CHEMICAL STRUCTURE AND

EFFECTIVENES

STUDENT NAME: TANVEER AHMED 1

(March 2012)
• Flame-retardant finishes provide textiles with an
important performance characteristic.
 Protection of consumers from unsafe apparel
 Firefighters and emergency personnel require protection
 Floor coverings, upholstery and drapery protection
 The military
 the airline industry

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• Combustion:
is an exothermic process
that requires three
components,
Heat
oxygen
suitable fuel.

3
• Pyrolysis temperature, TP,
• At this temperature, the fibre
undergoes irreversible chemical
changes, producing
 non-flammable gases (carbon
dioxide, water vapour and the
higher oxides of nitrogen and
sulfur),
 carbonaceous char,
 tars (liquid condensates) and
 flammable gases (carbon
monoxide, hydrogen and many
oxidisable organic molecules).
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• the combustion temperature, TC,
• At this point, the flammable gases combine
with oxygen in the process called combustion,
 which is a series of gas phase free radical
reactions.

 These reactions are highly exothermic

 and produce large amounts of heat and light.
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1. Heat Sink on / in the fibre

2. Insulating Layer

3. Condensed Phase: reaction to produce less

flammable volatiles and more residual char.

4. To interfere with the free radical reactions

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1. Heat Sink on / in the fibre
 by use of materials that thermally decompose through
strongly endothermic reactions.
 If enough heat can be absorbed by these reactions, the
pyrolysis temperature of the fibre is not reached and no
combustion takes place.
Examples of this method are
 the use of aluminium hydroxide or ‘alumina trihydrate’
 and calcium carbonate as fillers in polymers and coatings

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2. Insulating Layer
• to apply a material that forms an insulating layer around the
fibre at temperatures below the fibre pyrolysis temperature.

Boric acid and its hydrated salts function in this capacity. When
heated, these low melting compounds
 release water vapour
 and produce a foamed glassy surface on the fibre,
insulating the fibre from the applied heat and oxygen.

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• Condensed Phase: reaction to produce less
flammable volatiles and more residual char.
 This ‘condensed phase' mechanism can be seen in the
action of phosphorous-containing flame retardants
 which, after having produced phosphoric acid
 through thermal decomposition,
 crosslink with hydroxyl-containing polymers thereby
altering the pyrolysis to yield less flammable by-product.

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• But there are also other
explanations for
• the first steps of this
dehydration,
 including single
esterification without
crosslinking,
• for example, of the
primary hydroxyl group in
the C-6 position of the
cellulose units.

 These phosphorous esters

catalyse the dehydration (Fig. 8.6)
Esterification is a process involving the
 and prevent the formation of interaction of a compound possessing a
undesired levoglucosan (Fig. 8.7),
the precursor of flammable hydroxyl group (oH)with an acid, with the
volatiles. elimination of water.
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A phosphoric acid ester
The ‘condensed phase’ strategy includes the described mechanism
of removal of heat and the enhancement of the decomposition
temperature as in heat resistant fibres.

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4. To interfere with the free
radical reactions
• free radical reactions (that provide
the heat needed for the process
• to continue. Materials that act in
this ‘gas phase’ mechanism
include halogencontaining
• compounds which, during
combustion, yield hydrogen
halides that
• form relatively long lived, less
reactive free radicals, effectively
reducing the heat
• available for perpetuating the
combustion cycle, and which
decrease the oxygen content by
flame gas dilution (Fig. 8.8).

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• Condensed phase • Gas phase
• Pyrolysis chemistry • Flame chemistry

• Typical type of • Typical type of synergism

synergism (P/N) (Sb/Br or Sb/Cl)

• Effective for fibre type Mainly

• All kinds of fibres, because
cellulose, also wool, catalysing
their flame chemistry is similar
their dehydration to char.
(radical transfer reactions)

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• Condensed phase • Gas phase
Particularities Particularities

• Very effective because • Fixation with binder

dehydration and changes textile properties
carbonization decrease the such as
formation of burnable • handle and drape,
volatiles
preferably for back
coating,
• for example
• of furnishing fabrics
• and carpets 14
• Condensed phase • Gas phase
Application process Application process

• If for durable flame • Relatively simple,

• retardancy then standard methods of
demanding multi-step coating, but viscosity
processes control is important

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• Condensed phase • Gas phase
Environment, toxicity • Environment,
toxicity
• With durable flame retardancy,
formaldehyde emission
• Antimony oxide and
 during curing
organic halogen donators
 and after finishing,
(DBDPO and HCBC) are
• phosphorous compounds in the
waste water discussed as problems
• (for example possibility of
generating
polyhalogenated dioxins
and furanes) 16
17
• The most important commercial flame retardants can be
classified into three broad categories.
• Primary flame retardants based on phosphorous
(condensed phase mechanism) and halogens (gas phase
mechanism)
• synergistic retardancy enhancers that have only small
flame retarding effects by themselves, but greatly
enhance the flame retardancy of primary flame retardants
(nitrogen with phosphorous and antimony with halogens)
• adjunctive flame retardants that exhibit their activity
through physical effects (borates, alumina trihydrate,
calcium carbonate and intumescents.
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• Control the pH
• Organic nitrogen is thought to help control the pH
during the crosslinking reactions of phosphoric acid.
 The nitrogen can become protonated, reducing the
amount of acid available.
 If the pH is too low, cellulose will undergo acid hydrolysis
rather than crosslinking.
 If the pH is too high, the acid catalysed crosslinking
cannot take place.
• Organic nitrogen may be converted to phosphorous acid
amides that also catalyse the dehydration and
carbonisation of cellulose.

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• The synergistic
effect of antimony
comes from the
volatility of antimony
trihalides and the
effectiveness of
antimony compounds
in scavenging free
radicals over a broad
temperature range (for
example 245–565 °C).
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 • Synergistic combination • Generated
Suitable for primary active
P / N ----- For Cellulose compounds
 Halogen (X) / Sb2O3 ---------- for H3PO4, P-
Synthetic fibres, especially PAN, PP,
PA
amides
SbOX → SbX3
 P/ halogen (X) for PP, (PET, PAN,
PA)
POX3, PX3

 Halogen/radical generator ------ for

PP = Synthetic fibres,
polypropylene, PET especially
= polyethylene PET,
tetrachloride, PAN CT, Halogenated
= polyacrylonitrile, PA= polyamide, CT = cellulose
triacetate, 21
CA
CA = cellulose acetate. polymers
thermal degradation mechanism of cellulose fibres (cotton, rayon,linen,
etc.) is the formation of the small depolymerisation product
levoglucosan.
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• Levoglucosan:
• Levoglucosan and its volatile pyrolysis products are
extremely flammable materials and are the main
contributors to cellulose combustion.

• Compounds that are able to hinder levoglucosan

formation are expected to function as flame retardants for
cellulose. 23
 • Levoglucosan:
• The crosslinking and the single type of esterification of cellulose polymer chains
by phosphoric acid reduces levoglucosan generation, catalyses dehydration and
carbonisation, and thus functions as an effective flame retardant mechanism.

• This carbonisation of cellulose is similar to the well knowncarbonisation process

of wool with sulfuric acid, removing plant dirt and other cellulosics.
• In an idealised equation, flame-retardant finished cellulose (C6H10O5)n would
be decomposed to 6n C and 5n H2O. The first step of this reaction is shown in
Fig. 8.6.
• The resulting char is much less flammable than the volatile organic pyrolysis
products of untreated cellulose.
Esterification is a process involving the interaction of a compound possessing a hydroxyl group (oH)with an
acid, with the elimination of water. 24
• Chemicals that can yield phosphoric acid during the early
stages of fibre pyrolysis
• form the majority of successful flame retardants for cellulose.

• The presence of nitrogen has been found to provide

• a synergistic effect with phosphorous.

• Minimum levels of added phosphorous and nitrogen for

effective flame retardancy have been estimated
• at ~ 2% P and ~1 % N. depending on fabric construction and test
requirements.

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 Non-durable
• Inorganic salts have long been
known to provide flame retardancy
on cellulosic material that will not be
exposed to water, rain or
perspiration.
• The French chemist Gay-Lussac
proposed a borax and ammonium
sulfate treatment as a flame
retardant for cotton in 1820.
• Today, a mixture of boric acid and
borax is still an effective flame
retardant for cotton at ~ 10 % solids
add-on.
• Ammonium salts of strong acids,
especially phosphoric acid (P/N
synergism) are particularly useful as
nondurable flame retardants for
cellulose.

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 Non-durable
• Three commercially important products are
1. diammonium phosphate (DAP),
2. ammonium sulfamate
3. and ammonium bromide.
• These salts readily form the corresponding
strong acids upon heating.
• Diammonium phosphate and ammonium
sulfamate are used at ~ 15 % solids addon and
function as condensed phase flame retardants,
• not only by crosslinking but also by dehydrating
cellulose to polymeric char with reduced
formation of flammable by-products
• The water insoluble ammonium polyphosphate
is an effective flame retardant and is added to
coatings and binder systems, for example for
pigment printing. Ammonium bromide is applied
at ~ 10 % solids add-on and is effective in the
gas phase.

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• The most successful durable flame retardants for
cellulose are based on
 phosphorous- and nitrogen-containing chemical systems
 that can react with the fibre or form crosslinked structures on the fibre.

• The key ingredient of one of these finishes is

 tetrakis(hydroxymethyl)phosphonium chloride (THPC),
 made from phosphine, formaldehyde and hydrochloric acid

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• THPC reacts with urea to form an
insoluble structure on cellulose in a pad–dry–cure process

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• Treating the cured finish with hydrogen peroxide to
convert the phosphorous atoms
 to their highest oxidation state
 results in cellulosic goods with very durable flame retardancy.
• Applying 25 % THPC with 15 % urea yields a
 final phosphorous add-on of 3.5–4 %,
 which is adequate for most fabrics.
• Although the THPC–urea system can give highly
effective and durable flame retardancy to cellulose,
treated fabrics are
stiff and have significantly impaired tensile and tear strengths as well
as releasing formaldehyde during processing.
• Typically, carefully chosen softeners and mechanical
finishing techniques are used
 to provide commercially acceptable fabrics.
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• Variations on THPC-based systems have been the use of
the sulfate or hydroxy salts;
THP-S to eliminate the possible formation of highly toxic
bis(chloromethyl) ether during processing, and
THP-OH to reduce acidic tendering of the goods.
• A variation on the THPC–urea system was developed to
produce finishes with
 less stiffness and fibre damage (Proban process).
• A precondensate is prepared by
 the careful reaction of THPC with urea.
• This precondensate is padded onto the fabric and the
fabric is dried to a specific moisture content (~ 15 %).
The fabric is
then exposed to ammonia vapours in a special reaction chamber,
followed by oxidation with hydrogen peroxide (Fig. 8.13).
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• The polymer that forms is primarily located
 in the lumen of the cotton fibre.

• The final finish provides durable flame retardancy to

cotton
 with much improved fabric properties.

• It is important to note that very few direct or fibre reactive

dyes
 can withstand exposure to THP-based finishes.

• Almost all cellulosic goods that are to be flame retardant

treated with a THP finish should be dyed
 with vat dyes.

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the use of N-methylol dimethylphosphonopropionamide in
combination with
Trimethylol melamine and phosphoric acid as catalyst
in a pad–dry–cure process.

Another successful commercial approach to durable phosphorous-containing

finish
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The required add-on is 20–30 % depending on
the weight of the fabric.
 In this process, washing after curing is necessary to remove
the phosphoric acid,
leading to higher costs associated with the second drying step.
In addition, the finish may give rise to an unpleasant odour during
the curing step.

Novel developments
include higher product purity, decrease in formaldehyde emission during curing
and by the finished textile, and also higher fixation rates enabled by moderate
condensation conditions (accompanied by less fibre damage).

Another successful commercial approach to durable phosphorous-

containing finish
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 N-methylol
phosponopropionamide
Modified THPC–urea finish(‘Pyrocatex CP new’
finish(‘Proban’ type) type)
 Demanding process, including  Extra washing after curing
• moisture control, including
• ammonia vapour treatment
• and oxidation
• drying costs
 Smaller wash shrinkage  Softer handle
 Better stability to hydrolysis  Fewer dyestuff restrictions,
including brilliant shades After
 Somewhat better ripping handle
strength
 Much less free formaldehyde
 Less odour bothering development
 Also for fibre blends with small  Shorter after-burning time
cellulose content
 Less smoke development
 Preferably for large production
runs,  No licence required, including
• to minimise the process costs • corresponding restrictions and
including machinery requirements costs

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• Rayon can be flame retarded
by the same processes
• developed for cotton

• the majority of research

efforts have focused on
• additives to the viscose spinning
bath.

• One successful additive,

based on an
• Alkyl di-oxa-phos-phori-nane
disulfide
• is used at ~ 20 % for effective
flame retardancy.

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 • Name: Zirconium
Symbol: Zr
Atomic Number: 40
Atomic Mass: 91.224 amu
Melting Point: 1852.0 °C (2125.15 K, 3365.6
°F)
Boiling Point: 4377.0 °C (4650.15 K, 7910.6 °F)
Number of Protons/Electrons: 40
Number of Neutrons: 51
Classification: Transition Metal
Date of
Discovery: 1789 Crystal Structure: Hexagonal
Discoverer: Martin Density @ 293 K: 6.49 g/cm3
Klaproth
Name Origin: zircon Color: Grayish
(mineral)
Uses: nuclear Number of Energy Levels: 5
applications First Energy Level: 2
Obtained From: zircon,
baddeleyite Second Energy Level: 8
Third Energy Level: 18
Fourth Energy Level: 10
Fifth Energy Level: 2

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• wool fibres are inherently less
flammable
• One well known process
• (Zirpro, developed by Benisek for the IWS)
• is based on hexafluoro zirconate and titanate
salts
• These products can be applied
• by exhaustion
• and pad processes under acid conditions (at pH
< 3).
• The heavy metal complex anions
form
ionic and perhaps other polar bonds with the
wool fibre,
similar to dyestuff anions
The flame-retardancy mechanism is
thought to take place
 in the condensed phase
through zirconium ions or zirconium 39
compounds
 The hexafluoro titanium salt is
more effective and cheaper,
but a yellow shade is imparted to the treated
wool,
which is increased by exposure to light.
• The finish is durable
 to dry cleaning and water washing
up to 40 °C
at pH < 6.
At higher pH values ineffective zirconium
oxide is formed
Repellent finishes • This finish can be combined with
should be applied
after the Zirpro
dyeing
at pH < 3 (levelling acid
process
or 1:1 metal complex dyes).
• It is compatible with
shrink-resist and insect-resist finishes
• This finish was modified for wool
used for
thermal insulation material,
especially with skin contact,
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enabling less strength loss after heating
 • Another flame-retardant
treatment for wool based on
exhaustion of an anionic
species is the use of
Tetra-bromo-phthalic anhydride, TBPA
• Which hydrolyses
to the carboxylic form during
application.
• Use of TBPA at ~ 10 % on
weight of fabric under acid
conditions provides
effective flame retardancy that is
durable to dry cleaning
and mild laundering conditions (cold
water washing at neutral pH).
Tetra-bromo-phthalic • But TBPA is suspected to
anhydride, TBPA
generate polybrominated
dioxins 41
Under burning conditions.
 The three possible
approaches to flame-
retardant polyester –
additives to the polymer
melt,
 flame-retardant
copolymers
and topical finishes –
have all been used
commercially to produce
All the methods flame-retardant polyester
employ phosphorous- or bromine- textiles
containing compounds as the active flame
retardant.

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• One of the most useful flame-
retardant finishes for polyester was a
Bromine containing phosphate ester,
Tris-dibromo-propyl-phosphate, commonly
known as ‘Tris’
• Most simple phosphate triesters could
also have been given the
• name of ‘tris’ for simplicity but the best
known is
 the dibromo-propyl product
• ‘Tris’ was an extremely versatile and
effective product, being applied by
both
padding and exhaustion processes
(even though the substantivity and exhaustion
yields were low)
and provided excellent flame retardancy at
reasonable add-ons.
• ‘tris’ was shown to be a potential
carcinogen and was eventually
43
removed from the marketplace by legislation
 • Heat set conditions of
190–210ºC
for 0.5–2 min are adequate.

• This product when applied

at ~ 3–4 % add-on can
provide
One current commercial durable flame retardancy to a
flame retardant for polyester wide variety of polyester
is a mixture of
textiles.
Cyclic
phosphate/phosphonates
used in a pad–dry–heat set
process

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 • One particularly useful
material is
 hexa-bromo-cyclo-dodecane
(HBCD)

• To achieve durable flame

retardancy, fabric padded
with ~ 8% of a dispersion of this
Another approach to
durable flame retardant water insoluble material
finishes for polyester is the
use of must be heated above 190 °C
highly brominated or 375 °F
chemicals as topical
finishes to form a film of the flame
retardant on the fibre surface.
Polyester fabrics when burned exhibit a melt–drip behaviour. Since the fabric melts away
from the flame, some polyester fabric constructions can actually pass vertical flame tests
without any flame-retardant treatment.
The waiving of melt– drip specifications for children’s sleepwear has allowed untreated
polyester garments to be sold into that market. 45
46
• The topical flame-retardant
finishes for nylon that are of
special interest are the
treatments based on
 the condensation product of
thio-urea with formaldehyde and
urea.
• The flame-retardancy effect of
these products is attributed
 to the lowering of the melting
point of nylon by 40 ºC
 and allowing the fibre to drip
away from the ignition source
• Common practice in nylon flame
retardancy, especially for nylon
carpets, is
 back-coating with antimony
trioxide
 combined with bromine donators 47
and a binder as shown in Fig
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DIFFICULTIES ARE PART OF LIFE…..

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