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Polymer Combustion Processes. 3.

Flame Retardants for Polymeric Materials

Polymer Combustion Processes.


3. Flame Retardants for Polymeric Materials

S. Boryniec
Instytut Wlókien Chemicznych,
ul. M. Slodowskiej-Curie 19/27, 90-570 Lodz, Poland

W. Przygocki
Lódz Polytechnic,
ul. Zeromskiego 116, 90-924 Lódz, Poland

ECONOMIC IMPORTANCE OF FLAME RETARDANTS


The purpose of flame retardants or inhibitors(1), is to increase the fire
resistance of polymeric materials or to modify their behaviour in a flame.
They may carry out both of these functions simultaneously. The following
four groups of flame retardants are produced on industrial scales:

• bromine and chlorine compounds,


• organic phosphorus compounds,
• aluminium hydroxide, Al(OH)3,or ATH
• antimony trioxide, Sb2O3.

Apart from these, many other chemical substances have been used in
practice. These include certain organic nitrogen compounds and inorganic
compounds of phosphorus, manganese, molybdenum, boron, zinc and
silicon. These make it possible to provide specific flame retardant
characteristics required by users of polymeric materials. Polymeric materials
with additives altering their flammability are widely used in many areas of
the national economy. Their chief uses are in branches of industry such
as building and associated areas (furniture-making, production of settees,
mattresses, bed fabrics etc.), the electrical engineering and electronics
industry (insulation of cables and wires, sockets, plugs, cassettes, housings,
boards for integrated circuits etc.) and the transport industry.

*This paper was first published in International Polymer Science and Technology, Vol. 27,
No. 10, 2000 (in Polish)

Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001 127
S. Boryniec and W. Przygocki

Each of these markets for flame retardants has specific requirements


and expectations regarding the action and effectiveness of these agents.
For instance, in electrical engineering and electronics a potential source
of ignition is the electrical energy that is often present. The main objective
here is to prevent the formation of a flame and its conversion to a full-
blown fire. On the other hand, in the transport industry the main
requirement is to ensure that there is a fairly long period of time from the
appearance of fire to its propagation. This time is necessary for instance
for the safe evacuation of a train by its passengers. In building the degree
of fire risk depends on many factors. The risk is different in the case of the
spreading of a fire from one building to another, from what it is for the
propagation of a fire inside a building, e.g. for the ignition of a bed or
furniture in an enclosed space. These differences in expectations determine
the use of different technologies for fire retardance.
In the industrially developed countries the public are dependent on
industrial products based with polymeric materials and electronics. The
products formed as a result of fire may give rise to corrosion phenomena
in these devices, and this in turn may threaten to paralyse control and
communication systems. Results of this kind can be expected after a fire
involving flame retardants containing halogens. Ecological regulations are
another factor influencing the type of fire retardants employed. In recent
years, problems of environmental protection have been observed to have
a considerable influence on progress in the sphere of chemistry of flame
retardants(7,8).
There has been a dynamic growth in the demand for flame retardants
for many years now. For instance, in the USA in 1975 over 100,000 tons
of the flame retardants mentioned above were produced, and by 1990
production rose to about 320,000 tons(3). New consumers and outlets are
emerging. In 1975 the demand for combustion inhibitors in the electronics
industry was for practical purposes, zero, whereas currently it is one of the
main users of these. There has also been a marked increase in the demand
for these agents in the cable and electric wire industry.

THE PHENOMENON OF COMBUSTION OF POLYMERS


The combustion of polymers is a multi-stage process involving many
mutually associated chemical and physical phenomena(9-16). A general
simplified diagram of combustion is shown in Figure 1.
Combustion starts with the heating up of a solid polymeric material
following absorption from the environment of heat Q1 or radiation (e.g.
laser). After reaching the appropriate temperature, processes of
degradation, breakdown and pyrolysis begin in the polymer. These take

128 Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001
Polymer Combustion Processes. 3. Flame Retardants for Polymeric Materials

Figure 1 A simplified polymer combustion scheme: Q1: heat supplied; Q: heat


of combustion; Q': portion of heat Q absorbed by polymer (see text for
explanations)

Q1

O1
Polymer

Heat Gaseous
absorbed by products of
the polymer pyrolysis
Q'

Combustion
products Ignition
of polymer
Q

Light
radiation
and heat
dispersed

place in the slip phase and involve many chemical reactions which are
often mutually related. The speed of these is affected by the temperature
and accompanying physical phenomena connected with the transport of
heat and mass. Volatile products of pyrolysis are accumulated in the
vicinity of the surface of the material where they become mixed with
atmospheric oxygen and are transformed into a flammable mixture. The
rate of mixing depends on the diffusion of oxygen. Under favourable
conditions the flammable mixture may undergo ignition – induced or
spontaneous. A flame appears, in which exothermic oxidation reactions
take place and the heat Q and light radiation are emitted. Part of the heat
formed (Q') and the radiation is absorbed by the solid polymer. This
energy ensures the continuation of the formation of volatile pyrolysis
products and the maintenance of combustion in the flame. The heat and
radiation absorbed in another place generate new fire sites. The fire is
converted into a spontaneously propagating, unrestrained phenomenon
which rapidly reaches catastrophic dimensions.

Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001 129
S. Boryniec and W. Przygocki

The course of events described above raises the question whether by


precise design of the composition of the polymeric material it is possible
to a limited degree, to reduce the rapid spread of combustion and reduce
its consequences? The answer is yes. There are agents which will impede
ignition, combustion of polymers and flame propagation. These are
chemical agents which on being mixed with the polymer increase its
resistance to combustion and reduce the risk of an outbreak of fire. In the
English language literature they are referred to by the abbreviation FR
(from Fire Retardants or Flame Retardants).

RETARDATION OF COMBUSTION
The purpose of flame retardants is to increase the resistance of a
polymeric material to combustion under defined use conditions, connected
with the minimum possible deterioration in its service properties, and with
the lowest possible increase in product costs. From Figure 1 it is seen that
it is possible to interfere in the processes occurring in the solid phase of
the polymeric material and in the gaseous phase in the flame zone. The
action of flame retardants can therefore be described as follows:

a) Impeding processes of pyrolysis and changing the composition of


the decomposition products of the polymer so as to increase the
concentration of non-volatile components as against volatile and
flammable components. A poorly flammable mixture (i.e. a mixture
with an excessively low concentration of flammable components)
cannot ignite spontaneously and will not satisfactorily support
combustion in a flame. Active flame retardants in the solid phase
accelerate the formation of the carbonised part and the conversion
of the polymer to a coke. They can also enter into an endothermic
reaction with decomposition products. The consequence of this is a
loweri&Béof the temperatuqê and decrease in the rate of decomposition
of the polymer. This result can be achieved by flame retardants with
a high heat capacity and thermal conductivity. The former absorb the
heat and the latter conduct it out of the polymer, which causes a
reduction in the temperature.

b) The introduction of active inhibitors in the gaseous phase, taking


part in the chemical reactions occurring in the combustion zone in
the flame. Flame retardants or their products of decomposition can
capture free radicals or enter into a series of chemical reactions as
a result which the more reactive radicals are replaced by less reactive

130 Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001
Polymer Combustion Processes. 3. Flame Retardants for Polymeric Materials

ones. The end result is a reduction in the flame temperature or even


the initiation of a negative thermal feedback, leading to extinction of
the flame.

c) It is possible also to combine the two mechanisms. Combustion is


affected by the flame retardants also owing to the stimulation of
physical phenomena. Some active flame retardants break down in
the solid phase to form a large amount of inert gas (e.g. CO2 or N2),
which dilutes the flammable mixture or reduces the oxygen
concentration in the immediate vicinity of the polymeric material. In
such a case the contribution of the physical mechanism in the
process of extinguishing of the fire is clearly evident.

The action of flame retardants in the combustion of polymers is thus


as a rule complex and can take place according to several mechanisms
simultaneously. The complexity of the phenomenon is affected by many
factors including e.g. the chemical structure of the polymer and of the
flame retardant, the ambient conditions, the type of product and its
physical properties(17).

AGENTS RETARDING THE COMBUSTION OF POLYMERS


For the purpose of making conventional polymeric materials resistant to
ignition, flame combustion, fire propagation and the formation of smoke
and toxic gases, at a certain stage of production powdered chemicals are
added to them which should be homogeneously dispersed in them during
processing. Obviously the purpose is to fulfil all of the requirements
mentioned above simultaneously. It should be noted that it is of great
practical importance to counteract the formation of smoke and toxic
gases, since almost 80% of fatalities in fires involving polymeric materials
have been caused by the inhalation of smoke(18,19).

Metal hydroxides
Inorganic metal hydroxides make up more than 50% of the mass of all
flame retardants sold worldwide(6,20,21). Depending on the type of polymeric
material and its end-use, a flame retardant filler is added in amounts of
5 to as much as 65 mass %, especially in the case of Al(OH)3 (also known
by the abbreviation ATH). The advantages of ATH are primarily its
relatively low cost, ease of storage and the lack of toxicity or corrosive
effect of combustion products(22,23).

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S. Boryniec and W. Przygocki

Polymers with large amounts of flame retardant added, can be regarded


as composites. The high content of flame retardant in the final product
significantly reduces the concentration of potential flammable component,
which is the polymer. During combustion a lower amount of heat is
formed, and also significantly less smoke is released.
Apart from ATH the most frequently employed metal hydroxide is
magnesium hydroxide, Mg(OH)2. Both of these agents contain a large
quantity of combined water, 34.6% in the case of ATH and 31% in the
case of Mg(OH)2. The endothermic process of dehydration of Al(OH)3
absorbs a considerable amount of energy (around 1170 kJ/kg(23)). ATH
thus acts like an apparent 'thermal well', preventing the polymer from
heating up to the ignition temperature. The released water vapour
proceeds to the combustion zone in the flame, where as an additional
component it reduces the concentration of flammable gases and oxygen.
As a result there is a reduction in the temperature of the flame. And finally
the metal oxides derived from decomposition of the filler form a protective
layer on the surface of the material, impeding the transport of volatile
decomposition products to the flame and the transport of oxygen to the
interior of the plastic(24–26). This layer also suppresses smoke formation.
ATH breaks down at 205°C(27), but its decomposition temperature
depends on the particle size, and may vary between 190 to 230°C(28,29).
It is regarded as an excellent combustion retardant and belongs to the
group of compounds which are most frequently used. ATH is employed
to reduce the flammability of polyolefins, polyacrylonitrile, polyesters,
polystyrene, epoxy resins, synthetic rubbers, laminates, PVC and others.
Investigations of the combustion of epoxy resins containing ATH have
shown that this compound is active mainly in the solid phase and in its
effect on the physical flame diminishing mechanism(30). Very high molecular
weight polyethylene containing 50% ATH is a plastic with flammability
and smoke formation parameters close to those of heat resistant aromatic
polymers(31).
However, a high content of ATH can give rise to an increase in viscosity
of the molten plastic and hinder the conversion process. This prob lem can
be reduced by selecting a filler with a suitable particle size, structure and
surface roughness(32), and by using a mixing technique ensuring
homogeneous dispersion of the ATH in the plastic. ATH is added to
polymers whose processing temperature does not exceed ATH's
decomposition temperature.
Magnesium hydroxide Mg(OH)2 occupies second place based on sales
of mineral flame retardants. Because of its high decomposition temperature
(320°C), it has found applications in polymers which have to be processed

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Polymer Combustion Processes. 3. Flame Retardants for Polymeric Materials

at a higher temperature range(33-35). Mg(OH)2 is available in the form of a


powder with particle size 0.5 to 5 µm and specific surface from 7 to over
15 m2/g. It is more expensive than ATH, and its content in the plastic can
even exceed 50%. It is used for polyamides, unsaturated polyesters and
in many polymer blends of varying composition. Sometimes it promotes
an improvement in the physical and processing properties of a plastic(35).

Action mechanism of metal hydroxides


After heating to the appropriate temperature, metal hydroxides break
down with the release of water vapour. This is an endothermic process
which keeps the temperature of the plastic below the ignition temperature.
One of the products of decomposition consists of metal oxides with a high
heat capacity which also act as 'thermal wells'(28,33,34). Formulae (1) and (2)
illustrate the course of the decomposition process

2Al(OH)3 → Al2O3 + 3H2O ↑ (about 1500 J/g) (1)

Mg(OH)2 → MgO + H2O ↑ (about 1600 J/g) (2)

A protective ceramic layer is formed by the oxides on the surface of the


polymeric material(33).
Hydroxides limit the formation of smoke. The theory has been put
forward that absorption of the carbonised decomposition products occurs
on the surface of the oxide layer, and these are subsequently oxidised to
CO2(34). The only volatile decomposition product of hydroxides is water
vapour, thus there are no combustion products of the polymers with
corrosive properties(36,37).
Hydroxides are not the only examples of inorganic flame retardants.
This group of fillers also contains other substances used in the form of
powders such as talc, kaolin, graphite, mica or glass fibre. This last is
added as a flame retardant to unsaturated polyesters(38,39).

Organic halogen compounds


Chemical compounds containing halogen atoms in their molecules are
widely used as flame retardants for polymers(1-9,40-47). These are mainly
aliphatic, cycloaliphatic and aromatic compounds. Agents with the lowest
thermal stability are the most effective fire suppressants (Figure 2).

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S. Boryniec and W. Przygocki

Figure 2 Thermal stability of organochlorine compounds and their flame


retarding efficiency in polymer combustion

Aromatic Alicyclic Aliphatic

Heat stability of flame retardant

Halogen containing flame retardants have to meet a range of


requirements such as lack of toxicity, thermal stability at least up to a
temperature of 270°C, chlorine content >50 mass %, no discolouration,
molecular weight < 600 mol/g, lack of volatility during processing and
during use, and good miscibility with the polymer. The effectiveness of
inhibiting reactions in a flame shown by agents of the same chemical
structure but differing in the type of halogen atom, decreases in the order
I > Br > Cl > F.
Iodine containing substances, which are potentially the most effective,
have not been used in practice on account of their poor thermal stability.
On the other hand, the strong C–F bond is too thermally stable, and
released fluorine radicals F• radicals very rapidly enter into chemical
reactions in the solid phase. Therefore only flame retardants containing
chlorine or bromine are used in practice.
Halogen containing flame retardants can undergo pyrolysis in the solid
state or vapourise to the gaseous phase. One of the main products of
pyrolysis in a polymeric material is a hydrogen halide HX (X = Cl, Br).
After separation of a HX molecule, a macromolecule with an aliphatic
structure often is converted into an unsaturated system. Active flame
retardants in the condensed phase limit the quantity of volatile flammable
products formed by increasing the amount of non-volatile pyrolysis
products, (known as coke). The chemical process that take place in this
case are very complex and depend on the chemical structure of the
polymer and the flame retardant, the temperature, pressure, moisture
content etc.
Volatile decomposition products of the types HX, RX, RHn etc. easily
pass into a gaseous phase and take part in radical reactions occurring in

134 Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001
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the flame. Investigations have shown that they do not affect the
phenomenon of ignition and the combustion mechanism of the polymer,
but have an inhibiting effect on the oxidation of carbon monoxide CO to
CO2, which is the main source of heat in the flame.
The inhibiting action mechanism in the case of methane, which is one
of the volatile pyrolysis products of the polymer, can be represented
schematically as follows:

Fuel + O2 → CO2 + CO + H2O (3)

OH• + CO → CO2 + H• (4)

CH4 + O2 → CH•3 + H• + O2 (5)

H• + O2 → OH• + 0.5O2 (6)

OH• + CH4 → H2O + CH•3 (7)

CH•3 + O2 → CH2O + OH• (8)

CH2O + OH• → CHO• + H2O (9)

CHO• + O2 → CO• + H• + O2 (10)

The H• and OH• radicals take part in chain reactions. Reactions (5) and
(10) are examples of a chain reaction which results in an increase in the
number of radicals. The inhibiting reactions involving HBr take place as
follows:

HBr + OH• → H2O + Br• (11)

HBr + 0.5O2 → OH• + Br• (12)

HBr + H• → H2 + Br• (13)

HBr + CH•3 → CH4 + Br• (14)

H• + Br• + M → HBr + M (15)

In reaction (15) M denotes a neutral agent (e.g. H2, H2O).


In reactions (11) – (14) the more reactive radicals (H•, OH•, CH•3) are
replaced by the less active Br• radicals. In certain reactions (e.g. (15)) H•

Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001 135
S. Boryniec and W. Przygocki

radicals disappear. As a result a smaller amount of heat is generated in the


flame. Small additions of halogen inhibitors, (of the order of a few mol %),
can reduce by as much as ten times the rate of flame propagation and have
a marked effect on the ignition limits(48,49).
It has been found by spectroscopy that the introduction of halogen
containing inhibitors into the flame clearly reduces the concentration of
the radicals H•, OH•, and HCO•, whereas there is an increase in the
content of the biradicals C2•• and soot. As the concentration of inhibitor
is increased the flame temperature decreases. Halogen inhibitors accelerate
the formation of soot in the flame(50).
The most frequently used chlorine containing flame retardants are
chlorinated paraffins such as perchloro-pentacyclodecane or
hexachlorocyclopentadiene. These compounds decompose chemically
in the solid phase to form chlorine(51). Chlorinated paraffins are not used
in thermoplastic polymers owing to their low thermal stability at the
processing temperatures. They also give rise to a change in crystallinity
and other properties of polymers.
The cycloaliphatic compound known commercially as CFR has been
used on an industrial scale for this purpose for many years. Its chemical
structure is shown in formula (I)(45). It contains 65.1% by mass of chlorine,
and its high melting point means that it can be added to thermoplastic
polymers without causing them to break down or change colour.
As a filler it increases the heat capacity and the elastic modulus of the initial
polymer without altering its basic properties, such as water resistance or
insulating capacity. Migration of this compound has not been observed at
elevated temperatures or in an aqueous medium. CFR is only one example
among a large number of chlorine containing flame retardants.
After chlorine, the most widely used component of flame retardants is
bromine. In 1994 as much as 47% of the world production of bromine
was absorbed by the bromine flame retardant industry(52). Bromine
compounds are almost twice as effective as combustion inhibitors as
chlorine compounds. However, their drawback is their high cost and

(I)

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Polymer Combustion Processes. 3. Flame Retardants for Polymeric Materials

greater liability to photochemical degradation. The most active bromine


flame retardants include tetrabromophthalic acid and tetrabromobisphenol
A(53).
An important characteristic of a bromine flame retardant is the
temperature at which hydrogen bromide (HBr) is released. It should be
released at an early stage of combustion, and hence before ignition or
during the appearance of a flame. If the HBr is released in a later phase
of combustion its effect is much reduced. Most of the bromine flame
retardants commonly used decompose at temperatures of 200 to 400°C.
When choosing a bromine inhibitor it is best to be guided by the values of
its decomposition temperature and the ignition temperature of the
polymer. For example, polydibromostyrene breaks down only at
temperatures around 400°C, and is thus sufficiently stable at the processing
temperature of polyamides, and is used in their modification.
The release of HBr and other volatile components at the initial stage
of combustion is an important factor in retarding and suppressing this
process(53-55). HBr changes the mechanism of breakdown of the polymer
in the solid phase and is an active inhibitor of combustion in the gaseous
phase(11-15).
Among the bromine containing flame retardants, the most useful are
substances whose molecules contain the largest possible amount of this
element. Such compounds include for example decabromodiphenyl
oxide (formula II, Figure 2) with a melting point of 300 to 315°C and
bromine content of 83.3 % by mass.

(II)

It is used as a combustion retardant for polyethylene.

Phosphorus compounds
The literature shows that the annual demand for phosphorus flame
retardants in the USA is 25,000 tons, and the demand for halogenated
organophosphorus flame retardants is 18,000 tons(56). Western Europe
and Japan use three times this amount of these compounds. Phosphorus

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S. Boryniec and W. Przygocki

itself (the red form) and its numerous organic and inorganic compounds,
are widely used as combustion retardants for polymeric materials. The
chemical and physical mechanisms depend on the kind of polymer and
phosphorus compound, and also on the combustion conditions.
Phosphorus flame retardants can remain in the solid phase and affect
degradation processes or pass into the gaseous phase, in which they act
as eliminators of radicals(57- 67). In oxygen containing polymers (such as
poly(ethylene terephthalate) and poly(methyl methacrylate)), P–O bonds
play an important role in inhibiting combustion. In the presence of
phosphorus flame retardants, chemical reactions lead to a greater extent
to crosslinking of polyaromatic structures, which are subsequently converted
to a carbonised product (coke)(68).
Phosphorus flame retardants form a protective layer composed of high
viscosity poly(phosphoric acid)s on the surface of the polymeric material.
The surface layers have an open structure and are characterised by low
heat conductivity and also by a low coefficient of diffusion. They impede
the flow of heat to the interior of the material, and because of the reduction
in diffusion of volatile pyrolysis products, the restrict the access of fresh
fuel to the combustion zone in the flame. As a result the flame temperature
is reduced.
Volatile breakdown products of phosphorus compounds are among
the most effective inhibitors of combustion of gaseous mixtures(59-62). Their
mechanism is similar to that of the halogen flame retardants. This can be
illustrated by the case of triphenylphosphinic oxide(62), the breakdown
products of which include phosphoric acid. This is a source of radicals
which then attach themselves to the radicals formed as a result of the
combustion of polymers:

(C6H5)3PO → H3PO4 → HPO•2 + HPO• + PO• +… (16)

H• + PO• → HPO• (17)

H• + HPO• → H2 + PO• (18)

2OH• + PO• → H2 + PO2 + O• (19)

PO• + 0.5O2 → PO2• (20)

PO• + OH• → HOPO (21)

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Polymer Combustion Processes. 3. Flame Retardants for Polymeric Materials

The reagents taking part in the above reactions of phosphorus radicals


(e.g. PO•, PO2, PH•, HPO•, HPO2), were identified by spectroscopy.
Triphenyl phosphate, which is used as a plasticiser for some polymers
such as high impact polystyrene (PS-HI), at elevated temperatures
accelerates polymer melting and falling in the form of droplets from
burning plastic. This is followed by a decrease in the temperature of the
material and a decrease in the rate of pyrolysis. In thermoplastic
hydrocarbon polymers, phosphorus flame retardants affect the combustion
process in the gaseous phase. In cellulose and other polymers with
hydroxyl groups or oxygen, they inhibit combustion in the solid phase by
accelerating the formation of carbonised product or the formation of a
protective surface layer. The large number of hydroxyl groups in cellulose
considerably increases its liability to degradation under the influence of
acid catalysts. Phosphorus inhibitors accelerate dehydration, crosslinking,
cyclisation and hence reactions leading to the formation of a carbon
skeleton and coke, and also reduce the amount of volatile products. Owing
to the presence of phosphorus retardants, the coke content may be as
much as 80% wt of the initial polymer, and practically 75% of the
phosphorus used in converted into coke. The addition of phosphorus to
cellulose in amounts of barely 1%, increases the coke yield several 100%.

THE PHENOMENON OF SYNERGISM


The need to meet the demands set by the standards defining the resistance
of polymeric materials to combustion, means that large amounts of
halogen inhibitors must be added. Their content in the polymeric
materials may be as high as 40% wt. Such a large proportion of non-
polymer component normally has a bad effect on the physical and
processing properties of the polymer, reducing or eliminating its
transparency, changes the colour, accelerating degradation under
conditions of use and often raising the cost of the end product(69). It is
therefore necessary to make an effort to reduce the content of retardants
and to ensure optimum physical, mechanical and processing properties
of the plastic. This objective can be achieved with the aid of the
phenomenon of synergism. This means that the total effect in combustion
retardation of a mixture consisting of two or more components is greater
than the sum of the individual actions of these components.

Antimony trioxide
Tri- and pentavalent antimony compounds are among the most widely
used synergistic substances. The most important of these are antimony

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S. Boryniec and W. Przygocki

trioxide, Sb2O3, (also called antimony oxide), antimony pentoxide and


sodium antimonate. In the use of metal oxides as flame retardants, Sb2O3
occupies second place after Al2O3. Sb2O3 is available as a powder with
particle sizes of 0.3 to 15 µm; extremely small particles have a diameter
of as little as 0.03 mm(6,61).
Sb2O3 itself is not an active combustion inhibitor of polymers, but when
used together with halogens based polymers or FRs (Cl, Br) markedly
increases their effectiveness. This is the phenomenon of synergism in an
antimony/halogen system(3). Sb2O3 in combination with chlorinated
organic compounds, that break down at the ignition temperature to form
HCl, is regarded as an effective inhibitor of combustion of many polymeric
materials. Mixtures of this type show optimum flame retardant properties
at a molar ratio of Sb:Cl = 1:3(62,71-80). The synergistic effect here consists
in the catalysis of reactions of synthesis of a volatile antimony trihalide
SbX3, which has string effect on the course of chemical reactions in the
flame(74,76,80,81). The larger the amount of SbCl3 that is present in the
gaseous phase, the higher is the value reached by the oxygen index of the
polymeric material(82). The disappearance of H• and OH• radicals in the
presence of SbCl3 has been noted many times experimentally. The
antimony halide breaks down in the zones in front of the flame and the
combustion zone. The breakdown products include antimony and its
oxide SbO, which are excellent catalysts of the recombination of radicals.
The chemical reactions of SbCl3 in the flame probably take place
according to the following formulae(62):

SbCl3 + H• → SbCl2 + HCl (22)

SbCl2 + H• → SbCl + HCl (23)

SbCl + H• → Sb + HCl (24)

Sb + OH• + M → SbOH + M (25)

Sb + 0.5O2 + M → SbO + M (26)

SbO + H• → SbOH (27)

SbOH + H• → Sb + H2O (28)

HCl + H• → H2 + Cl• (29)

(M is a neutral particle such as N2 or O2).

140 Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001
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Some metal oxides (e.g. TiO2, Fe2O3, CuO), reinforce the synergistic
effect of Sb2O3, whereas others (CaO, MgO, ZnO) can weaken it(82).
Volatile metal halides, in which the Me-X bonds are very weak, have a
strong inhibiting effect on the combustion of polymers; e.g. a small
content (1–5 ppm) of FeCl3 in ABS terpolymer increases its oxygen index
from 18.5 to 30(83).
Metal compounds, including also Sb2O3, are active combustion inhibitors
in the solid phase and accelerate the formation of high molecular weight
carbon structures and coke. During the synergistic action of Sb2O3 with
organic compounds containing chlorine or bromine, antimony halides are
formed, which are Friedel-Crafts catalysts accelerating the formation of
a crosslinked structure and carbonisation.
The process of combustion in the solid state of unsaturated polyester
resins and polyurethane foams containing a mixture of tetrabromophthalic
anhydride and Sb2O3(84,85) was studied using infrared photography. It was
found that in the presence of antimony/halogen system as an antioxidant
a closed homogeneous carbonised layer is formed which separates the
flame from the interior of the polymeric material. This layer blocks the
transport of volatile decomposition products to the flame, which in turn
causes a decrease in its temperature. The SbCl3 with strongly acidic
properties formed during pyrolysis, is a catalyst of the processes of
dehydration and crosslinking of cellulose. The final product is a carbonised
residue and hydrogen chloride. The hydrogen required for the synthesis
of the latter is derived from a radical reaction between the products of
decomposition of the macromolecules and Cl• or Br• radicals. This
reaction leads to the formation of carbon aggregates of high molecular
weight(86).
Investigations of the thermal decomposition of chlorinated polyethylene
have shown that Sb2O3 causes an extension of the induction period of
pyrolysis (under conditions of the same rate of heating), and accelerates
dehydrochlorination(87-89).

Synergism in a nitrogen/phosphorus system


The nitrogen present in the macromolecules of natural polymers gives
them considerable resistance to combustion. Wool, silk and leather are
thus relatively resistant to combustion. On the other hand polyamides
burn much more easily, despite the fact that they are more resistant to
combustion than many other synthetic polymers. It is presumed that this
is due to the relatively low melting point of polyamides. Polyurethanes in
turn are counted among the readily flammable polymers.

Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001 141
S. Boryniec and W. Przygocki

Agents containing nitrogen and inhibiting the combustion of polymers


include triazine, ureas, isocyanates and guanidine(89). These can be
introduced as separate additives or in combination with phosphorus
compounds. They are most often used in cellulose fibres, polyamides,
polyacrylonitrile and polyurethanes.
The inhibition of combustion of polymers by a nitrogen/phosphorus
system is a very complicated phenomenon. It is affected by the type of
nitrogen compound and the accompanying phosphorus compound, the
chemical structure and physical structure of the plastic and the concentration
of inhibitors(90,91).
One of the possible reasons for the effectiveness of nitrogen compounds
as combustion inhibitors is the liberation of nitrogen, which reduces the
concentration of volatile decomposition products and restricts their
flammability(92). A very effective agent recommended for retarding the
combustion of nitrogen containing polymers, particularly polyurethanes,
is the organometal cobalt complex Co(NH3)6Cl3, one mole of which
during thermal decomposition releases almost 6 moles of volatile non-
flammable products into the gaseous phase(89,93):

6Co(NH3)6Cl3 → 6CoCl2 + N2↑ + 6NH4Cl↑ + 28NH3↑ (30)

As we have already mentioned, nitrogen flame retardants are often


used in conjunction with phosphorus compounds. Phosphoric acid in
combination with nitrogen bases, (guanidine, urea etc.), is recognised
because of the phenomenon of synergism as an effective combustion
inhibitor of cellulose materials, (e.g. cotton, rayon fibre). The nitrogen
reinforces the bond between the phosphorus and the polymer and
prevents leaching of the phosphorus agent from the fibre. The synergistic
effect here depends on the type of group containing the N–H bond. The
effect of inhibition by different compounds containing amine groups
therefore varies considerably(94,95).
Nitrogen compounds increase condensation of phosphoric acid to
poly(phosphoric acid)s, which are excellent catalysts of the phosphorylation
of cellulose. Amine groups facilitate the decomposition of carbohydrates
at lower temperatures to form a carbonised product and water. Nitrogen
oxides in turn act as collectors of radicals in the combustion zone of the
flame. Compounds containing P-N units accelerate to a higher degree
than phosphoric acids the phosphorylation of hydroxyl groups in the
polymer. Gaseous nitrogen reduces the decomposition temperature of
cellulose, which reduces the yield of volatile products(96-99).

142 Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001
Polymer Combustion Processes. 3. Flame Retardants for Polymeric Materials

Synergism in a phosphorus/halogen system


Flame retardants containing compounds of phosphorus and a halogen
(Cl, Br) are more effective combustion inhibitors than either of them on
its own, since the anticipated effect in fire suppression is greater than the
sum of the effects of action of phosphorus compounds and halogen
compounds used separately(100,101). The mechanism of this phenomenon
is highly complex and depends to a large extent on the type of compounds
containing the phosphorus and halogen, and also on the chemical
structure of the polymer. In certain polymers, these compounds are active
in the solid phase (e.g. cotton, polyesters)(58,63,102,103). They give rise to a
process of coke formation, in which a predominant amount of bromine
from the decomposing inhibitor is trapped. On the other hand after
thermal decomposition of poly(ethylene terephthalate) (PET) in the
presence of tripropyl phosphate, the presence of phosphorus was not
detected in the coke. On subjecting PET to degradation in the presence
of tri(2,3-dibrompropyl) phosphate or tri(2,3-dichloropropyl) phosphate,
it was found that 75% of the initial phosphorus remained in the solid phase
(coke), whereas the halogens passed into the gaseous phase(104).
The occurrence of synergism in a bromine/phosphorus system has
been confirmed in studies of the combustion of polypropylene, high
impact polystyrene and poly(methyl methacrylate)(105-107). For these studies
triphenyl phosphate, a phosphorus compound of high volatility, was
employed. This was introduced together with decomposition products of
a bromine compound into the combustion zone in a flame, where these
reagents showed activity typical of radical acceptors.
Phosphorus and halogen compounds break down during pyrolysis of
a polymer. The phosphoric acids remaining in the solid phase, are suitable
for the formation of a barrier layer on the surface of the material formed
from the carbonised polymer, whereas the radicals located in this phase,
by accelerating depolymerisation and lowering the melting point of the
polymer, facilitate the formation of droplets which fall from the surface of
the material and cool it down. Volatile decomposition products containing
bromine in turn inhibit the chemical reactions in the flame and also have
the effect of reducing its temperature.
The occurrence of synergism of P/Br has also been confirmed by
studies of the combustion of mixtures of polycarbonate and poly(ethylene
terephthalate)(52,61).

CONCLUSION
The information presented in this article on the fundamental ideas in
reducing flammability of polymers and agents used for this purpose covers

Progress in Rubber and Plastics Technology, Vol. 17, No. 2, 2001 143
S. Boryniec and W. Przygocki

only a small part of the vast amount of knowledge in this sphere


accumulated worldwide over many years. The constant involvement of
science and industry with the problems that have been discussed, is due
to the huge scale of losses and damage caused by the flammability of
polymeric materials. In the articles published up to now, we have
presented certain aspects of the problem of reducing the flammability of
polymers and fibres(108-111). In the study quoted(111) and in the present article
we have concentrated on the chemical aspect of combustion and its
prevention. The flammability of all materials, including polymers, also has
a physical aspect. In fact, experience shows that the structural characteristics
of an object, the degree of fineness of the particles of the flame retardant
and the state of surface structure have an important contribution in
determining the flammability and ignitability of materials. However, these
problems, have not so far been adequately studied.

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