CHEMICAL STRUCTURE AND

EFFECTIVENES

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• 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.

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• 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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• Limiting Oxygen Index (LOI) This is the amount of oxygen in the
fuel mix needed to support combustion. The higher the number, the
more difficult it is for combustion to occur
• Flammability Parameters for Fibers

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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)

 and prevent the formation of

undesired levoglucosan (Fig. 8.7), the
precursor of flammable volatiles. Esterification is a process involving the interaction of a
compound possessing a hydroxyl group (oH)with an
acid, with the elimination of water.

A phosphoric acid ester 11

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 their
cellulose, also wool, catalysing their
flame chemistry is similar (radical
dehydration to char.
transfer reactions)

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• Condensed phase
Particularities
• Very effective because
dehydration and carbonization
decrease the formation of
burnable volatiles
• Gas phase
Particularities
• Fixation with binder changes
textile properties such as
• handle and drape,
preferably for back coating,
• for example
• of furnishing fabrics
• and carpets
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• Condensed phase • Gas phase
Application process Application process

• If for durable flame • Relatively simple, standard

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

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• Condensed phase
Environment, toxicity
• With durable flame retardancy,
formaldehyde emission
 during curing
 and after finishing,
• phosphorous compounds in the
waste water
• Gas phase
• Environment, toxicity
• Antimony oxide and organic
halogen donators (DBDPO
and HCBC) are discussed as
problems
• (for example possibility of
generating polyhalogenated
dioxins and furanes)
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18
• 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 primary
Suitable for active compounds
P / N ----- For Cellulose H3PO4, P-amides
 Halogen (X) / Sb2O3 ---------- for SbOX → SbX3
Synthetic fibres, especially PAN, PP, PA

 P/ halogen (X) for PP, (PET, PAN, PA) POX3, PX3

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

Synthetic fibres, especially PET, CT, CA
polymers
PP = polypropylene, PET = polyethylene tetrachloride, PAN = polyacrylonitrile, PA= polyamide, CT = cellulose triacetate,
CA = cellulose acetate. 22
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.
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 • 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 known carbonisation process of wool
with sulfuric acid, removing plant dirt and other cellulosic's.
• 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. 25
• 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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 Modified THPC–urea N-methylol phosponopropionamide
finish(‘Proban’ type) finish(‘Pyrocatex CP new’ 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 strength handle
 Less odour bothering  Much less free formaldehyde
 Also for fibre blends with small development
cellulose content  Shorter after-burning time
 Preferably for large production  Less smoke development
runs,
• to minimise the process costs including  No licence required, including
machinery requirements • corresponding restrictions and costs

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