-workers
co-workers designed
designed andand applied
applied UV-curable
UV-curable flameflame retardants
retardants coatings
coatings able
able to
to
cotton fabrics from heat penetration and flame spread [21]. In particular, as shown in Figure 5,
protect
protect cotton
cotton fabrics
fabrics from
from heat
heat penetration
penetration and
and flame
flame spread
spread [21].
[21]. In
In particular,
particular, as
as shown
shown in
in Figure
Figure
tri (acryloyloxyethyl) phosphate (4) and triglycidyl isocyanurate acrylate (5) were synthesized and
5, tri
5, tri (acryloyloxyethyl)
(acryloyloxyethyl) phosphate
phosphate (4) and and triglycidyl isocyanurate
isocyanurate acrylate (5) (5) were
were synthesized
synthesized andand
employed for impregnating cotton(4) fabrics,triglycidyl
using 1:1 weight ratio acrylate
of the two monomers in acetone
employed
employed for impregnating
for0.05
impregnating cotton fabrics, using 1:1 weight ratio of the two monomers in acetone
solution with g/mL, 0.10cotton
g/mL fabrics,
and 0.20using
g/mL1:1 weight ratio
of reactive of the two
compounds. Themonomers
monomersin acetone
were then
solution with
solution with 0.05
0.05 g/mL,
g/mL, 0.100.10 g/mL
g/mL and
and 0.20
0.20 g/mL
g/mL of
of reactive
reactive compounds.
compounds. The The monomers
monomers werewere then
then
cured using 4 wt % of photoinitiator under a UV-lamp.
cured using
cured using 44 wt
wt %% of
of photoinitiator
photoinitiator under
under aa UV-lamp.
UV-lamp.
Polymers 2016, 8, 319 10 of 36
Polymers 2016, 8, x FOR PEER 10 of 36

Polymers 2016, 8, x FOR PEER 10 of 36

Figure5.5.Schematic
Figure Schematicsynthesis
synthesis of
of UV-curable
UV-curable monomers
monomers(4)
(4)and
and(5).
(5).
Figure 5. Schematic synthesis of UV-curable monomers (4) and (5).
The formation of the UV-cured flame retardant coatings on the cotton surface was confirmed
The formation of the UV-cured flame retardant coatings on the cotton surface was confirmed using
usingThe Attenuated Total Reflectance (ATR) and Scanning Electron Microscopy (SEM)was analyses. The
Attenuatedformation of the
Total Reflectance UV-cured
(ATR) and flame retardant
Scanning coatings
Electron on the
Microscopy cotton surface
(SEM) analyses. confirmed
The flame
flame retardancy
using Attenuated of the treated
Total fabrics
Reflectancefabrics was also assessed: in particular, LOI values were found to
retardancy of the treated was (ATR) and Scanning
also assessed: ElectronLOI
in particular, Microscopy
values were(SEM) analyses.
found The
to increase
increase
flame with
retardancy increases
of flame in the
the treated flame retardants’
fabricscontent. content.
was alsoAassessed: A similar trend was also noticed from
with increases in the retardants’ similar in particular,
trend was also LOI valuesfrom
noticed wereMicro-scale
found to
Micro-scale
increase with Combustion
increases in Calorimetry measurements.
the flame retardants’ Furthermore,
content. A similar cotton
trend fabrics treated
waswith with
also flame
noticed flame
from
Combustion
retardant
Calorimetry
monomers (4)
measurements.
and (5) showed
Furthermore,
good
cotton
durability to
fabrics
laundry.
treated
The MCC results
retardant
after
Micro-scale
monomers Combustion
(4) showed
and (5) showed Calorimetry
good measurements.
durability toReleaseFurthermore,
laundry.Capacity
The MCC cotton
resultsfabrics
aftertreated with flame
launderingvalues,
showed
laundering a slight increase in Heat and
retardant monomers (4) and (5) showed good durability to laundry. The MCC results after Total Hydrocarbons
a slight
which,increase
however, in were
HeatstillRelease Capacity and Total Hydrocarbons values, thewhich, however, were
laundering showed a slightlower thanin
increase those
HeatofRelease
untreated cotton. and
Capacity In general, UV-curable
Total Hydrocarbons flame
values,
stillretardant
lower than thosebased
coating of untreated cotton. In(4)general,(5) the UV-curable flame retardant coating based
which, however, were stillon monomers
lower than those and
of untreatedshowed
cotton.condensed
In general,phase mode
the UV-curable action
flame as
on confirmed
monomersby(4) and (5)
the increased showed condensed phase mode action as confirmed by the increased char
retardant coating based onchar formation(4)
monomers of the
andtreated cotton. condensed phase mode action as
(5) showed
formation Very ofrecently,
the treated cotton.et al. [22] synthesized novel UV-curable flame retardants obtained from
Edwards
confirmed by the increased char formation of the treated cotton.
theVery recently,
reaction Edwards et al. [22] synthesized
of hexachlorotriphosphazene,
Very recently, Edwards et al. [22] synthesized in the novel UV-curable
presence
novel
flame retardants
of triethylamine,
UV-curable
obtained
with different
flame retardants obtainedmolar
from
from
thethe reaction
equivalents ofofhexachlorotriphosphazene, in the presence
1-(acry-loyloxy)-3-(methacryloyloxy)-2-propanol, of triethylamine,
affording
reaction of hexachlorotriphosphazene, in the presence of triethylamine, with different molar with
monomers different
(6), (7) molar
and
(8), (Figureof6).
equivalents
equivalents 1-(acry-loyloxy)-3-(methacryloyloxy)-2-propanol,
of 1-(acry-loyloxy)-3-(methacryloyloxy)-2-propanol, affording affording monomers
monomers (6), (6), (7)
(7)andand(8),
(Figure 6).
(8), (Figure 6).

Figure 6. Representative schematic synthesis of UV-curable monomers (6), (7) and (8).
Figure6.6.Representative
Figure Representativeschematic
schematic synthesis
synthesis of
of UV-curable
UV-curablemonomers
monomers(6),
(6),(7)(7)and
and(8).
(8).
Polymers
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2016, 8,
Polymers 2016, x
x FOR
FOR PEER
8, 319 PEER 11
11 of
11 of 36
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36

The
The fabric
fabric samples
samples were were impregnated
impregnated with with UV-curable
UV-curable monomers
monomers in in acetone
acetone solutions,
solutions,
The fabric
containing samplesconcentrations
were impregnated with UV-curable monomers in acetone solutions, containing
containing different concentrations of monomers and photoinitiator. All three synthesized
different of monomers and photoinitiator. All three synthesized
different
monomers concentrations of monomers and photoinitiator. All three synthesized monomers showed
monomers showed showed an an increase
increase in
in coating
coating yield
yield with
with increases
increases in
in the
the monomer
monomer concentration
concentration andand UVUV
an increase
exposure in coating yieldthe
with increases inconcentration
the monomer concentration and UV yield.
exposure time;
exposure time; conversely, the photoinitiator concentration did not affect the coating yield. As far
time; conversely, photoinitiator did not affect the coating As far as
as
conversely,
flammability the photoinitiator concentration did not affectsamples
the coating yield.enhanced
As far as flammability tests
flammability tests tests are
are considered,
considered, allall the
the treated
treated cotton
cotton samples showed
showed enhanced flameflame retardancy
retardancy
are
with considered, all the atreated cotton samples showed enhanced flame retardancy with the formation
with the
the formation
formation of of a coherent
coherent char.
char. In
In particular,
particular, the
the higher
higher phosphorus
phosphorus content
content inin monomers
monomers (6) (6)
of
anda coherent char. In particular, the higher phosphorus content in monomers (6) and (7) allowed
and (7)
(7) allowed
allowed achieving
achieving better
better fire
fire performances
performances as as compared
compared withwith monomer
monomer (8).(8).
achieving
Pursuingbetter fire research,
performances same as compared [23]with monomer (8).two new UV-curable monomers,
Pursuing this this research, the the same groupgroup [23] synthesized
synthesized two new UV-curable monomers,
namely Pursuing this research, the same group [23] synthesized two new UV-curable monomers, namely
namely di(allylamino)ethyl
di(allylamino)ethyl phosphate
phosphate (9) (9) and
and di(allylamino)dimethyl
di(allylamino)dimethyl phosphoramide
phosphoramide (10), (10), and
and
di(allylamino)ethyl
their phosphate (9) and di(allylamino)dimethyl phosphoramide (10), and their flame
their flame retardant efficacy was compared to that of hexa(allylamino)cyclotriphosphazene (11)
flame retardant efficacy was compared to that of hexa(allylamino)cyclotriphosphazene (11)
retardant
(Figure 7).efficacy was compared to that of hexa(allylamino)cyclotriphosphazene (11) (Figure 7).
(Figure 7).

Figure
Figure 7.
7. Representative
Representative schematic
Representative schematic synthesis
synthesis of
of UV-curable monomers (9),
UV-curable monomers (9), (10)
(10) and
and (11).
(11).
(11).

The obtained
The obtained monomers
monomers were dissolved in
were dissolved acetone together
in acetone together withwith different
different amounts
amounts of of
photoinitiators
photoinitiators and
photoinitiators and then
andthen applied
thenapplied onto
appliedonto cotton
ontocotton fabrics.
cottonfabrics. It
It It
fabrics. waswas found
found
was found that
that monomers
monomers
that monomers (9)
(9) (9) and
andand (10)
(10)(10)
werewere
not
were
not
not suitable
suitable for
for UV-curing
for UV-curing
suitable polymerization
polymerization
UV-curing reactions:reactions:
polymerization this finding
reactions: this
was
this finding was
wastoattributed
attributed
finding to
to the
the fast
the fast evaporation
attributed of
fast
evaporation
the monomers of the
once monomers
they were once
exposed they
to were
UV exposed
radiation. to
Thus,UV radiation.
cotton Thus,
fabrics were
evaporation of the monomers once they were exposed to UV radiation. Thus, cotton fabrics were cotton fabrics
impregnated were
these
impregnated
monomers
impregnated andthese
were monomers
these tested without
monomers and were
were tested
andundergoing without
without undergoing
the UV-curing
tested the
the UV-curing
process. Although
undergoing the treatedprocess.
UV-curing fabrics
process.
Although
did
Although the
not burn treated
thewhen
treated fabrics
subjected did not
to flame
fabrics did burn
spread
not burn when subjected
tests,
when to
hence revealing
subjected flame
to flamegood spread tests,
flame
spread hence
hence revealing
retardant
tests, features,
revealing
good
they flame
goodcould retardant
flamenot features,
be subjected
retardant they
to the
features, they could
could not
UV-curing be
be subjected
subjected to
notprocess. to the
the UV-curing
UV-curing process.
process.
In order to overcome
In order to overcome
overcome thisthis problem,
this problem, Mayer-Gall and co-workers
problem, Mayer-Gall and co-workers [24] [24] synthesized
synthesized allylallyl
functionalized polyphosphazenes
functionalized polyphosphazenes (12) (12) starting
starting from
from hexachlorotriphosphazene
from hexachlorotriphosphazene
hexachlorotriphosphazene (Figure (Figure 8).
(Figure 8).
8).

Figure
Figure 8.
8. Synthesis
Synthesis of allyl-functionalized polyphosphazene (12).
Figure 8. Synthesis of
of allyl-functionalized polyphosphazene (12).
allyl-functionalized polyphosphazene (12).

The obtained
The obtained product
obtained product was
product was then
was then used
then used for
used for cotton
for cotton and
cotton and different
and different cotton/polyester
cotton/polyester blended
different cotton/polyester blended fabrics,
The blended fabrics,
fabrics,
using
using an
an impregnation
impregnation method
method (1
(1 mL/g
mL/g of
of 25
25 wt
wt %
% of
of a
a solution
solution of
of monomer
monomer (12)
(12) in
in acetylacetone)
acetylacetone)
using an impregnation method (1 mL/g of 25 wt % of a solution of monomer (12) in acetylacetone)
followed
followed byby UV-grafting
by UV-grafting
UV-grafting inin inert
in inert atmosphere
inert atmosphere (argon).
(argon). The
atmosphere (argon). The treated fabrics exhibited good flame
followed The treated
treated fabrics exhibited good
fabrics exhibited good flame
flame
retardancy with
retardancy with char
withchar formation,
charformation,
formation, hence,
hence, confirming
confirming a condensed
a condensed phase mode of action of
of the
retardancy hence, confirming a condensed phase phase
mode of mode
actionofofaction the
the designed
designed
designed flame
flame retardant
retardant system.
system. The
The UV-cured
UV-cured FR
FR coatings
coatings showed
showed also
also a
a good
good washing
washing fastness.
fastness.
flame retardant system. The UV-cured FR coatings showed also a good washing fastness.
Polymers 2016, 8,
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36
Polymers 2016, 8, x FOR PEER 12 of 36
Very recently, Yildiz et al. synthesized a UV-curable epoxy based oligomer adhesive
Very
Very recently, Yildiz et al.etsynthesized
recently, a UV-curable epoxy based oligomer
basedadhesive formulation
formulation (13), by Yildiz al. synthesized
reacting acrylic acid with abisphenol-A-diglycidylether
UV-curable epoxy oligomer
(DGEBA) adhesive
[25]. The
(13), by reacting
formulation acrylic
(13), by acid with
reacting bisphenol-A-diglycidylether
acrylic acid with (DGEBA) [25]. The
bisphenol-A-diglycidylether reaction
(DGEBA) is shown
[25]. in
The
reaction is shown in Figure 9.
Figure
reaction9.is shown in Figure 9.
OH
O O
O O OH O O O
O O
O O O nO O
OH
n
OH

PPh3
100
PPh3°C-120 °C
100 °C-120 °C

OH OH OH
O OH O O OH O O OH O
O O O O nO O
O O
n
O O

13
13
Figure 9. Schematic synthesis of oligomer (13).
Figure 9.
Figure 9. Schematic
Schematic synthesis
synthesis of
of oligomer
oligomer (13).
(13).
The system was employed to adhere cord fabrics (i.e. a polyester/polyamide blend) onto the
rubberThesurfaces.
The system was
system was employed
employed
Vinyl to adhere
to
phosphonic adhere cord
acid cord fabrics
wasfabrics (i.e. aa polyester/polyamide
(i.e.,
then incorporated polyester/polyamide blend)
blend) onto
into the epoxyacrylate-based onto the
the
rubber
rubber
adhesive surfaces.
surfaces. Vinyl
Vinylweight
at different phosphonic
phosphonic
ratiosacid acid was
was then
to enhance the then incorporated
incorporated
flame retardancy into the into the epoxyacrylate-based
ofepoxyacrylate-based
the treated fabrics; 3adhesive
wt % of
adhesive
at at
photoinitiator different
different weight
in methylweight
ratios to ratios
enhance
ethyl ketoneto enhance
thewas
flame the flame
retardancy
also added. The retardancy
of the treated
fabrics of the
fabrics;
were treated fabrics;
3 wt % and
dip-coated 3 wt % of
of photoinitiator
the solution
photoinitiator
in
wasmethyl
then ethyl in methyl ethyl
ketone wasspread
homogeneously ketone
also added. was
using Thealso added. The
fabrics were
a squeezing fabrics
roller. were
dip-coated dip-coated
The coatingand layer and
the solution the
was then solution
wascured
then
was then
homogeneouslyhomogeneously
exposing both sides spreadofusing spread using
a squeezing
the treated fabrics a squeezing
roller.
to aThe UVcoating roller. The coating layer
layer was then cured(TG)
lamp. Thermogravimetric was
exposing then cured
both sides
measurements
exposing
of
showed both
the treated
that sides of
fabrics
thermal to the
a UV
stabilitytreated
lamp.
and fabrics
char to a UV
Thermogravimetric
formation lamp.
of the Thermogravimetric
(TG)
treated measurements
fabrics increases (TG)
withmeasurements
showed that thermal
increasing the
showed
stability that char
and
concentration thermal stability
of formation
vinyl ofand char
the treated
phosphonic formation
acid. fabrics of the treated
increases
Furthermore, with
LOI fabrics increases
increasing
values with increasing
increasing
the concentration
improved with the
of vinyl
the
concentration
phosphonic
concentrationacid.of vinyl
of vinyl phosphonic
Furthermore,
phosphonic LOI acid.
acid valuesFurthermore,
in the improved LOI values
with
adhesive formulation. improved
increasing with increasing
the concentration the
of vinyl
concentration of vinyl phosphonic acid
phosphonic acid in the adhesive formulation. in the adhesive formulation.
4.3 Triazine-Based Flame Retardants
4.3 Triazine-Based
4.3. Triazine-Based Flame
Flame Retardants
Retardants
Cyanuric chloride is the main starting material for obtaining triazine-based flame retardants:
Cyanuric
indeed, chloride isshows
this product the main starting
a high materialreactivity
chemical for obtaining andtriazine-based
is suitable for flamesynthesizing
retardants:
indeed, this productflame
phosphorus-nitrogen shows a high with
retardants chemical
differentreactivity
phosphorus and is suitable for
to suitable
nitrogen for synthesizing
ratios,synthesizing
either via
phosphorus-nitrogen flame retardants with
nucleophilic substitution or Michaelis-Arbuzov reaction. different phosphorus to nitrogen ratios, either via
nucleophilic
Chang and substitution
co-workersor Michaelis-Arbuzov
or Michaelis-Arbuzov
synthesized diethyl reaction.
reaction.
4,6-dichloro-1,3,5-triazin-2-ylphosphonate (14),
Chang and co-workers
co-workers synthesized
synthesized
tetraethyl 6-chloro-1,3,5-triazin-2,4-diyldiphosphonatediethyl
diethyl 4,6-dichloro-1,3,5-triazin-2-ylphosphonate
(15) via Michaelis-Arbuzov reaction(14),
4,6-dichloro-1,3,5-triazin-2-ylphosphonate (as
tetraethyl
tetraethyl 6-chloro-1,3,5-triazin-2,4-diyldiphosphonate
shown in 6-chloro-1,3,5-triazin-2,4-diyldiphosphonate
Figure 10), and used these monomers for conferring (15)(15) via Michaelis-Arbuzov
via Michaelis-Arbuzov
flame reaction
retardant properties reaction
(as (as
to shown
cotton
shown
in Figure
fabrics in10),
Figure
[26]. and 10),
usedand used
these these monomers
monomers for conferringfor conferring
flame retardantflameproperties
retardant to properties to cotton
cotton fabrics [26].
fabrics [26].

Figure 10. Representative synthesis of monomers (14) and (15) via Michaelis-Arbuzov reaction.
Figure 10.
Figure Representative synthesis
10. Representative synthesis of
of monomers
monomers (14)
(14) and
and (15)
(15) via
via Michaelis-Arbuzov
Michaelis-Arbuzov reaction.
reaction.
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36

The chlorine atoms of the two synthesized oligomers were exploited to react with hydroxyl
The chlorine atoms of the two synthesized oligomers were exploited to react with hydroxyl
group of the cellulose, through the formation of ether bonds, hence permanently linking the FR
group Theofchlorine atoms of
the cellulose, the twothe
through synthesized
formationoligomers
of ether were
bonds, exploited to react with hydroxyl
hence permanently linking thegroup
FR
additives to the cellulosic substrate [27]. Thermogravimetric analyses showed the formation of a
of the cellulose,
additives through the formation of ether bonds, hence permanently linking the FR additivesoftoa
char at 600to
°C,the cellulosic
which proved substrate [27]. Thermogravimetric
the condensed phase mode of action analyses showed
of the synthesized formation
FRs. LOI values
◦ C,
the
charcellulosic
at 600 °C,substrate [27]. Thermogravimetric
which proved the condensed phaseanalysesmode ofshowed
action ofthe
theformation
synthesized of aFRs.
charLOI
at 600
values
were found to increase up to 48% (for treated fabrics) with increases in the flame retardant
which provedtotheincrease
were found condensedup phase
to 48% mode(foroftreated
action of the synthesized
fabrics) FRs. LOI
with increases in values wereretardant
the flame found to
concentration. From an overall point of view, the synthesized oligomers acted as good flame
increase up to 48% (for treated fabrics) with increases in the flame retardant
concentration. From an overall point of view, the synthesized oligomers acted as good concentration. From an
flame
retardants for cotton fabrics when at least 10 wt % add-on was achieved. As triazine-based flame
overall
retardantspoint
forofcotton
view, the synthesized
fabrics when atoligomers
least 10 wtacted as good was
% add-on flameachieved.
retardantsAs fortriazine-based
cotton fabrics flame
when
retardants are believed to be of interest for textile industries, the durability of the flame retarded
at least 10 wt
retardants are%believed
add-on wasto beachieved. As triazine-based
of interest flame retardants
for textile industries, are believed
the durability of the to be ofretarded
flame interest
cotton fabrics has not been reported yet.
for textile
cotton industries,
fabrics has notthe
beendurability
reportedofyet.
the flame retarded cotton fabrics has not been reported yet.
Slopek and co-workers exploited a nucleophilic reaction for synthesizing dimethyl
Slopek and co-workers exploited a nucleophilic reaction for synthesizing dimethyl
(4,6-dichloro-1,3,5-triazin-2-yloxy)methyl phosphonate (16), (6-chloro-1,3,5-triazine-2,4-diyl)bis
(4,6-dichloro-1,3,5-triazin-2-yloxy)methyl
(4,6-dichloro-1,3,5-triazin-2-yloxy)methylphosphonate phosphonate (16), (6-chloro-1,3,5-triazine-2,4-diyl)bis(oxy)bis
(16), (6-chloro-1,3,5-triazine-2,4-diyl)bis
(oxy)bis(methylene) diphosphonate (17), diethyl 2-(4,6-dichloro-1,3,5-triazin-2-ylamino)
(methylene) diphosphonate
(oxy)bis(methylene) (17), diethyl 2-(4,6-dichloro-1,3,5-triazin-2-ylamino)
diphosphonate (17), diethyl ethylphosphonate (18)
2-(4,6-dichloro-1,3,5-triazin-2-ylamino)
ethylphosphonate (18) and tetraethyl 2,2’-(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)bis(ethane-
and tetraethyl 2,2’-(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)bis(ethane-
ethylphosphonate 2,1-diyl) diphosphonate
(18) and tetraethyl 2,2’-(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)bis(ethane-
2,1-diyl) diphosphonate (19). The reactions are shown in Figure 11.
(19). The diphosphonate
2,1-diyl) reactions are shown in Figure
(19). The 11. are shown in Figure 11.
reactions
O O
Cl O Cl
Cl P O Cl O
P O Cl
N N HO O P O Cl 2 HO P O N N
O O
N N HO O N N 2 HO O N N O
OO O
Cl N O P 0 °C N N 0 °C-RT OP O N O PO
O O P
Cl N O P
O 0 °C
pH =6
Cl N Cl 0 °C-RT
pH = 7-8 O O N O OP O
Cl N Cl O O
16 O pH = 6 pH = 7-8 O 17 O
16 17

Cl H3N O Cl H3N O
Cl H3N O O
P Cl H3N O O O O
P
Cl
P O Cl P O O P O
O
Cl O O P
O Cl O
O N N N N 2 O H
OO
P N N N N 2 HN N N
H O
O P O N N Cl HN N N P
H 0 °C-RT Cl N Cl 0 °C-RT O P O
O N N Cl N N
H 0pH
°C-RT
=6 Cl N Cl 0 °C-RT
pH = 9-10 OO
pH = 6 pH = 9-10 N N O
Cl
18 Cl19
18 19
Figure 11. Synthesis of flame retardants (16)–(19) via nucleophilic reaction.
Figure
Figure 11.
11. Synthesis
Synthesis of
of flame
flame retardants (16)–(19) via
retardants (16)–(19) via nucleophilic
nucleophilic reaction.
reaction.
The obtained FR products were applied onto cotton fabrics [28,29]. From an overall point of
The
view,The obtained
theobtained FRproducts
FR
treated cottonproducts were
fabricswere applied
applied
showed onto
onto
a fire cotton
cotton
behavior fabrics
fabrics
similar to [28,29].
[28,29].
thatFrom From an
by overall
an overall
provided pointpoint
monomers of
of view,
(14)
view, the
the treated treated cotton fabrics showed a fire behavior similar to that provided by monomers (14)
and (15). cotton fabrics showed a fire behavior similar to that provided by monomers (14) and (15).
and (15).
Recently, dioxo(3-triethylphosphite-5-chlorin-triazine) neopentyl glycol (20)(20)
was was
synthesized from
Recently, dioxo(3-triethylphosphite-5-chlorin-triazine) neopentyl glycol synthesized
from Recently,
reaction
reaction dioxo(3-triethylphosphite-5-chlorin-triazine)
of monomer
of (14) with
monomer (14)almost half equivalent
with almost half equivalentneopentyl
of neopentyl glycol
glycol
of neopentyl (20) 12);
(Figure
glycol was synthesized
the
(Figure obtained
12); the
from reaction
product was of monomer
applied (14) fabrics
with almost half equivalent of neopentyl glycol (Figure 12); the
obtained product wasonto cotton
applied [30].
onto cotton fabrics [30].
obtained product was applied onto cotton fabrics [30].

Figure
Figure 12.
12. Schematic
Schematic synthesis
synthesis of
of oligomer
oligomer (20).
(20).
Figure 12. Schematic synthesis of oligomer (20).
Cotton fabrics
fabrics were
were impregnated
impregnated in inaaasolution
solutioncontaining
containing(20)(20)and
andNa 2PO4·H2O as a catalyst at
Cotton
Cotton fabrics were impregnated in solution containing (20) and Na
Na 2 PO4 ·H2 O as a catalyst
2PO4·H2O as a catalyst at
40
at °C.◦ After drying, the samples were then cured at 160 °C.◦ LOI values increased with increases in
40 40
°C. C. After
After drying,
drying, thethe samples
samples werewerethenthen cured
cured at at
160160
°C. C.
LOILOI values
values increased
increased withwith increases
increases in
the
in concentration of the oligomer in the treated cotton fabrics. Furthermore, the effect of the catalyst
thethe concentration
concentration of oligomer
of the the oligomerin theintreated
the treated
cottoncotton fabrics.
fabrics. Furthermore,
Furthermore, theofeffect
the effect of the
the catalyst
concentration
catalyst on the treated
concentration on thefabrics
treatedwas investigated:
fabrics it was found
was investigated: it wasthat withthat
found increases in the catalyst
with increases in the
concentration on the treated fabrics was investigated: it was found that with increases in the catalyst
concentration,
catalyst the LOI
concentration, values of the treated fabrics increased. This finding was ascribed to the
concentration, the LOIthe LOI values
values of the of the treated
treated fabricsfabrics increased.
increased. This finding
This finding was was ascribed
ascribed to
to the
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presence of the catalyst that promoted the grafting reaction between the oligomer and the fabric
presence of the catalyst that promoted the grafting reaction between the oligomer and the fabric
the presence
substrate. of the flammability
Vertical catalyst that promoted
tests showedthe agrafting
gradualreaction
decreasebetween
of charthe oligomer
length and the of
and increase fabric
the
substrate. Vertical flammability tests showed a gradual decrease of char length and increase of the
substrate.
char residue Vertical
with flammability
increases in tests
the FRshowed a gradual Furthermore,
concentration. decrease of char length
with and increase
increases in the of the
flame
char residue with increases in the FR concentration. Furthermore, with increases in the flame
char residue
retardant with increasestoinattheleast
concentration FR concentration.
20 wt %, theFurthermore,
treated sampleswith increases
did not in the flame
show retardant
any afterglow
retardant concentration to at least 20 wt %, the treated samples did not show any afterglow
concentration to at least
phenomena. Finally, the20 wt %,
flame the treated
retarded samples
fabrics didanot
showed show any
significant afterglow
washing phenomena.
fastness Finally,
that makes the
phenomena. Finally, the flame retarded fabrics showed a significant washing fastness that makes the
the flame retarded fabrics showed a significant washing
synthesized oligomer a durable flame retardant for cotton fabrics. fastness that makes the synthesized oligomer
synthesized oligomer a durable flame retardant for cotton fabrics.
a durable
Zhang flame
et al.retardant
preparedfor cotton fabrics. flame retardant containing triazine ((21), Figure 13) by
a sulfur-Nitrogen
Zhang et al. prepared a sulfur-Nitrogen flame retardant containing triazine ((21), Figure 13) by
Zhang
reacting et al. prepared
cyanuric chloride awith
sulfur-Nitrogen flame retardant containing
sodium 2-aminoethane-sulfanilate, and triazine
then with((21), Figure 13) by
diethanolamine
reacting cyanuric chloride with sodium 2-aminoethane-sulfanilate, and then with diethanolamine
reacting
[31]. cyanuric chloride with sodium 2-aminoethane-sulfanilate, and then with diethanolamine [31].
[31].

Figure 13. Synthesis of S-N flame retardant containing triazine (21).

Figure 13.
Figure Synthesis of
13. Synthesis of S-N
S-N flame
flame retardant
retardant containing
containing triazine
triazine (21).
(21).
The obtained flame retardant was dissolved in water at different concentrations and applied
The obtained
obtainedflame
flameretardant
retardantwas was dissolved
dissolved in in
water at different
water concentrations
at different and applied
concentrations onto
and applied
onto cotton fabrics. The thermal stability oftreated
the treated fabrics was investigated using TG analyses in
onto cotton fabrics. The thermal stability of the treated fabrics was investigated using TG analysesair
cotton fabrics. The thermal stability of the fabrics was investigated using TG analyses in in
air atmosphere. The treated cotton fabrics showed an increase of the char residue◦at 600 °C, which
atmosphere.
air TheThe
atmosphere. treated cotton
treated fabrics
cotton showed
fabrics an increase
showed of the of
an increase chartheresidue at 600 at
char residue C, 600
which
°C,proved
which
proved
the the condensed
condensed phase phaseaction
mode modeofaction
the of the obtained
obtained flame flame retardant.
retardant. However, However,
no no standard
standard burning
proved the condensed phase mode action of the obtained flame retardant. However, no standard
burning
tests tests
weretests were reported
reported and therefore it was not possible to assess the flame retardant
burning wereand therefore
reported andit was not possible
therefore it wasto notassess the flame
possible to retardant
assess theperformance of the
flame retardant
performance of the treated cotton fabrics.
treated cottonoffabrics.
performance the treated cotton fabrics.
A similar
A similar approach was adopted
approach was adopted by by Zhao
Zhao and
and co-workers,
co-workers, whowho synthesized
synthesized the
the flame
flame retardant
retardant
22 (shown inin Figure
Figure 14),
14), suitable
suitable for
for cotton
cotton fabrics
fabrics [32].
[32].
22 (shown

Figure 14. Synthesis of S-N flame retardant containing triazine (22).

Figure
Figure 14.
14. Synthesis
Synthesis of
of S-N
S-N flame
flame retardant
retardant containing triazine (22).
containing triazine (22).

The flame retardant performances of the treated fabrics were evaluated using LOI and vertical
The
The flame
flame retardant performances
retardant performances of the treated fabrics
fabrics were evaluated
evaluated using
using LOI
LOI and
and vertical
vertical
flammability tests. Cotton fabrics couldofreach
the treated
self-extinction were
when treated with 10 wt % add-on of
flammability
flammability tests. Cotton fabrics could reach self-extinction when treated with 10 wt
tests. Cotton fabrics could reach self-extinction when treated with 10 wt % add-on of% add-on of
the FR.
the
the FR.
FR.
Pursuing this research, (22) was reacted with POCl33, affording 6-chloro-4-(diethylamino
Pursuing thisresearch,
Pursuing phosphoryl
this research,
(22) (22) was reacted
was reacted with POClwith, affording
POCl3, 6-chloro-4-(diethylamino
affording 6-chloro-4-(diethylamino
phosphorate
phosphorate chloride)-2-(sodium 4-aminobenzensulfonate)-1,3,5-triazine
3 (23) (Figure
phosphorate
phosphoryl phosphoryl
chloride)-2-(sodiumchloride)-2-(sodium 4-aminobenzensulfonate)-1,3,5-triazine
4-aminobenzensulfonate)-1,3,5-triazine (23) (Figure 15) (23) (Figure
[33].
15) [33].
15) [33].

Figure 15.
Figure 15. Representative synthesis of
Representative synthesis of monomer
monomer (23).
(23).
Figure 15. Representative synthesis of monomer (23).
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4.4. HybridOrganic-Inorganic
4.4 Hybrid Organic-Inorganic Flame
Flame Retardants
Retardants
4.4 Hybrid Organic-Inorganic Flame Retardants
Hybrid
Hybrid organic-inorganic flame retardants
organic-inorganic flame retardants are
are materials that usually
materials that favor the
usually favor the formation
formation ofof a
a
Hybrid organic-inorganic flame retardants are materials that usually favor the formation of a
carbonaceous layer upon exposure to a heat source [34]. Among the different strategies
carbonaceous layer upon exposure to a heat source [34]. Among the different strategies that can be that can be
carbonaceous layer upon exposure to a heat source [34]. Among the different strategies that can be
successfully
successfully exploited,
exploited, the
thesol-gel
sol-geltechnique
techniqueisisoneoneofofmany
manytechniques
techniques developed
developed forfor
incorporation
incorporationof
successfully exploited, the sol-gel technique is one of many techniques developed for incorporation
these hybrid organic-inorganic flame retardants onto textiles
of these hybrid organic-inorganic flame retardants onto textiles [35]. [35].
of these hybrid organic-inorganic flame retardants onto textiles [35].
In
In this
this context,
context, several
several phosphorus-based
phosphorus-based siliconsilicon containing
containing flame
flame retardants
retardants have
have been
been
In this context, several phosphorus-based silicon containing flame retardants have been
developed.
developed. Hu Huand
and co-workers
co-workers [36][36] exploited
exploited the
the reaction
reaction of of isophorone
isophorone diisocyanate
diisocyanate with
with
developed. Hu and co-workers [36] exploited the reaction of isophorone diisocyanate with
(3-aminopropyl)triethoxysilane
(3-aminopropyl)triethoxysilane and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO),
(3-aminopropyl)triethoxysilane and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
obtaining oligomer oligomer
(DOPO), obtaining 24 of Figure 16.Figure 16.
24 of
(DOPO), obtaining oligomer 24 of Figure 16.

Figure 16.
16. Representative synthesis of hybrid organic-inorganic flame retardant precursor (24) and
and
Figure 16. Representative
Figure Representative synthesis
synthesis of
of hybrid
hybrid organic-inorganic
organic-inorganic flame
flame retardant
retardant precursor
precursor (24)
(24) and
its
its hydrolysis.
its hydrolysis.
hydrolysis.

After the
After the hydrolysis
hydrolysis of of the
the product
product in in acidic
acidic media,
media, aa sol-gel
sol-gel solution
solution waswas obtained
obtained and and used
used for
for
treating
treating cotton fabrics by dipping. The treated samples were then dried in the oven at 80 °C
◦ and then
treating cotton
cotton fabrics
fabrics byby dipping.
dipping. The treated
treated samples
samples werewere then
then dried
dried inin the
the oven
oven at at 80
80 °CC and then
130 ◦°C.
130 TG analyses
C. TG analyses showed
showed aa decreased
decreased onsetonset temperature
temperature and and an
an increased
increased char
char with
with increases
increases in in
130 °C.
the concentration of the sol-gel precursor on cotton fabrics: these findings were
the concentration of the sol-gel precursor on cotton fabrics: these findings were attributed to the acid attributed to the acid
environment promoted
environment promoted bythethe degradation of organophosphorus
the organophosphorus partto and to the stability
thermal
environment promotedbyby degradation
the degradation of theof the organophosphorus part and
part andthe thermal
to the thermal
stability
of of
Si–O bondsSi–O bonds
that that
exerted exerted a protection on the underlying fabric. A similar trend wasinfound
stability of Si–O bonds thataexerted
protection on the underlying
a protection fabric. Afabric.
on the underlying similarAtrend
similarwas found
trend was MCC
found
in MCC
tests: tests:
PHRR PHRR
and HRCandand HRC
values values
showed showed a decrease with increases in the concentration of the
in MCC tests: PHRR HRC valuesashowed
decreasea with increases
decrease with in the concentration
increases of the precursor.
in the concentration of the
precursor.
All All these
these results proved results proved
that the sol-gelthat the sol-gel
precursor acts inprecursor acts in
the condensed the by
phase condensed
increasingphasethe charby
precursor. All these results proved that the sol-gel precursor acts in the condensed phase by
increasing
formation the
of char
the formation
treated cotton of the treated
samples, whichcotton samples,
reduces the which
heat reduces
release. the heat release.
increasing the char formation of the treated cotton samples, which reduces the heat release.
Quite recently,
Quite recently, Vasiljević
Vasiljević and co-workers
co-workers [37] exploited an an addition
addition reaction
reaction of of DOPO
DOPO to to
recently, Vasiljević and and co-workers [37] exploited exploited
vinyltrimethoxysilane in
vinyltrimethoxysilane inthe
thepresence
presenceof Azobisisobutyronitrile (AIBN) as as
initiator, giving riserise
to the
in the presence ofofAzobisisobutyronitrile
Azobisisobutyronitrile (AIBN)
(AIBN) initiator,
as initiator, giving
giving to
rise to the
formation
the of
formation the
of flame
the retardant
flame (25)
retardant shown
(25) shownin Figure
in 17.
Figure 17.
formation of the flame retardant (25) shown in Figure 17.

Figure 17. Synthesis of hybrid organic-inorganic flame retardant (25).

Figure
Figure 17.
17. Synthesis
Synthesis of
of hybrid
hybrid organic-inorganic flame retardant
organic-inorganic flame retardant (25).
(25).

Different concentrations of the obtained flame retardant were prepared in ethanol and were
Different concentrations
Different concentrations of the obtained
of the obtained flame
flame retardant
retardant were
were prepared
prepared in
in ethanol
ethanol and
and were
were
hydrolyzed using HCl. The cotton fabrics were then treated by the pad-dry-cure method at 20 °C,
hydrolyzed using HCl. The cotton fabrics were then treated by the pad-dry-cure method at 20 °C,
hydrolyzed using HCl. The cotton fabrics were then treated by the pad-dry-cure method at 20 ◦ C,
subsequently dried at 120 °C and then cured at 150 °C. TG analyses showed a decrease of the
subsequently dried at 120 °C and then cured at 150 °C. TG analyses showed a decrease of the
thermal stability and an increase of the char formation with increases in the amount of dry solid on
thermal stability and an increase of the char formation with increases in the amount of dry solid on
Polymers 2016, 8, 319 16 of 36

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subsequently dried at 120 ◦ C and then cured at 150 ◦ C. TG analyses showed a decrease of the thermal
stability
the andcotton
treated an increase
fabrics.ofIn
the char formation
addition, the flame with increases
retardant in the amount
performance of dry solid
of treated onfabrics
cotton the treated
was
cotton fabrics.using
investigated In addition,
verticalthe flamespread
flame retardant performance
tests: by increasingof treated cotton
the solid dryfabrics
add-on,wasan
investigated
increased
using vertical
flaming flame spread
combustion after tests: by increasing
the removal of thetheflame
solid dry
wasadd-on,
found;anconversely,
increased flaming combustion
LOI values were
after the
improved. removal of the flame was found; conversely, LOI values were improved.
Pursuing this
this research,
research,thethesame
samegroup
group exploited
exploited thethe
combination
combination of the sol-gel
of the precursor
sol-gel (25) (25)
precursor and
tetraethoxysilane (TEOS), which was utilized as a sol-gel finishing for polyamide
and tetraethoxysilane (TEOS), which was utilized as a sol-gel finishing for polyamide 6 (PA6) fabrics 6 (PA6) fabrics [38].
The obtained
[38]. hybridhybrid
The obtained systemsystem
decreased the Total
decreased theHeat
TotalRelease
Heat values of values
Release the treated fabrics,
of the increasing,
treated fabrics,
at the sameattime,
increasing, the char
the same yield
time, thewith
charrespect to the
yield with use oftoprecursor
respect the use of (25) alone, hence
precursor proving
(25) alone, the
hence
synergistic behavior of the combined hybrid system.
proving the synergistic behavior of the combined hybrid system.
Yang etetal.al.[39] reacted
[39] reacted(3-aminopropyl)trimethoxysilane
(3-aminopropyl)trimethoxysilane withwith
diphenylphosphinic
diphenylphosphinic acid in order
acid in
to prepare the flame retardant precursor (26) shown in Figure
order to prepare the flame retardant precursor (26) shown in Figure 18. 18.

Figure
Figure 18.
18. Synthesis
Synthesis of
of hybrid
hybrid organic-inorganic
organic-inorganic flame
flame retardant (26).
retardant (26).

The
The obtained precursor was
obtained precursor was dissolved
dissolved in in aqueous/ethanol
aqueous/ethanol solutionssolutions at at different
different concentrations
concentrations
and applied as a hybrid organic-inorganic flame retardant for cotton
and applied as a hybrid organic-inorganic flame retardant for cotton fabrics. After treatment, fabrics. After treatment, the
the fabrics
fabrics were dried ◦ at 140 °C. The thermal stability and the flammability
were dried at 140 C. The thermal stability and the flammability behavior of the treated fabrics were behavior of the treated
fabrics
assessed;were assessed; furthermore,
furthermore, the washingthe washing
fastness wasfastness
evaluated. wasTG evaluated. TG measurements
measurements showed
showed an increase
an
of char formation of the treated cotton fabrics at 500 C. Vertical flame spread tests revealed tests
increase of char formation of the treated cotton fabrics
◦ at 500 °C. Vertical flame spread char
revealed
formationchar formation
quickly quicklyand
after ignition afterthe
ignition
specimensand the specimens
achieved achieved after
self-extinction self-extinction
the removal after
of the
the
removal of the flame. In addition, the treated fabrics did not lose their flame
flame. In addition, the treated fabrics did not lose their flame retardancy after several laundry cycles, retardancy after several
laundry cycles,
thus proving thethus provingofthe
durability thedurability
proposedof the proposed
flame retardant flame retardant treatment.
treatment.
Very recently, Liu
Very recently, Liu et et al.
al. exploited
exploited aa similar
similar synthetic
synthetic approach
approach for for obtaining
obtaining hybridhybrid
organic-inorganic 3-aminopropyl triethoxysilane derivatives on
organic-inorganic 3-aminopropyl triethoxysilane derivatives on cotton fabrics [40]. To this cotton fabrics [40]. To this aim,
aim,a
nucleophilic substitution was carried out (Figure 19). A 10 wt % solution of
a nucleophilic substitution was carried out (Figure 19). A 10 wt % solution of the hybrid precursor (27) the hybrid precursor (27)
was
was prepared
prepared and and thenthen the
the cotton
cotton fabrics
fabrics were
were immersed
immersed for for different times before
different times before aa subsequent
subsequent
thermal treatment.
thermal treatment.
In
In aa similar
similar way,
way, WangWang and and co-workers
co-workers synthesized
synthesized the the precursor
precursor (27) (27) shown
shown in in Figure
Figure 19, 19,
which was applied onto cotton fabrics at different concentrations [41]. TG
which was applied onto cotton fabrics at different concentrations [41]. TG data of the fabrics treated data of the fabrics treated
with
with precursor
precursor (27)(27) showed
showed an an increase
increase of of the
the thermal
thermal stability
stability with
with increases
increases of of final
final dry
dry add-on.
add-on.
Conversely,
Conversely, the the cotton
cotton fabrics
fabrics treated
treated with
with precursor
precursor (28) exhibited aa lower
(28) exhibited lower thermal
thermal stability
stability as as
compared to the other hybrid system. However, both flame retardants
compared to the other hybrid system. However, both flame retardants showed an increase of the showed an increase of the
char
char residue
residue with
withincreases
increasesininthe theadd-on
add-onononthe thetreated
treated fabrics.
fabrics.A similar
A similartrend waswas
trend foundfoundwhen whenthe
treated fabrics
the treated werewere
fabrics subjected to vertical
subjected flammability
to vertical flammabilitytests.tests.
Therefore, from an
Therefore, fromoverall point of
an overall view,
point of
the designed hybrid coating systems were able to provide improved
view, the designed hybrid coating systems were able to provide improved fire retardancy to cotton, fire retardancy to cotton,
exploiting
exploiting thetheformation
formationofof a thermally
a thermally stable
stable charchar that prevents
that prevents the underlying
the underlying substratesubstrate from
from ignition
ignition and limits the release of flammable gases during the thermal degradation
and limits the release of flammable gases during the thermal degradation process. Finally, the washing process. Finally,
the washing
fastness of thefastness
flame of the flame
retardant was retardant
assessed: was inassessed:
particular, in the
particular,
specimens the treated
specimens withtreated with
the sol-gel
the sol-gel(28)
precursor precursor (28) did
did not exhibit any not exhibit
change anyphosphorus
of the change of the phosphorus
content content
after the first aftercycle.
washing the first
washing cycle.
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Figure 19. Representative schematic synthesis of precursors (27) and (28).

Figure
Figure 19.
19. Representative
Representative schematic synthesis of
schematic synthesis of precursors
precursors (27)
(27) and
and (28).
(28).
4.5 Flame Retardants as Polymer-Additives
4.5 Flame
4.5. FlameRetardants
RetardantsasasPolymer-Additives
Polymer-Additives
Another possible strategy, differing from those described in the previous paragraphs, exploits
Anotherofpossible
the design
Another possible strategy,differing
phosphorus-based
strategy, differing
polymeric from
from those
flame
those described
retardants,
described in in the
rather
the previous paragraphs,
thanparagraphs,
previous low molecular exploits
weight
exploits the
the design
counterparts.
design of phosphorus-based
Indeed, the former
of phosphorus-based polymeric
are being
polymeric flame
widely
flame retardants,
investigated
retardants, rather
rather than
because
than low low molecular
of their weight
durability and
molecular
counterparts. Indeed,
ecofriendly character: the
Indeed,this former
thehas pushed
former are
arethebeing widely
scientific
being widely investigated
community
investigated because
to employ of theirpolymeric
becausedifferent durabilityflame
and
retardants as
ecofriendly thisfor
additives
character: haseither
pushed the scientific
textiles community
or engineering to employ
plastics. different polymeric
In addition, flame
polymeric flame
retardantsasas
retardants additives
bearing
additives forfor
hydroxyl either
eitheror textiles
carboxyl
textiles or engineering
groups
or engineering were plastics.
found
plastics. to beInvery
In addition, addition, polymeric
effective
polymeric flame
for retardants
flame cellulosic
retardants
materials.
bearing bearing
hydroxyl or hydroxyl or carboxyl
carboxyl groups groups
were found to were
be very found to be
effective for very effective
cellulosic for cellulosic
materials.
materials.
Liu and
Liu and co-workers
co-workers [42][42] synthesized
synthesized poly(1,2-dicarboxyl
poly(1,2-dicarboxyl ethylene
ethylene spirocyclic
spirocyclic pentaerythritol
pentaerythritol
Liu and co-workers
bisphosphonate)
bisphosphonate) (29) by
(29) [42] synthesized
by reacting
reacting spirocyclicpoly(1,2-dicarboxyl
spirocyclic ethylene spirocyclic
pentaerythritol bisphosphorate
pentaerythritol bisphosphorate pentaerythritol
disphosphoryl
disphosphoryl chloride
chloride
bisphosphonate)
with tartaric
with tartaricacid (29) by reacting
acid(Figure
(Figure 20).Cotton
20). spirocyclic
Cotton fabrics pentaerythritol
fabricswere
were washed
washed bisphosphorate
with
with NaOH
NaOH disphosphoryl
solution
solution andand
thenthen chloride
soaked
soaked in
in an
with
an tartaric
aqueous acid (Figure
solution 20).
containing Cotton
30 wt fabrics
% of were
(28) andwashed
a with
catalyst. NaOH
After solution
drying,
aqueous solution containing 30 wt % of (28) and a catalyst. After drying, the samples were cured at the and then
samples soaked
were in
cured
an
160 ◦ C °C
aqueous
at 160 andandsolution
washed
washed containing
withwith sodium
sodium 30 wt % of (28)
carbonate
carbonate and and
a catalyst.
solution
solution and
thenthen After
dried
dried at ◦70
atdrying,
70 the samples were cured
C.°C.
at 160 °C and washed with sodium carbonate solution and then dried at 70 °C.

Figure 20.20.
Figure Synthetic
Synthetic approach
approach of poly(1,2-dicarboxyl
of poly(1,2-dicarboxyl ethylene
ethylene spirocyclic spirocyclic bisphosphonate).
pentaerythritol pentaerythritol
Figure 20. Synthetic approach of poly(1,2-dicarboxyl ethylene spirocyclic pentaerythritol
bisphosphonate).
bisphosphonate).
The flame retardant performance was investigated by LOI, vertical burning tests and TG analyses.
The flame retardant performance was investigated by LOI, vertical burning tests and TG
LOI values showed an increase up to 33.8% by increasing the add-on up to 21.2 wt %. Furthermore,
analyses. flame
The retardant
LOI values performance
showed was
an increase upinvestigated
to 33.8% by by LOI, vertical
increasing burning
the add-on up tests and
to 21.2 wtTG
%.
analyses. LOI values showed an increase up to 33.8% by increasing the add-on up to 21.2 wt %.
Polymers 2016, 8, 319 18 of 36
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Polymers 2016, 8, x FOR PEER 18 of 36

Furthermore, vertical burning tests performed on the treated samples showed a reduction of the
vertical burning
Furthermore, tests performed
vertical on the
burning tests treated samples
performed on the showed
treated asamples
reduction of the afterglow
showed a reduction timeof and
the
afterglow time and of the char length, without after-flame phenomena, as compared to the untreated
of the char length, without after-flame phenomena, as compared to the untreated fabric.
afterglow time and of the char length, without after-flame phenomena, as compared to the untreated As assessed
fabric. As assessed by TG analyses, an anticipation of the onset thermal decomposition, as well as an
by TG analyses,
fabric. As assessedan by
anticipation of the
TG analyses, anonset thermalofdecomposition,
anticipation the onset thermal as well as an increase
decomposition, as of theas
well char
an
increase of the char formation by increasing the add-on was found: once again, this latter finding
formation
increase ofby
theincreasing the add-on
char formation was found:
by increasing theonce again,
add-on wasthis latter once
found: finding proves
again, thisthe condensed
latter finding
proves the condensed phase mode of action of the flame retardant.
phase
provesmode of action of
the condensed the flame
phase moderetardant.
of action of the flame retardant.
Dong et al. reacted phenyl dichlorophosphate with ethylenediamine, in order to obtain the
Dong et al. reacted
reacted phenyl
phenyl dichlorophosphate
dichlorophosphate withwith ethylenediamine,
ethylenediamine, in in order
order to obtain the
poly(phoshorodiamidate) (30), shown in Figure 21. The product was applied onto cotton fabrics [43].
poly(phoshorodiamidate) (30), shown in Figure 21. The product was applied onto cotton fabrics [43].

Figure 21. Representative synthesis of poly(phoshorodiamidate) (30).

Figure
Figure 21.
21. Representative
Representative synthesis
synthesis of
of poly(phoshorodiamidate) (30).
poly(phoshorodiamidate) (30).
More specifically, cotton fabrics were dipped in solutions of (30) at different concentrations, in
More
More specifically,cotton
specifically, cottonfabrics
fabricswere
weredipped
dipped in solutions of of (30) at different concentrations, in
the presence of tetraethyl orthosilicate employed inas solutions
a crosslinker (30) at different
to permanently concentrations,
link the polymerin the
to
the presence
presence of tetraethyl orthosilicate employedaas a crosslinker to permanently link
the the polymer to
the fabricofsubstrate.
tetraethyl orthosilicate
The samples employed
were thenasdriedcrosslinker
and cured to permanently
at 160 °C. All linksamples
polymer
weretothen
the
the fabric
fabric substrate.
substrate. The The samples
samples werewere
then then dried
dried and cured
and cured at of
160the◦at 160
All °C.
C.treated All samples
samples were then
washed before testing. The flame retardant performance cottonwere
was then washed
investigated
washed
before before
testing. Thetesting. The flame
flame retardant retardant
performance performance
of untreated of the
the treatedfabrics,
cotton wastreated cotton
investigated was investigated
through vertical
through vertical burning tests: as compared with shorter after-glow time and char
through
burning vertical
tests:found burning
as compared tests: as compared
with the
untreated with untreated fabrics, shorter after-glow time and char
lengths were by increasing add-onfabrics, shortersamples.
of the treated after-glow time and char lengths were
lengths were
foundAbou-Okeil
by found by
increasing the increasing the
the add-on of the treated samples.
et add-on
al. of
[44] treated samples.
exploited the bulk polymerization process of
Abou-Okeil
Abou-Okeil et
et al.
al. [44]
[44] exploited
exploited the
the bulk
bulk polymerization
polymerization process of
methacryloyloxyethylorthophosphortetraethyldiamidate monomer in the presenceprocessof benzoyl of
methacryloyloxyethylorthophosphortetraethyldiamidate
methacryloyloxyethylorthophosphortetraethyl-diamidate monomer inin the the presence of benzoyl
peroxide as radical initiator, for synthesizing polymer (31)monomer exploiting a three-step presence of benzoyl
reaction (Figure
peroxide
peroxide as
as radical
radical initiator,
initiator, for
for synthesizing
synthesizing polymer
polymer (31)
(31) exploiting
exploiting a a three-step
three-step reaction
reaction (Figure
(Figure 22).
22).
22).

Figure 22.
Figure 22.Representative
Representative synthesis
synthesis of methacryloyloxyethylorthophosphorotetraethyl-diamidate
of methacryloyloxyethylorthophosphorotetraethyl-diamidate polymer.
Figure 22. Representative synthesis of methacryloyloxyethylorthophosphorotetraethyl-diamidate
polymer.
polymer.
Cotton fabrics were dipped into aqueous solutions of polymer (31) at different concentrations,
Cotton
in theCotton
presencefabrics were
of a were
binder dipped into aqueous
and a crosslinker. solutions
The of
treated of polymer
fabrics (31)
were(31)
thenat different concentrations,
fabrics dipped into aqueous solutions polymer atsqueezed, dried and then
different concentrations,
in the
cured presence
at 150 ◦ C. of a
Afterbinder
the and a
treatments,crosslinker.
the fabricsThe treated
increased fabrics
their LOIwere then
values; TGsqueezed, dried and
measurements then
revealed
in the presence of a binder and a crosslinker. The treated fabrics were then squeezed, dried and then
cured
the at 150 of
formation °C.a After the
stable the treatments,
char.treatments, the fabricsthe
Despite these increased their LOI values; TG measurements
cured at 150 °C. After theresults, observed
fabrics increased changes
their LOI were notTG
values; very significant as
measurements
revealed
compared the
to formation
untreated of a
cotton.stable char. Despite these results, the observed changes were not very
revealed the formation of a stable char. Despite these results, the observed changes were not very
significant as compared
Recently, Dong et al.toto[45]
untreated cotton.
synthesized a guanidyl- and phosphorus-containing polysiloxane flame
significant as compared untreated cotton.
Recently,
retardant (32): Dong
for thiset al.
purpose,[45] synthesized
according a guanidyl-
to Figure and phosphorus-containing
23, 3-aminopropylethoxysilane polysiloxane
waspolysiloxane
hydrolyzed
Recently, Dong et al. [45] synthesized a guanidyl- and phosphorus-containing
flame
and retardant
then reacted (32):
with for this
dicyandiamidepurpose,
and according
P O to
(Figure Figure
23). 23, 3-aminopropylethoxysilane was
flame retardant (32): for this purpose, according 2 5 to Figure 23, 3-aminopropylethoxysilane was
hydrolyzed and then reacted with dicyandiamide and P2O5 (Figure 23).
hydrolyzed and then reacted with dicyandiamide and P2O5 (Figure 23).
Polymers 2016, 8, 319 19 of 36
Polymers 2016, 8, x FOR PEER 19 of 36

Figure
Figure 23.
23. Schematic
Schematic synthesis
synthesis of
of guanidyl-
guanidyl- and
and phosphorus-containing polysiloxane (32).
phosphorus-containing polysiloxane (32).

After washing, cotton fabrics were soaked in a bath containing the FR polymer,
After washing, cotton fabrics were soaked in a bath containing the FR polymer,
2-phosphonobutane-1,2,4-tricarboxylic acid and urea at room temperature, then squeezed in
2-phosphonobutane-1,2,4-tricarboxylic acid and urea at room temperature, then squeezed in laboratory
laboratory scale padder, rinsed with water, dried at 80 °C and cured at 160 °C. The flame retardant
scale padder, rinsed with water, dried at 80 ◦ C and cured at 160 ◦ C. The flame retardant performance of
performance of the treated samples was tested by cone calorimetry and thermogravimetric analyses.
the treated samples was tested by cone calorimetry and thermogravimetric analyses. Cone calorimetry
Cone calorimetry measurements showed that by increasing the add-on of the FR polymer, HRR and
measurements showed that by increasing the add-on of the FR polymer, HRR and THR decreased
THR decreased accordingly, hence, indicating that the flame retardant hinders the formation of
accordingly, hence, indicating that the flame retardant hinders the formation of combustible volatile
combustible volatile species. In addition, the CO2/CO ratio decreased dramatically with increases in
species. In addition, the CO2 /CO ratio decreased dramatically with increases in the FR add-on.
the FR add-on. TG measurements performed on the treated cotton fabrics showed an increase of the
TG measurements performed on the treated cotton fabrics showed an increase of the decomposition
decomposition temperature with, at the same time, an increase of char formation. It is worthy to
temperature with, at the same time, an increase of char formation. It is worthy to mention that,
mention that, in addition to the enhanced flame retardant performances, the treated fabrics showed
in addition to the enhanced flame retardant performances, the treated fabrics showed an effective
an effective antimicrobial behavior against E. coli and S. aureus [46].
antimicrobial behavior against E. coli and S. aureus [46].
Very recently, the same group synthesized a novel nitrogen and phosphorus-containing
Very recently, the same group synthesized a novel nitrogen and phosphorus-containing
polysiloxane ((33), Figure 24), starting from poly(4-iodo-n-butoxy)methylsiloxane and
polysiloxane ((33), Figure 24), starting from poly(4-iodo-n-butoxy)methylsiloxane and
N-methylo-3-(dimethoxy dibenzyloxyphosphoryl) acrylic amide [47].
N-methylo-3-(dimethoxy dibenzyloxyphosphoryl) acrylic amide [47].
By adopting a similar approach, the polymeric additive ((34), Figure 24) was also synthesized
By adopting a similar approach, the polymeric additive ((34), Figure 24) was also synthesized
using poly (4-iodo-n-butoxy) methylsiloxane and guanidine sulfamate [48].
using poly (4-iodo-n-butoxy) methylsiloxane and guanidine sulfamate [48].
Both polymeric flame retardant additives were applied onto cotton fabrics, using an
Both polymeric flame retardant additives were applied onto cotton fabrics, using an impregnation
impregnation bath also containing urea and zirconium oxide. The samples were then dried and
bath also containing urea and zirconium oxide. The samples were then dried and cured at 160 and
cured at 160 and 150 °C (for treated fabrics with (33) and (34), respectively). Cone calorimetry and
150 ◦ C (for treated fabrics with (33) and (34), respectively). Cone calorimetry and TG analyses were
TG analyses were exploited for assessing the performances of the samples treated with polymer (33):
exploited for assessing the performances of the samples treated with polymer (33): more specifically,
more specifically, the treated fabrics showed an enhancement of the flame retardancy by decreasing
the treated fabrics showed an enhancement of the flame retardancy by decreasing HRR, THR and
HRR, THR and CO2/CO ratio. TG data showed a decrease of the onset decomposition temperature
CO2 /CO ratio. TG data showed a decrease of the onset decomposition temperature and an increase of
and an increase of the char yield for all treated samples. Furthermore, LOI values of the treated
the char yield for all treated samples. Furthermore, LOI values of the treated samples did not show
samples did not show a significant drop after several washing cycles, hence, proving the durability
a significant drop after several washing cycles, hence, proving the durability of flame retardant (33).
of flame retardant (33). A similar FR performance was also assessed for the cotton fabrics treated
A similar FR performance was also assessed for the cotton fabrics treated with polymer (34): unlike
with polymer (34): unlike (32), the treated fabrics also showed water repellency, which was
(32), the treated fabrics also showed water repellency, which was attributed to the reaction of the flame
attributed to the reaction of the flame retardant with cotton fibers, leading to methyl group
retardant with cotton fibers, leading to methyl group orientation on the fiber surface.
orientation on the fiber surface.
Polymers 2016, 8, 319 20 of 36
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Polymers 2016, 8, x FOR PEER 20 of 36

Figure 24. Representative synthetic approach for flame retardants (33) and (34).
Figure 24. Representative synthetic approach for flame retardants (33) and (34).
Figure 24. Representative synthetic approach for flame retardants (33) and (34).
Very recently, Chen and co-workers synthesized a polymeric sulfur-containing flame retardant
Very recently, Chen and co-workers synthesized aa polymeric sulfur-containingflame
flame retardant
((35),Very recently,
Figure 25) Chen
for and co-workers
nylon fabrics,synthesized polymeric
using thiourea, sulfur-containing
phosphoric acid, water retardant
soluble
((35), Figure
((35), 25) for25)
Figure nylon fabrics,
for nylon using thiourea,
fabrics, phosphoric
using acid,phosphoric
thiourea, water soluble isocyanate-terminated
acid, water soluble
isocyanate-terminated crosslinker (WIT) and epichlorohydrin [49].
crosslinker (WIT) and epichlorohydrin
isocyanate-terminated [49].
crosslinker (WIT) and epichlorohydrin [49].
O O H H
H OP H N N
Cl O O H H
O H N N
Cl OH S PO S
OP O nH
Cl O OH S O S
O POH H2N NH2 n
Cl OH O OH
OH H2N NH2
HO O
P OH OH OH
HO OH
P OH Cl
OH Cl

O S O O O WIT
H O
P S O WIT O O O WIT
O N N N N N Nylon 66
H P
O H H n
N WIT
H H H p H
O
O N H Nylon 66
N N N N N O p H
O H H nH H H H H O
O H H H O
N N N N O H
Cl O H WIT H
N
H
N
H
N
O
p H
N
Cl O WIT O O O
p
O O 35 O
35

H
N
H O
N S ONa
O O
OS ONa
O
NH O
O NH
O
OO
O O
O
H O
WIT = N N O H O O
S
NaO O H N O ONa
= S H O O N S
WIT O N N H H ONa
NaO O H O N N O
S
O O H
O O
O
Figure 25. Synthetic route of polymeric additive (35).
Figure 25.Synthetic
Figure 25. Synthetic route
route of
of polymeric
polymeric additive
additive(35).
(35).
Polymers 2016, 8, 319 21 of 36
Polymers 2016, 8, x FOR PEER 21 of 36

In particular, nylon fabrics

fabrics were
weredip-treated
dip-treatedin inaafinishing
finishingsolution
solutioncontaining
containingthe FRFR
the polymer, a
polymer,
acrosslinker
crosslinkerand
andpotassium
potassiumthiocyanate.
thiocyanate.After
Afterdrying,
drying,the thesamples
sampleswere
werecured
cured at
at 150 ◦ C and then
150 °C
soaked in water/soap
water/soapsolution,
solution,rinsed
rinsedwith
withwater
waterand
and dried again.
dried As As
again. assessed by TG
assessed analyses,
by TG the
analyses,
onset
the decomposition
onset decomposition temperature
temperature of of
thethetreated
treatedfabrics
fabricswas
was anticipated,
anticipated, notwithstanding
notwithstanding a
substantial increase of the char formation with respect to the untreateduntreated counterparts.
counterparts. MCC analyses
showed an important decrease of HRR, THR and HRC, together with a significant char formation. formation.
durabilityof
The durability ofthe
theflame
flameretardant
retardanttreatment
treatment was
was also
also assessed:
assessed: 10 washing
10 washing cycles
cycles did did not have
not have any
any detrimental effect on the flame retardants’ performances.
detrimental effect on the flame retardants’ performances.

4.6. PhosphoramidateFlame
4.6 Phosphoramidate FlameRetardants
Retardants
Phosphoramidate derivatives
derivatives are promising flame retardant additives, due to the synergistic
effect provided by
by phosphorus
phosphorus and and nitrogen.
nitrogen.
Gaan and
andco-workers
co-workers [50][50]
synthesized different
synthesized phosphoramidate
different derivatives
phosphoramidate as flame as
derivatives retardant
flame
additives for cotton fabrics, following the Atherton-Todd reaction in the presence of dialkylphosphites
retardant additives for cotton fabrics, following the Atherton-Todd reaction in the presence of
as starting materials
dialkylphosphites as(Figure
starting26).
materials (Figure 26).

R
O
H2N OH O
P R = methyl; 36
N OH R = ethyl; 37
O H
R

O 1/2 HN NH R O O R
O P N N P O R = methyl; 38
O P H CCl4
R = ethyl; 39
R O O O
R R R

R
NH2 R O
O H
1/2 H2N O N P R R = methyl; 40
P N O R = ethyl; 41
H O
O R
Figure 26. Scheme
Figure 26. Scheme of
of the
the synthesis of phosphoramidate
synthesis of phosphoramidate derivatives
derivatives (36)–(41).
(36)–(41).

The products
The productswere were
appliedapplied onto fabrics
onto cotton cotton from
fabrics fromsolutions
acetone acetonewith solutions
differentwith different
concentrations
concentrations
of phosphoramidatesof phosphoramidates
(36)–(41). LOI (36)–(41).
values were LOIfound
valuestowere found
increase bytoincreasing
increase by theincreasing
phosphorus the
phosphorus content of the
content of the treated cotton. treated cotton.
Nguyen and
Nguyen and co-workers
co-workersfurther furtherinvestigated
investigatedthe theflame
flameretardant
retardantperformance
performance of of
(36) and
(36) and(37) at
(37)
different
at add-ons
different add-ons on on
cotton
cotton fabrics [51]:[51]:
fabrics in particular, the fabrics
in particular, treated
the fabrics withwith
treated an add-on beyond
an add-on 5 wt
beyond
% showed no afterflame or afterglow time, providing the fabrics with self-extinction.
5 wt % showed no afterflame or afterglow time, providing the fabrics with self-extinction. The effect The effect of
chemical structure on the performance of these flame retardants was
of chemical structure on the performance of these flame retardants was studied using MCC. It was studied using MCC. It was
found that
found that THR
THR values
values decreased
decreased with with increases
increases in in the
the add-on
add-on of of product
product (36).
(36). Conversely,
Conversely, THR THR
values were found to increase by increasing the add-on of (37). Product
values were found to increase by increasing the add-on of (37). Product (39) promoted char formation (39) promoted char
formation
and and decreased
decreased the THR of the theTHR of thesamples
treated treated with
samples with increases
increases in the on
in the add-on add-on on the treated
the treated fabrics.
fabrics. On the other hand, vertical flammability tests performed on cotton
On the other hand, vertical flammability tests performed on cotton fabrics treated with (39) showed fabrics treated with (39) an
showed an increase after flame and no
increase after flame and no afterglow phenomena [52].afterglow phenomena [52].
As aa comparison
As comparison to to (39),
(39), the
the same
same group
group [53]
[53] synthesized
synthesized new new flame
flame retardants
retardants using
using dimethyl
dimethyl
phosphorochloridothionate and diethyl phosphorochloridate as starting
phosphorochloridothionate and diethyl phosphorochloridate as starting material (Figure 27). From material (Figure 27). From an
an overall point of view, it was found that the flame retardant performance
overall point of view, it was found that the flame retardant performance of the fabrics treated with 39 of the fabrics treated
withmuch
was 39 was much
better thanbetter than
that of thethat of the substrates
substrates treated withtreated with same
same add-on add-on
of (42). of (42). Furthermore,
Furthermore, when cotton
when cotton fabrics were treated with (39) and (43), they showed
fabrics were treated with (39) and (43), they showed almost the same FR performances. almost the same FR performances.
Polymers 2016, 8, 319 22 of 36
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Polymers 2016, 8, x FOR PEER 22 of 36

Figure 27. Synthesis of (42) and (43).

Figure 27. Synthesis
Figure 27. Synthesis of
of (42)
(42) and
and (43).
(43).
The phosphoramidate (43) was also investigated as flame retardant additives for cotton twill
The
The phosphoramidate
phosphoramidate(43) (43)was
wasalso investigated
also investigated as as
flame retardant
flame additives
retardant for cotton
additives twilltwill
for cotton and
and cotton print cloth [55]. The flame retardant performance of the treated fabrics was found to
cotton
and cotton print cloth [55]. The flame retardant performance of the treated fabrics was found on
print cloth [55]. The flame retardant performance of the treated fabrics was found to depend to
depend on the type of treated fabrics: in particular, the add-on being equal, the treated cotton twill
the type on
depend of treated
the typefabrics: in particular,
of treated theparticular,
fabrics: in add-on being equal, the
the add-on treated
being cotton
equal, twill showed
the treated cottonbetter
twill
showed better FR performances as compared with the treated print cloth.
FR performances
showed better FRas compared with
performances the treatedwith
as compared printthe
cloth.
treated print cloth.
Recently [56], ditrimethylolpropane di-N-hydroxyethyl phosphoramide (44) was synthesized
Recently
Recently [56], ditrimethylolpropane di-N-hydroxyethyl phosphoramide
[56], ditrimethylolpropane di-N-hydroxyethyl phosphoramide (44) (44) was
was synthesized
synthesized
using ditrimethylolpropane and phosphoryl chloride as starting materials (Figure 28).
using ditrimethylolpropane and phosphoryl chloride as starting materials
using ditrimethylolpropane and phosphoryl chloride as starting materials (Figure 28). (Figure 28).

Figure 28. Representative schematic synthesis of (44).

Figure 28.
Figure 28. Representative
Representative schematic
schematic synthesis
synthesis of
of (44).
(44).
The obtained FR additive (44) was applied to cotton, nylon and polyester fabrics, using a
The obtained
The obtainedFR FRadditive
additive(44)(44)
was was applied to cotton, nylon and polyester fabrics, using a
dipping method. The fabrics were thenapplied
dried and to cotton,
cured at nylon andThe
160 °C. polyester
flame fabrics,
retardant using a dipping
performance
dipping
method. method.
The fabrics The
fabrics was fabrics
weretested were
then using then dried
dried vertical
and cured and cured ◦ at
at 160 C. tests:160 °C.
The flame The flame retardant performance
of the treated flammability it wasretardant
found that performance of the
the treated nylon
of the treated
treated fabrics fabrics
was was using
tested testedvertical
using vertical flammability
flammability tests: it tests:
was it wasthat
found foundthe that the treated
treated nylon nylon
fabrics
fabrics showed better flame retardant performances as compared with the other treated fabrics.
fabrics
showed showed
better flamebetter flame retardant
retardant performances performances
as comparedas compared with the other treated fabrics.
Shariatinia and co-workers [57] synthesized differentwith the other treated
phosphoramidates fabrics.
and phosphoramides
Shariatinia and
Shariatinia and co-workers
co-workers [57] [57] synthesized
synthesized different
different phosphoramidates
phosphoramidates and and phosphoramides
phosphoramides
starting from their corresponding phosphoramidic dichloride in an ultrasonic bath, obtaining the
starting from
starting fromtheirtheircorresponding
corresponding phosphoramidic
phosphoramidic dichloride
dichloride aninultrasonic
an ultrasonic
bath, bath, obtaining the
flame retardant additives (45)–(49) shown in Figure 29. Allinthese flame retardant obtaining the flame
additives were
flame retardant
retardanttoadditives additives
(45)–(49)(45)–(49) shown in Figure 29. All these flame retardant additives were
applied cotton fabrics. Theshown
cottoninfabrics
Figurewere29. All thesewith
treated flame anretardant
aqueous additives
solution of were
eachapplied
flame
applied
to cotton tofabrics.
cottonThe fabrics.
cottonThe cottonwere
fabrics fabrics werewith
treated treated
an with an solution
aqueous aqueousofsolution
each of each
flame flame
retardant
retardant additive at different concentrations and in the presence of a thermal initiator. The treated
retardantatadditive
additive different atconcentrations
different concentrations theand in the of presence of ainitiator.
thermal The initiator. Thesamples
treated
samples were then dried and cured and at 121in °C presence
and their flame a thermal
retardant performance treated
was assessed
samples
were then were then
dried burningdried
and cured and cured
at 121 ◦ at 121 °C
C andretardant and
their flame their flame
retardant retardant performance was assessed
through vertical tests: the flame additives (46)performance
and (48) showed was aassessed through
lower degree of
throughburning
vertical vertical tests:
burningthe tests:
flame the flame retardant
retardant additives additives
(46) and (46) showed
(48) and (48) ashowed
lower a lowerofdegree
degree graftingof
grafting and an increased char length, as compared with the samples treated with the same
grafting and
and an increased an increased
char(47)
length, char length,
as compared as compared with the samples treated with the same
concentration of (45), and (49) additives. with the samples
In general, the char treated
lengthwith wasthefoundsame concentration
to decrease with
concentration
of (45), (47) andof (49)
(45),additives.
(47) and (49) In additives.
general, theInchar
general,
length thewascharfound
lengthtowas foundwith
decrease to decrease
increases with
in
increases in the degree of grafting, which in turn depended on the additive concentration in the
increases in the
the degree of grafting, degree of
which grafting, which in turn depended on the additive
in turn depended on the additive concentration in the corresponding concentration in the
corresponding treatment solutions.
corresponding
treatment treatment solutions.
solutions.
Polymers 2016, 8, 319 23 of 36
Polymers 2016, 8, x FOR PEER 23 of 36

Figure 29. Representative synthesis of flame retardant additives (45)–(49).

Figure 29. Representative synthesis of flame retardant additives (45)–(49).

4.7 Miscellaneous
4.7. Miscellaneousand
andPotential
PotentialPhosphorus-Based
Phosphorus-BasedFlame
Flame Retardants
Retardants for
for Textile
Textile Applications
Applications
In addition
In additiontotothe
thelistlist
of of chemical
chemical structures
structures and and chemical
chemical classifications
classifications that
that are are mentioned
mentioned earlier,
earlier, it is worth listing some miscellaneous and promising flame retardants based on
it is worth listing some miscellaneous and promising flame retardants based on their chemical structure their
chemical structure and
and behavior (Table 2). behavior (Table 2).
Polymers 2016, 8, x FOR PEER 24 of 36
Polymers 2016,
Polymers 2016,8,8,x319
FOR PEER 24 of 36 24 of 36
Polymers 2016, 8, x FOR PEER 24 of 36

Table 2. Miscellaneous and potential promising flame retardants for textile applications.
Table
Table 2. Miscellaneous
2. Miscellaneous and and potential
potential promising
promising flameflame retardants
retardants for textile
for textile applications.
applications.
Table 2. Miscellaneous and potential promising flame retardants for textile applications.
Chemical structure Textile material Highlights Ref.
Chemical
Chemical structure Textile material Highlights Ref. Ref.
Chemical structure
structure Textile
Textile material
material Highlights
Highlights Ref.
The FR monomer was grafted onto cotton fabrics using gamma chamber.
The FR monomer was grafted onto cotton fabrics using gamma chamber.
Theanalysis
TG FRThe
monomer
FRof thewas
ofmonomer grafted
treated ontoshowed
fabrics
wasfabrics
grafted cotton fabrics
a decrease
onto cotton usingofusing
fabrics gamma
the onset chamber.
gamma decomposition
chamber. temperature
cotton TG analysis the treated showed a decrease of the onset decomposition temperature [58]
cotton TG analysis
and increase
TG of
analysis the
of char treated
of formation.
the fabrics
treated showed
fabrics showed a decrease
a decrease of the
of onset
the decomposition
onset decomposition temperature
temperature [58]
cotton
cotton and increase of char formation. [58] [58]
and burning
The increase of char
test
and increase offormation.
showed charthat treated fabrics burnt much slower than untreated fabrics.
formation.
The burning test showed that treated fabrics burnt much slower than untreated fabrics.
The burning
The burning test showed
test showed that treated
that treated fabricsfabrics
burnt burnt
much much slowerslower than untreated
than untreated fabrics.fabrics.
The FR was applied to viscose fiber fabric through grafting polymerization.
The FR was applied to viscose fiber fabric through grafting polymerization.
The FR
LOI wasFR
values
The applied
increased tobyviscose
was applied increasingfiber the
to viscose fabric through
grafting
fiber fabric grafting
percentage.
through polymerization.
grafting polymerization.
LOI values increased by increasing the grafting percentage.
Viscose fiber LOI values
LOI increased
were
values almost by
increased increasing
unchanged
by the
increasing grafting
after many
the percentage.
washing
grafting cycles
percentage. which showed the durability of
Viscose fiber LOI values were almost unchanged after many washing cycles which showed the durability of [59]
Viscose
fabricfiber LOIcovalent
the values were
LOI valuesbond. almost
were almost unchanged unchanged after many washing
after many cyclescycles
washing which showed
which the durability
showed of [59]
the durability
fabric
Viscose fiber fabric the covalent bond. [59] [59]
fabric the covalent
Cone of bond. data
the covalent
calorimetry bond. of treated fabric showed a significant decrease of PHRR and THR
Cone Cone
calorimetry data of treated fabric showed a significant decrease of PHRR and THR
tocalorimetry
Cone calorimetry
compared untreated data
datafabric. of treated
of treated fabricfabric showed
showed a asignificant
significantdecrease
decrease of of PHRR and andTHRTHR
compared to untreated
compared to fabric.fabric.
untreated
compared to untreated fabric.
The FR was used as sol-gel precursor.
The FRThewasFR used
wasas sol-gel precursor.
The
It FRhydrolyzed
was was used used
as sol-gel
with 3-aminopropyltriethoxysilane
as sol-gel precursor.
precursor. (APTES) in deionized water in presence of
It was It
hydrolyzed with 3-aminopropyltriethoxysilane (APTES) in deionized water inwaterpresence
in of
It was
HCl was hydrolyzed
hydrolyzed
followed by the with 3-aminopropyltriethoxysilane
additionwith of 3-aminopropyltriethoxysilane
a crosslinker. (APTES) (APTES) in deionized
in deionized water in presence of
HCl followed
presence byof the
HCl addition
followed of by
a crosslinker.
the addition of a crosslinker.
HCl fabrics
The followed wereby treated
the addition of a crosslinker.
by impregnation in solutions and cured at 150 °C after processing.
cotton The fabrics were treated
The fabrics were treatedby impregnation
by impregnation in solutions and cured
in solutions at 150at
and cured °C150 ◦ Cprocessing.
after after processing. [60]
cotton
cotton The fabrics
burning weretesttreated
showed by that
impregnation
all treatedincottonsolutions and cured
fabrics burnedat completely
150 °C after withprocessing.
significant [60] [60]
cotton The burning
The burning test showed
test showed that that all treated
all treated cotton
cotton fabrics
fabrics burnedcompletely
burned completelywith significant [60]
with significant
The burning
reduction test showed
of burning time and thatburning
all treatedrate cotton
compared fabrics burned completely
to untreated fabrics. with significant
reduction
reduction of burning of burning
time and time and burning
burning rate compared
rate compared to untreated
to untreated fabrics.fabrics.
reduction
The of
FR exhibitedburning time
condensed andphase
burning mode rateofcompared
action as toTG untreated
analysis fabrics.
showed an increase of char
The FRThe FR exhibited
exhibited condensed condensed phasephasemodemode of action
of action as TG asanalysis
TG analysis showedshowed an increase
an increase of
of char
The FRchar
formation.exhibited
formation. condensed phase mode of action as TG analysis showed an increase of char
formation.
formation.
The cotton fabrics were treated by soaking in finishing bathsof of FR, each at different
The cotton
The cotton fabricsfabrics
were were treated
treated bybysoaking
soaking in in finishing
finishingbaths baths of FR,FR,
eacheach
at different
at different
The cotton
concentrations fabrics
concentrationsbut allwere at pH
but alltreated
= 5.pH =by
at 5. soaking in finishing baths of FR, each at different
Polymers 2016, 8, x FOR PEER concentrations but all at pH = 5. 25 of 36
concentrations
The FRThe
canFR react but
can all at
with
react pH cellulose
cellulose
with = 5.without using using
without other crosslinkers.
other crosslinkers.
cotton
cotton The FR can react with cellulose without using other crosslinkers. [61] [61]
cotton The FR
LOI canvalues
values
LOI react
of with
treated cellulose
fabrics
of treated without
increased
fabrics by
increased using other
increasing
by crosslinkers.
the FRthe
increasing concentration.
FR concentration. [61]
cotton LOI valuesTable
of treated2. Cont.
fabrics increased by increasing the FR concentration. [61]
LOI treated
The values of
The treated treated
fabrics fabrics
were fabricswere
found increased
found
durable byupincreasing
durable to up to 50the
50 washing FR
washing concentration.
cycles cycles
as no as no change
change had been
had been noticed
The treated
noticed fabrics
on the were
LOI found
valuesdurable up to 50performance
orperformance
the physical washing cycles as no
of the change
treated had been noticed
fabrics.
Chemical structure Textile material Thethe
on treated fabrics
LOI values orwere found
the physical durable upHighlights
to 50 ofwashing
the treated cycles as no
fabrics. change had been noticed Ref.
on the LOI values or the physical performance of the treated fabrics.
on the LOI values or the physical performance of the treated fabrics.
The cotton
The cottonfabrics werewere
fabrics treated
treated bybyimpregnation
impregnationin in an aqueoussolution
an aqueous solutionof ofFR,FR, binder,
binder,
crosslinker and pyrovatex.
crosslinker and pyrovatex.
cotton
cotton [44] [44]
LOI values of theoftreated
LOI values the treated fabrics withwith
fabrics different binders
different bindersandand crosslinkers
crosslinkers were
werebelow
below 2121which
which
meansmeans
they can they can ignite
ignite easily easily
and burn andrapidly.
burn rapidly.

The fabrics were treated by immersion in an aqueous solution of the FR in the presence of a
buffer and shrinking agent.
LOI measurements showed an increase in LOI values with increases in the FR concentration.
cotton The treated fabrics showed durability up to 30 laundry cycles which was considered as [62]
semi-durable flame-resistant.
The vertical burning test showed no afterflame or afterglow and a decrease in the char length
with an increase in the FR concentration.
The fabrics were treated by immersion in an aqueous solution of the FR in the presence of a
shrinking agent
The treated fabrics showed durability up to 30 laundry cycles which was considered as
cotton [63]
semi-durable flame-resistant
The vertical burning test showed no afterflame or afterglow and a decrease in the char length
Polymers 2016,
Polymers 2016, 8,
8, xx FOR
FOR PEER
PEER 25 of
25 of 36
36
Polymers
Polymers 2016,
2016, 8,
8, xx FOR
FOR PEER
PEER 25
25 of
of 36
36
Table 2.
Table 2. Cont.
Cont.
Table
Table 2.
2. Cont.
Cont.
Chemical
Polymers 2016, Chemical
8, 319 structure
structure Textile material
Textile material Highlights
Highlights Ref.
Ref. 25 of 36
Chemical
Chemical structure
structure Textile
Textile material
material Highlights
Highlights Ref.
Ref.
The cotton
The cotton fabrics
fabrics were
were treated
treated byby impregnation
impregnation in in anan aqueous
aqueous solution
solution of of FR,
FR, binder,
binder,
The
The cotton
cottonand fabrics
fabrics were
were treated
treated byby impregnation
impregnation in in an
an aqueous
aqueous solution
solution of of FR,
FR, binder,
binder,
crosslinker
crosslinker and pyrovatex.
pyrovatex.
cotton
cotton crosslinker and Table 2. Cont.
pyrovatex. [44]
cotton
cotton
crosslinker
LOI
LOI values
values
and
of
of
pyrovatex.
the
the treated
treated fabrics
fabrics with
with different
different binders
binders and
and crosslinkers
crosslinkers were
were below
below 21
21 which [44]
which [44]
[44]
LOI values
LOI values of the treated fabrics with different binders and crosslinkers were below 21 which
Chemical structure means
Textile material means they of
they canthe
can
treated
ignite
ignite
fabrics
easily
easily and
with rapidly.
and burn
burn different binders and crosslinkers were below 21 which
rapidly. Highlights Ref.
means they can ignite easily and burn
means they can ignite easily and burn rapidly. rapidly.
The fabrics
The fabrics were treated
were
The fabrics treated
were by immersion
by
treated immersion
by immersionin an
in aninaqueous
aqueous
an aqueous solution
solution of the
of
solution the FR FR
FR
of the in the
in the presence
presence
in the presenceofof
of aa a
The
The fabrics
fabrics were
were treated
treated by
by immersion
immersion in in an
an aqueous
aqueous solution
solution ofof the
the FRFR in
in the
the presence
presence ofof aa
buffer
buffer and
and shrinking
shrinking
buffer agent.
agent.
and shrinking agent.
buffer
buffer and shrinking
and measurements
shrinkingshowedagent.
agent.
LOI
LOI measurements
LOI
measurements showed an increase
showed
an increase in LOI
LOIinvalues
an increase
in values with increases
LOI values
with increases in the
with increases
in theinFRthe
FR concentration.
FR concentration.
concentration.
LOI measurements
LOI measurements showed
showed an increase
andurability
increase in LOI
inup
LOI values with
with increases in
in the FR concentration.
cotton
cotton
cotton The
The treated
treated fabrics
The treated showed
fabrics
fabrics showed
showed durability
durability up uptovalues
to 3030laundry
to30 laundry
laundry increases
cycles which
cycles which
which
the was
FR
was
was
concentration.
considered
considered
considered as [62]
as as [62] [62]
cotton
cotton The
The treated
treated
semi-durable
fabrics
fabrics
semi-durable
showed
showed durability
durability up
flame-resistant.
flame-resistant. up toto 3030 laundry
laundry cycles
cycles which
which was was considered
considered as as [62][62]
semi-durable
semi-durable flame-resistant.
flame-resistant.
semi-durable
The
The vertical flame-resistant.
vertical
vertical burning burning
burning test test
test showed showed
showed no no afterflame
no afterflame
afterflame or or afterglow
or afterglow
afterglow and and a decrease
and aa decrease
decrease in in
in the the char
the char length
char length
length
The
The
The vertical
with with
vertical
an anburning
increase increase
burning test
in showed
FRthe
thetest
in the
no
no afterflame
afterflame or
FR concentration.
showed
concentration. or afterglow
afterglow andand aa decrease
decrease in in the
the char
char length
length
with
with an increase in FR concentration.
with an
an increase
increase in in the
the FR
FR concentration.
concentration.
The fabrics
The fabrics were
were treated
treated byby immersion
immersion in in an
an aqueous
aqueous solution
solution of
of the
the FRFR in
in the
the presence
presence ofof aa
The
The fabrics were
were treated
The fabrics
fabrics were
treated by
by immersion
treated by immersion
immersion in
in an
aninaqueous
an aqueous
aqueous solution of
of the
solution
solution FR
of the
the in
in the
FR FR in presence
thethe presence
presence of
ofofaa a
shrinking
shrinking agent
agent
shrinking
shrinking
shrinking agent
agent agent
The
The treated
treated fabrics
fabrics
The treated showed
showed
fabrics showed durability
durability upup
up
durability to to30
to 3030laundry
laundry cycles which
laundry cycles whichwas
which wasconsidered
was considered
considered as
as as
cotton
cotton
cotton The
The treated
treated fabrics
fabrics showed
showed durability
durability upup toto 3030 laundry
laundry cycles
cycles which
which was was considered
considered as as [63][63] [63]
cotton
cotton semi-durable
semi-durable flame-resistant
flame-resistant
semi-durable flame-resistant [63]
[63]
semi-durable
semi-durable flame-resistant
flame-resistant
The
The vertical
The
vertical burning
vertical
burning test showed
burning
test showed
test no afterflame
showed
no afterflame
no or afterglow
afterflame
or afterglow
or andand
afterglow
and a decrease
a decrease
a decreasein the
in the
in char
the length
char
char length
length
The
The vertical
vertical burning test showed no
no afterflame
afterflame or or afterglow
afterglow andand aa decrease
decrease in in the
the char
char length
with
with an
with
an anburning
increase
increase thetest
in the
increase
in in
FR
showed
FRthe
concentration.
FR concentration.
concentration.
length
with
with an
an increase
increase in in the
the FR
FR concentration.
concentration.
Meltable flame
Meltable flame retardant
retardant which
which facilitates
facilitates the
the compounding
compounding process.process.
Meltable
Meltable flame
Meltable
flame retardant
flame
retardant which
retardant
which facilitates
which the compounding
facilitates
facilitates theFR the compounding
compounding process.
process.
Rheological
Rheological measurements
measurements showed
showed that
that this
this FR behaves
behaves as aa process.
as plasticizer for PA6.
Rheological
Rheological measurements
Rheological
measurements showed
measurements
showed that
showed
that this
that
this FR
FR behaves
this as
FR behaves
behaves as aa plasticizer
plasticizer for
for PA6.
PA6.
as a plasticizer
plasticizer for PA6.
PA6 fibers
PA6 fibers TG analysis
TG analysis showed
showed higher
higher char
char formation
formation of of formulated
formulated PA6 PA6 with theforFR
with the FRPA6.
compared to
compared to neat
neat [64]
[64]
PA6
PA6 fibers
PA6 fibers
fibers TG analysis
TG
TG analysis showed
analysis
showed higher
showed
higher char
higher formation
char of
formation
char formation formulated
of formulated
of formulated PA6 with
PA6
PA6 with the
with FR
the compared
FR to
compared
the FR compared neat
to to neat [64]
neat [64] [64]
PA6,
PA6, while PCFC
while PCFC showed
showed a predominant
a predominant action
action in the
in the gas-phase
gas-phase mode.
mode.
PA6,
PA6, PA6,
while
while while
PCFC
PCFC PCFC
showed
showed showed a predominant
aa predominant
predominant action
action action
in
in the
the in the gas-phase
gas-phase
gas-phase mode.
mode. mode.
UL-94 UL-94
UL-94 test showed
test showed aa V0
test showedV0 rating
rating with 15
with
a V0 rating 15 wt %
wt
with % of
15of FR
wtFR in
% in PA6.
of PA6.
FR in PA6.
UL-94
UL-94 test
test showed
showed aa V0 V0 rating
rating with
with 15
15 wt
wt %% ofof FR
FR in
in PA6.
PA6.

PET and
PET and PBT
PBT
PET and
and PBT
PETfibersPBT The UL-94
The UL-94 test
test for
for the
the formulated
formulated PET
PET and
and PBT
PBT fibers
fibers with
with FR
FR showing
showing aa V0
V0 rating.
rating. [65]
[65]
and PBT fibers The
fibers
PET fibers The UL-94
UL-94 test
test for
The UL-94 the
fortest formulated
thefor
formulated PET
PET and
and
the formulated PBT
andfibers
PBT
PET fibers with
with FR
PBT fibersFR showing
showing
with aa V0
V0 rating.
FR showing rating.
a V0 rating. [65]
[65] [65]
fibers
Polymers 2016, 8, 319 26 of 36

5. Phosphorus-Containing Biomacromolecules as Flame Retardants

The design of environmentally friendly flame retardant systems for textiles involves another
possible strategy, recently studied [66–68], which is based on the use of some biomacromolecules
(in particular proteins like caseins, hydrophobins and whey proteins, and DNA—deoxyribonucleic
acid). Indeed, the chemical structure of some of these products shows the presence of phosphorus and
other elements (like nitrogen and/or sulphur), which can confer flame retardant features to different
fibers and fabrics.
The use of biomacromolecules as FRs represents a potential innovative strategy that goes far
beyond the chemical approach behind the design of standard flame retardants for textiles. Up to 5 years
ago, the utilization of these biomacromolecules was undoubtedly delineated to other application fields.
Among them, biomacromolecules have been used as edible films, adhesives, food emulsifiers, printing,
papermaking, leather finishing systems, as well as for the design of biosensors and environmental
monitoring systems.
Several advantages can be conferred from the exploitation of proteins and DNA in providing FR
features to textiles [67]: in particular, their ease of manipulation, the possibility of exploiting application
techniques that are already designed and optimized for fabric finishing (like impregnation/exhaustion,
spray, or even the layer-by-layer deposition [69]) and the set-up of low impact/sustainable finishing
recipes (thanks to the use of water-based solutions/dispersions).
In addition, caseins and whey proteins are somehow by-products or even wastes recovered
from the agro-food industry: therefore, their use as possible FRs may represent a new way toward
the valorization of agro-food crops, reducing and/or preventing their landfill confinement. Finally,
the high price of DNA with respect to standard chemical FRs is being overcome, as large scale extraction
and purification processes have been developed [70].
The next paragraphs will describe the main outcomes and accomplishments resulting from
the use of these P-based sustainable products as a valuable, potentially eco-friendly alternative to
traditional chemical FRs for cotton, polyester and cotton-polyester blends. Table 3 summarizes the
main results achieved so far. In particular, some fresh examples of textile fireproofing provided by these
phosphorus-based biomacromolecules will be thoroughly described, highlighting some structure–fire
behavior relationships for the chosen biomacromolecules.
Polymers 2016, 8, 319 27 of 36

Table 3. Main results achieved by treating fabrics with biomacromolecules.

Durability
Type of P-based FR Textile material Highlights Ref.
(washing fastness)
Anticipation of cotton degradation as assessed by TG analyses (T10%onset values:
285 ◦ C vs. 329 ◦ C for treated and untreated fabrics, respectively).
High residue (18%) at 600 ◦ C in nitrogen (TG analyses).
Significant increase of the total burning time (+40%), and strong reduction of the
Casein Cotton No [71]
total burning rate (−35%) with respect to untreated cotton in flammability tests.
Remarkable increase of the final residue after flammability tests (+34%).
Strong reduction of TTI (−52%) and of PHRR (−27%) with respect to untreated
cotton (Cone calorimetry tests).
Anticipation of polyester degradation as assessed by TG analyses (T10%onset values:
315 ◦ C vs. 400 ◦ C for treated and untreated fabrics, respectively).
Increase of LOI after the biomacromolecule treatment (from 21% to 26%).
High residue (22%) at 600 ◦ C in nitrogen (TG analyses).
Significant reduction of the total burning rate (−67%) with respect to untreated
Casein Polyester polyester in flammability tests. No [72]
Remarkable increase of the final residue after flammability tests (+77%).
In cone calorimetry tests, strong reduction of TTI (from 112 to 62 s, for untreated and
treated polyester) and increase of the residue (from 2, neat polyester, to 11%,
treated fabric).
Melt dripping phenomena also observed for the treated fabrics.
Anticipation of fabric blend degradation as assessed by TG analyses (T10%onset
values: 332 ◦ C vs. 304 ◦ C for treated and untreated fabrics, respectively).
High residue (22%) at 600 ◦ C in nitrogen (TG analyses).
Remarkable increase (+64%) of the total burning time and decrease of the total
Cotton-polyester
Casein burning rate (−36%) in flammability tests. No [72]
blend (35%–65%)
Cone calorimetry tests: strong reduction of TTI (from 30 to 12 s, for untreated and
treated fabric blend) and of PHRR (−15%) and increase of the residue (from 3, neat
blend, to 5%, treated fabric).
Slight increase of LOI after the biomacromolecule treatment (from 19% to 21%).
Polymers 2016, 8, 319 28 of 36

Table 3. Cont.

Durability
Type of P-based FR Textile material Highlights Ref.
(washing fastness)
Anticipation of cotton degradation as assessed by TG analyses (T10%onset values:
244 ◦ C vs. 335 ◦ C for treated and untreated fabrics, respectively).
High residue (34%) at 600 ◦ C in nitrogen (TG analyses).
DNA Cotton No [73]
Self-extinction; flame out reached within 2 s.
Cone calorimetry tests: no ignition under a heat flux of 35 kW/m2 .
Significant increase of LOI (from 18, untreated cotton, to 28%, DNA-treated cotton).
10 wt % is the minimum biomacromolecule add-on necessary to reach the flame out
of cotton.
DNA Cotton No [74]
Cone calorimetry tests performed at 50 kW/m2 : remarkable decrease of PHRR
(−60%).
Being equal the final dry add-on on the fabrics, low MW DNA (100–200 bp) is more
effective in enhancing the fire behavior of cotton, with respect to high MW DNA
(3000–10,000 bp), providing the highest residues after horizontal flame spread tests
DNA Cotton No [75]
and self-extinction for about the 86% of the tested samples impregnated at pH = 4.
Cone calorimetry tests performed at 35 kW/m2 on fabrics treated with low MW
DNA: reduction of THR (−36%) and of PHRR (−40%).
LbL treatments with chitosan (20 bi-layers, BL) provide self-extinction to the fabric.
Cone calorimetry tests performed at 35 kW/m2 show a significant decrease of TTI
DNA Cotton (from 39 s, for untreated cotton, to 23 s, for 20 BL-treated fabric), of PHRR (−41%) No [76]
and of THR (−32%); the LbL treatment provide an increase of the residue (from 2%
for untreated cotton, to 13%, for 20 BL-treated fabric).
Polymers 2016, 8, 319 29 of 36

5.1. Caseins
Caseins are phosphorylated proteins that represent the main fraction of milk proteins (around 80%)
and, possibly, the most widely investigated food proteins, obtained as co-products during the
production of skim milk.
Their main constituents are:

• αS1 -caseins: They contain eight or nine bound phosphate groups/mol and represent the major
protein fraction of bovine milk;
• αS2 -caseins: They show a structure similar to αS1 -casein, as they contains, according to its four
differentially phosphorylated isoforms, around 10–13 phosphate groups/mol;
• β-caseins: They are less phosphorylated with respect to αS1 - and αS2 - counterparts. They include
glutamines bearing amino groups and they display a single major phosphorylation site near the
N-terminus. Bovine β-caseins can be sourced in a single, fully phosphorylated form containing
five phosphate groups/mol;
• κ-caseins: As regard to any other casein, these constituents have the smallest phosphate
component. In particular, the phosphorylated regions, present as single sites, are positioned
in the C-terminal region of the biomacromolecule.

Notwithstanding their standard cheese farming uses, these proteins have been mainly employed
as a food ingredient for improving different physical properties like foaming and whipping,
water binding and thickening, texture and emulsification. Furthermore, they have been exploited
as coatings, specifically referring to papermaking, leather finishing, printing and manufacturing of
synthetic fibers [77].
As far as fire retardancy goes, cotton, polyester and cotton polyester blend fabrics (polyester
content: 65 wt %) were treated with a caseins aqueous suspension (5 wt %) in a climatic chamber
(30 ◦ C and 30% R.H.): the suspension was spread onto the samples with a spatula and the excess
was removed by gently pressing with a rotary drum; then the coated samples were dried to constant
weight. The final dry add-on was 20 wt % [71,72].
The presence of the casein coatings promoted a strong anticipation of both cellulose and polyester
decomposition: this behavior, observed for all the types of treated fabrics, was attributed to the
phosphate groups located on the shell of casein micelles, which, upon heating, release phosphoric acid
that favors the degradation of cellulose or polyester toward the formation of a stable char. This latter
exerts a protective effect on the underlying textile, limiting the oxygen diffusion and absorbing the
heat evolved during the combustion [78].
Therefore, the anticipation of the fabric degradation occurs, but, at the same time, is accompanied
by the formation of a thermally stable char.
The fire behavior of the treated fabrics was assessed by flammability tests performed in horizontal
configuration and by LOI tests. In the presence of the casein coatings, a remarkable reduction of the
total burning rate and a strong increase of the final residue were observed, irrespective of the type of
fabric. In particular, the casein coatings provided self-extinction to cotton fabrics, even after a second
flame application; as far as PET is considered, the protein coatings significantly reduced its burning
rate and blocked the flame propagation within 30 mm, giving rise, at the same time, to a remarkable
increase of the final residue. Conversely, the biomacromolecule was not able to suppress the melt
dripping of the synthetic fabric. Furthermore, the protein coatings were responsible for a notable
increase of LOI values of both cotton and polyester (respectively +6% and +5% as compared to the
untreated fabrics); on the other hand, they did not considerably modify the LOI value of the blend.
Finally, cone calorimetry tests were performed at 35 kW/m2 heat flux: both time to ignition and
combustion rate were strongly influenced by the presence of the casein coating, irrespective of the type
of fabric substrate. In particular, despite a significant TTI decrease (indeed, the fabrics were found
to ignite earlier in the presence of the proteins), the peak of heat release rate showed a substantial
Polymers 2016, 8, 319 30 of 36

decrease for coated cotton (−19%) and for the blend (−15%). Finally, the char-forming character of the
proteins on PET was confirmed by a significant increase of the final residue.

5.2. Deoxyribonucleic Acid

It is very well known that deoxyribonucleic acid (DNA) consists of two long polymer chains of
nitrogen-containing bases—namely, adenine (A), guanine (G), cytosine (C) and thymine (T)—with
backbones made of five-carbon sugars (i.e., the deoxyribose units), as well as of phosphate groups tied
by ester bonds. The chains are rolled-up around the same axis and bonded together: this way, a double
helix is formed, which exploits the presence of H-bonds between the bases located side by side and
paired in a specific mode (cytosine bases are combined with guanine, while adenine bases are paired
with thymine).
In the obtained 3D organization, the phosphoric residues and deoxyribose units are oriented
toward the outside of the biomacromolecule; conversely, the paired bases are located in the inner
portion of the polymer and are stabilized by hydrophobic interactions.
The ability of DNA to form double-stranded arrangements has been already utilized for
obtaining several DNA-based nanomaterials, exploitable for applications ranging from life science to
computing: some examples refer to DNA-linked metal nanoparticles, DNA-directed nanowires and
DNA-functionalized carbon nanotubes [79,80].
The use of DNA as a sustainable flame retardant is quite recent and can usually be attributed to the
structure of this biomacromolecule, which represents an all-in-one intumescent system [73–75,81–83].
More specifically, the double helix comprises all three constituents of an intumescent material, namely:
(i) the phosphate groups that form phosphoric acid; (ii) the deoxyribose units, which act as a carbon
source and as blowing agents and (iii) the four nitrogen-containing bases that may give rise to the
formation of NH3 .
Like an intumescent material, when DNA is exposed to a heat source, it develops a multicellular
foamed char, which limits the heat and mass transfer between flame and polymer, hence providing
flame extinction.
The first pioneering work dealing with the flame retardant properties of this biomacromolecule
was published in 2013 and dealt with the use of DNA derived from herring sperm for self-extinguishing
cotton fabrics. To this aim, a standard impregnation/exhaustion method for reaching the desired final
dry add-on (19 wt %) was employed [74]. Among the most important achievements, an improved
thermal and thermo-oxidative stability of the treated fabrics in nitrogen and air, in terms of char residue
formed at high temperatures, was demonstrated. Furthermore, the combustion was blocked, reaching
the flame out within 2 s, after the application of a methane flame in horizontal configuration for 3 s
to the fabrics treated with this biomacromolecule. The remarkable flame retardant features of DNA
were further confirmed by LOI (28 vs. 18% for DNA-treated fabrics and untreated cotton, respectively)
and cone calorimetry tests: these latter showed that none of the DNA-treated specimens ignited upon
exposure to 35 kW/m2 heat flux.
The high char-forming character of deoxyribonucleic acid was attributed to its chemical structure,
where the phosphate groups are able to form phosphoric acid that catalyzes the dehydration of cotton,
favoring its auto-crosslinking toward the formation of a stable aromatic char (that is also formed by
the deoxyribose units) and inhibiting the production of volatile flammable species. This char behaves
as a physical protective barrier on the underlying substrate, limiting the heat, fuel and oxygen transfer
between the fabric and the flame. At the same time, the decomposition of pyrimidine and purine bases
could promote the formation of azo-compounds able to further induce the char development and the
formation of non-combustible gases, like nitrogen, carbon monoxide and carbon dioxide.
Pursuing this research, the effect of different DNA add-ons on cotton flammability was
investigated: for this purpose, three different add-ons (namely 5, 10 and 19 wt %) were deposited
on cotton fabrics, exploiting the same impregnation/exhaustion method [75]. Similarly to other
biomacromolecules, the presence of the coating strongly anticipated the cellulose decomposition,
 Polymers 2016, 8, x FOR PEER 31 of 36

biomacromolecule, which decompose at about 200 °C, releasing phosphoric acid, hence favoring the
Polymers 2016, 8, 319 31 of 36
dehydration of the fabrics, and finally giving rise to the formation of a residue, thermally stable up to
500–600 °C [73,83]. Flammability tests performed in horizontal configuration clearly demonstrated
that was
which the self-extinction
directly relatedoftothe thetreated fabrics in
DNA add-on: strictly depends
particular, on the biomacromolecule
as assessed by TG analyses in add-on:nitrogenin and
particular, the fabrics having the lowest DNA add-on (i.e. 5 wt %) burnt
air, the higher was the biomacromolecule add-on, the lower was the temperature, at which degradation completely, while the other
specimens
started (having
to occur. This10finding
or 19 was wt attributed
% add-on) towere able to achieve
the phosphate groups theof flame out. SEM-EDS
the biomacromolecule,
measurements of the char zone◦ of the residue left by the self-extinguishing coatings proved that the
which decompose at about 200 C, releasing phosphoric acid, hence favoring the dehydration of the
original texture of the fabrics was still preserved and the fibers appeared almost undamaged.
fabrics, and finally giving rise to the formation of a residue, thermally stable up to 500–600 ◦ C [73,83].
Furthermore, their surface was covered by small spherical structures finely dispersed, mainly
Flammability tests performed in horizontal configuration clearly demonstrated that the self-extinction
consisting of C, O and P elements: this was a clear indication of the intumescent character of the
of the treated fabrics strictly depends on the biomacromolecule add-on: in particular, the fabrics
biomacromolecule.
having the lowest DNA add-on (i.e., 5 wt %) burnt completely, while the other specimens (having
Pursuing this research, very recently, Bosco et al. deeply studied the effect of different
10 parameters
or 19 wt % add-on) were able
(i.e. molecular size,to pH
achieve the flame
of aqueous out. SEM-EDS
solutions, numbermeasurements
of impregnations) of theoncharthezone
fire of
thebehavior
residue of leftdeoxyribonucleic
by the self-extinguishing coatings proved that the original texture
acid [75]. Flame spread and cone calorimetry tests showed that the of the fabrics was
still preserved
coatings and from
derived the fibers appeared size
low molecular almost
DNA undamaged.
significantly Furthermore,
improved thetheir fire surface
behaviorwas covered
of the fabric by
small spherical structures finely dispersed, mainly consisting of C, O
substrate, which they were applied to. In addition, the fire behavior was better enhanced when and P elements: this was a clear
indication of the intumescent character of the biomacromolecule.
multiple impregnations were used instead of a single one, for achieving the same final add-on. In
Pursuingthe
particular, thisuseresearch, very impregnations
of multiple recently, Bosco at et pH
al. deeply
4 and 8studied
provided the 86%
effectandof different
74% of the parameters
tested
(i.e., molecular
samples size, pH of aqueous
with self-extinction, solutions,
respectively; numberthese
furthermore, of impregnations)
treated fabrics showedon the fire45%behavior
and 25% of
reduction of THRacid
deoxyribonucleic and [75].
pkHRR whenspread
Flame were exposed
and cone to 35calorimetry
kW/m2 heat tests flux, with
showed respect
thattothe
untreated
coatings
cotton.from
derived These low results were attributed
molecular size DNA to the higher ease
significantly of diffusion
improved the fireofbehavior
the low molecular
of the fabricsizesubstrate,
DNA
coating
which within
they werethe fabric microfibrillar
applied to. In addition, surfaces,
the and
fire to its higher
behavior thermal
was betterstability
enhanced in air.
when multiple
Quite recently,
impregnations were used DNA was also
instead of a exploited
single one, asfor a component
achieving the of same
layer final
by layer (LbL)Incoatings:
add-on. particular,
indeed, its assemblies were found to improve the flame
the use of multiple impregnations at pH 4 and 8 provided 86% and 74% of the tested retardant features of the treated
samplesfabrics,
with
keeping, at the same time, a green character.
self-extinction, respectively; furthermore, these treated fabrics showed 45% and 25% reduction of THR
and pkHRR In particular,
when were Carosio and to
exposed co-workers
35 kW/m[76] combined
2 heat flux, with DNA (negatively
respect to untreatedcharged)
cotton.with chitosan
These results
layers (positively charged) on cotton, thus building up an assembly containing up to 20 bi-layers.
were attributed to the higher ease of diffusion of the low molecular size DNA coating within the fabric
The structure of the obtained LbL assembly is schematized in Figure 30.
microfibrillar surfaces, and to its higher thermal stability in air.
The formation of the LbL architecture was investigated and confirmed through infrared
Quite recently, DNA was also exploited as a component of layer by layer (LbL) coatings: indeed,
spectroscopy and SEM analyses. In the presence of chitosan, DNA layers were found to favor the
its assemblies were found to improve the flame retardant features of the treated fabrics, keeping, at the
char forming character of the former biomacromolecule. In particular, the deposited coatings were
same
abletime, a greencotton
to provide character.
fabrics with self-extinction in horizontal flame spread tests and to increase
In particular, Carosio
LOI values from 18% (uncoated and co-workers
cotton) to [76]24%
combined
(cotton DNA treated(negatively charged)Finally,
with 20 bilayers). with chitosan
cone
layers (positively
calorimetry testscharged)
showed aon HRRcotton, thusofbuilding
decrease 40% andup an assembly
a remarkable containing
increase of the up
finaltoresidue
20 bi-layers.
for
The structure of the obtained LbL assembly
the fabrics treated with the highest number of layers. is schematized in Figure 30.

1 cycle

1 Bi-layer

FABRIC

Adsorption Washing Adsorption from Washing

from chitosan DNA solution
solution

Repeat

Figure30.
Figure 30.Scheme
Scheme of
of the
the chitosan-DNA
chitosan-DNALbL
LbLassembly.
assembly.

6. Conclusions
The formation of the LbL architecture was investigated and confirmed through infrared
spectroscopy and SEM analyses. In the presence of chitosan, DNA layers were found to favor the char
forming character of the former biomacromolecule. In particular, the deposited coatings were able to
provide cotton fabrics with self-extinction in horizontal flame spread tests and to increase LOI values
from 18% (uncoated cotton) to 24% (cotton treated with 20 bilayers). Finally, cone calorimetry tests
Polymers 2016, 8, 319 32 of 36

showed a HRR decrease of 40% and a remarkable increase of the final residue for the fabrics treated
with the highest number of layers.

6. Conclusions
This work has clearly depicted the wide potentialities offered by the use of novel
phosphorus-based flame retardants as a real (and not only potential) alternative to the toxic flame
retardant products. Indeed, the wide possibility of tailoring the structures of the phosphorus-based
additives allows exploiting an almost infinite number of FR systems that show high efficiency and
suitability for different fibers and fabrics. Furthermore, the concurrent presence of phosphorus and
other elements (like nitrogen, silicon and sulphur) may be very important in order to develop additive
or synergistic effects during the exposure of the treated textiles to a flame or to a heat source.
Though the phosphorus based flame retardants are being developed as an alternative to toxic
halogenated counterparts, before they can find real application, they need to be screened thoroughly
for toxicity. It is encouraging to see that there are some efforts by researchers where the toxicity of new
phosphorus based flame retardants has been evaluated and these latter have shown a low toxicity
profile [7,8].
Despite the high flame retardant efficiency observed for most of the chemical and low impact FRs,
there are still some unresolved issues that deserve further attention.
First of all, the design of any new P-based flame retardant product requires large investment
either for assessing its suitability for the desired application (especially from a toxicological point of
view) or for scaling-up the production from a lab-scale quantity to at least a pre-industrial scale, trying
to maximize yields and reduce expenses.
Particularly referring to biomacromolecules, the possibility of adjusting the green technological
approach to a larger scale than the lab scale (at least to pre-industrialization) is still under assessment
and the final decision will be largely based on the cost-effectiveness of the described biomacromolecules.
Definitely, the cost of some of the discussed biomacromolecules, such as DNA, is presently very high:
therefore, their use as low impact FRs could be foreseen only on the basis of a significant cost reduction.
Second, the industrial world working in the field of flame retardant finishing for textiles is fully
conscious that any novel flame retardant product should exhibit, apart from a high efficiency, durability
to laundering: At present, some of the proposed P-based FRs (like the proposed phosphorus-containing
biomacromolecules) cannot accomplish this goal. Indeed, they show no washing fastness at all, or, in
some cases, a limited durability up to few washing cycles. This surely represents a current drawback
that limits the use of the treated textiles to those restricted applications for which durability to washing
treatments is not required. Thus, further research will also have to consider the design of new strategies
able to overcome this challenging issue.

Acknowledgments: The European COST Action “Sustainable flame retardancy for textiles and related materials
based on nanoparticles substituting conventional chemicals”, FLARETEX (MP1105) is gratefully acknowledged.
Author Contributions: Khalifah A. Salmeia, Sabyasachi Gaan and Giulio Malucelli equally contributed to the
writing of the review manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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