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EMG | Clariant | Feature Article on FR for Biobased Plastics/Composites Page 1 of 5

Bio-based and flame retardant?


Fire protection for bio-based polymers and plastics composites can ensure that renewable
alternatives meet high-end industry requirements. But do proven solutions exist to maintain the
improved environmental features with effective, more environmentally-friendly flame retardants?

By dr. muriel rakotomalala, elke schlosser, dr. sebastian Hörold

Bio-based polymers are here to stay. With a total capacity forecast of 12 million tons by 2020 – a
tripling of 2011 levels [1] – there is definite interest in integrating these polymers into industrial
applications. As early as 2010, approximately 20 different bio-based polymer families were
commercial, while another 6 were at pilot scale. Around half of these were bio-based versions of
well known traditional polymers, while the other half were new to the market, for example,
polylactic acid (PLA) specialties for electronics and automotive [2] applications.

Within the E&E and Building & Construction segments in particular, flammability of the plastics
used is a priority issue. To gain acceptance in these industries, bio-based polymer matrices and
plastic composites must pass the same standards as their petrochemical counterparts, such as UL94
Vertical Test and the Limit Oxygen Index (LOI) fire test. Consequently there is a need for advanced
halogen-free flame retardants that align with the environmental and health profile of the compound
they are treating.

Initiatives such as the “Design for Environment” projects of the U.S. Environmental Protection
Agency and the ENFIRO project sponsored by the European Union, are identifying non-
halogenated flame retardants for different materials and conclude that – next to a favorable
environmental and health profile – these flame retardants also represent real alternatives from a
technical and commercial view. This is a step forward in easing the decision-making and selection
of safer, more environmentally-conscious solutions in many application areas. Research institutions,
but also flame retardant producers and compounders are attending to the development and/or
evaluation of halogen-free flame retardant alternatives for bio-based plastics and composites.

Halogen-free in the E&E and Building sectors

Demand for biomass derived plastics is certainly rising in the E&E and Building & Construction
industries. Of potential relevance to these industries, academic research groups are focusing on
halogen-free flame retardants, often in combination with renewable fillers such as wood, lignin,
starch and oyster shell, for the bio-based plastics and composites of interest. Here, it is being shown
that non-halogenated flame retardants have proven efficiency in bio-based polymer matrices,
providing mechanical properties fit to use for certain applications.

Flame retardant products from specialty chemicals producer Clariant, marketed under the name
Exolit®, have been used in both independent third-party research and internally-led research to
assess the effectiveness of non-halogenated solutions. As a founding member of pinfa (the
Phosphorus, Inorganic and Nitrogen Flame Retardants Association) and a Sector Group within
Cefic (the European Chemical Industry Council), Clariant has shown its commitment to
continuously improving the environmental and health profile of its flame retardant products.
Halogen-free Exolit products can ensure effective flame retardancy in key bio-based polymers and
composites used in Building & Construction and E&E applications. This is demonstrated in the
following examples.
EMG | Clariant | Feature Article on FR for Biobased Plastics/Composites Page 2 of 5

Wood-plastic Composites

European produced Wood-Plastic Composites (WPCs) are primarily used for extrusion purposes in
the decking market (67% of market production). This is followed by their use as natural fiber
composites in automotive interior parts (23%). [3]

Ammonium polyphosphate flame retardant Exolit AP 422 can be used to confer flame resistance to
polyolefin compounds. It is an efficient flame retardant that maintains the physical properties of
WPC compounds and is easy to process. Exolit AP 422 leads to increased char formation,
functioning as a protective layer, assisted by intumescence or swelling/foaming of the thermoplastic
material on exposure to flame. This effect can lead certain applications to be self-extinguishing.
Exolit AP 422 has a favorable environmental and health profile, and is both halogen-free and bio-
degradable. [4]

For building and construction applications, the performance of wood-filled polypropylene (70%
wood / 30% PP) against German Fire Test DIN 4102 B2 shows positive indication for effective fire
protection using Exolit AP 422 treated compounds. Five specimens measuring 190mm x 90mm
were assessed with and without flame retardant. As shown in Figure 1, DIN 4102 B2 was passed
but the specimens burnt completely. The specimens in Figure 2 of 55% wood, 30% PP and 15%
Exolit AP 422 were self-extinguishing.

For the E&E sector, the performance of 60% wood-based WPC in the UL94 Test for electrical and
electronic applications shows possibilities to achieve V-0 classification using a minimum of 10%
Exolit AP 422 in the compound, as highlighted in Table 1.

plA

Possibilities to develop bio-based flame retardant PLA have also been revealed. In certain electrical
and electronic applications, the selection of a flame retardant package can improve the fire
resistance of PLA. One laptop computer manufacturer, for example, has developed a model with a
cover made from a flame-retardant blend of PLA and polycarbonate. [5] Similar blends are under
development for other office equipment.

A fully independent study carried out at Unité Matériaux et Transformations (UMET, Lille
University, France) investigated the efficiency of Exolit AP in PLA reinforced with different bio-
based fillers that could act as a char former in the intumescent system. Both lignin and starch from a
different source allowed the material to reach the UL94 V-0 classification, while the non-reinforced
material only achieved a V-2 rating (see Table 2). Moreover both lignin and starch increase the LOI
and showed a reduction of both peak of heat release (pHRR) in the cone calorimeter test. AP has
therefore been shown to be an effective flame retardant additive for a bio-based plastic reinforced
with bio-based fiber.

polyamides (pA)

Phosphinates can be used to provide reliable flame retardants in applications involving elevated
temperatures. Flame retardants based on aluminum salts of diethylphosphinic acid (DEPAL)
developed and marketed by Clariant under the Exolit OP name, are used most widely to incorporate
non-halogenated flame retardancy into engineering plastics. In most cases, a relatively small
loading is sufficient to meet stringent fire safety regulations.
A fully independent study carried out at Unité Matériaux et Transformations (UMET, Lille
University, France) investigated the efficiency of Exolit AP in PLA reinforced with different bio-
based fillers that could act as a char former in the intumescent system. Both lignin and starch from a
different source allowed the material to reach the UL94 V-0 classification, while the non-reinforced
material only achieved a V-2 rating (see Table 2). Moreover both lignin and starch increase the LOI
and showed a reduction of both peak of heat release (pHRR) in the cone calorimeter test. AP has
therefore been shown to be an effective flame retardant additive for a bio-based plastic reinforced
EMG | Clariant fiber.
with bio-based | Feature Article on FR for Biobased Plastics/Composites Page 3 of 5

polyamides
In an in-house (pA)
study, Clariant investigated the effectiveness of Exolit OP products in partially bio-
based PA10T commercialized by Evonik [6]. This polyphthalamide, whose monomers are largely
Phosphinates can be used
derived from naturally to provide
sourced reliable flame
raw materials, retardants
significantly in applications
reduces involving compared
the CO₂ emissions elevated to
temperatures. Flame retardants
pure petroleum-based polyamides. basedForonthis
aluminum salts ofwas
study, PA10T diethylphosphinic
compounded with acid30%
(DEPAL)
glass fibers
developed and marketed by Clariant under the Exolit OP name, are used
and different flame retardant systems based on Exolit OP grades in order to evaluate themost widely to incorporate
both flame
non-halogenated
EMG | Clariant | flame
Feature retardancy
Article
retardancy and mechanical properties. oninto
FR engineering
for Biobased plastics. In most cases,
Plastics/Composites a relatively small
Page 3 of 5
loading is sufficient to meet stringent fire safety regulations.
In comparison to the commercially available non-flame retardant glass reinforced PA10T [7] that
In an in-house
reaches study, Clariant
the classification HB in investigated
the UL94 test,the effectiveness
the compoundofwithExolit
theOPnewproducts in partially
Exolit product bio-
Exolit
based PA10T commercialized by Evonik [6]. This polyphthalamide, whose
OP 1400 (TP) [8] showed the best balance between flame retardancy efficiency and mechanical monomers are largely
derived from
properties. Thenaturally sourced
comparison raw materials,
is shown in Table significantly
3. reduces the CO₂ emissions compared to
pure petroleum-based polyamides. For this study, PA10T was compounded with 30% glass fibers
®*
and different
Another flamePA
bio-based retardant
is PA410systems based on Exolit
commercialized by DSMOP grades in order
under the to evaluate
tradename the both
EcoPaXX flame
. The
retardancy
evaluation ofandtwomechanical
Exolit OPproperties.
systems in PA410 reinforced with 30% glass fiber showed that both
systems could reduce the flammability of EcoPaXX while maintaining the impact strength required
In
forcomparison to the commercially
E&E applications. However, theavailable non-flame retardant
highest classification glass
V-0 could notreinforced
be achievedPA10T
for all[7] that
reaches
thicknesses, see Table 6. This demonstrates the challenge of developing a compound that Exolit
the classification HB in the UL94 test, the compound with the new Exolit product
OP 1400 (TP) [8]
simultaneously showed
reaches thethe best balance
highest between
flammability flame retardancy
classification efficiency and
while maintaining goodmechanical
mechanical
properties. The comparison is shown in Table 3.

Another bio-based PA is PA410 commercialized by DSM under the tradename EcoPaXX®*. The
evaluation
pHBV of two Exolit OP systems in PA410 reinforced with 30% glass fiber showed that both
systems could reduce the flammability of EcoPaXX while maintaining the impact strength required
PolyE&E
for 3-hydroxybutyrate-co-3-hydroxyvalerate, more commonly
applications. However, the highest classification known
V-0 could notasbePHBV, is afor all
achieved
biodegradable,
thicknesses, seenon-toxic plastic
Table 6. This product alternative
demonstrates to synthetic
the challenge non-biodegradable
of developing a compoundpolymers
that made
from petroleum. Its low thermal stability is often seen as a drawback.
simultaneously reaches the highest flammability classification while maintaining good mechanical
properties.
A study carried out at the BAM Federal Institute for Materials Research & Testing, focused on a
two component flame retardant system to achieve a UL94 V-0 rating and with a relatively high
pHBV
oxygen index (LOI) value. In comparison to the non-flame retardant compound both peak of heat
release (pHRR) and total heat release (THR) were reduced (Figure 3). FT- IR analysis demonstrated
Poly 3-hydroxybutyrate-co-3-hydroxyvalerate,
that the combination of Exolit OP 1240 and Ironmore commonly
Trioxide known astoPHBV,
(Fe) contribute is a of an
formation
biodegradable, non-toxic plastic product alternative to synthetic non-biodegradable
additional residual char that can act as a protection layer between the heat source and polymers
the made
from petroleum.
combustible Its lowplastic.
bio-based thermal[10]
stability is often seen as a drawback.

A study carried out at the BAM Federal Institute for Materials Research & Testing, focused on a
two component
Market flame retardant system to achieve a UL94 V-0 rating and with a relatively high
availability
oxygen index (LOI) value. In comparison to the non-flame retardant compound both peak of heat
The acceptance
release (pHRR) of andhalogen-free flame (THR)
total heat release retardant solutions
were reducedwithin the3).
(Figure focus
FT-industries
IR analysisofdemonstrated
E&E and
Building
that & Construction
the combination is notOP
of Exolit yet1240
widely
andknown. The presence
Iron Trioxide of commercially
(Fe) contribute available
to formation of an
additional residual char that can act as a protection layer between the heat source and the there is a
compounds incorporating more environmentally-compatible flame retardants shows that
demand for such
combustible materials.
bio-based However,
plastic. [10] availability is currently limited, with only a few compounders
advancing into this area. The following examples provide a selection of halogen-free flame
retardant bio-based plastics currently available. EuroStar Engineering Plastics has introduced flame
Market
retarded availability
thermoplastic compounds based on a renewable oyster shell filler using Clariant’s Exolit®
AP non-halogenated flame retardants. [11] DSM’s EcoPaXX® development is a polyamide 410 that
Theonly
not acceptance
derivesof halogen-free
from flame materials
70% renewable retardant solutions
but is alsowithin
proventhetofocus industries
be 100% carbonofneutral
E&E and
from
Building & Construction is not yet widely known. The presence of commercially
cradle-to-gate. One halogen-free grade reaches UL94V-0 classification and is promoted for E&Eavailable
compounds incorporating
applications. moreunder
[12] In addition, environmentally-compatible
the general term GreenLine, flame retardants shows
EMS-GRIVORY ® that there is a
* markets a
demand
wide for of
range such materials.
bio-based However,which
polyamides availability is currently
are partially limited,
or wholly with only afrom
manufactured few renewable
compounders
advancing
raw into[13]
materials. this GreenLine
area. The following examples
includes two provideflame
halogen-free a selection of halogen-free
retarded flame PPA
grades of a bio-based
retardant bio-based plastics
that achieve UL94 V-0 rating. currently available. EuroStar Engineering Plastics has introduced flame
retarded thermoplastic compounds based on a renewable oyster shell filler using Clariant’s Exolit®
A study carried out at the BAM Federal Institute for Materials Research & Testing, focused on a
two component flame retardant system to achieve a UL94 V-0 rating and with a relatively high
oxygen index (LOI) value. In comparison to the non-flame retardant compound both peak of heat
release (pHRR) and total heat release (THR) were reduced (Figure 3). FT- IR analysis demonstrated
that the combination of Exolit OP 1240 and Iron Trioxide (Fe) contribute to formation of an
additional residual char that can act as a protection layer between the heat source and the
EMG | Clariant
combustible | Feature
bio-based Article[10]
plastic. on FR for Biobased Plastics/Composites Page 4 of 5

Market availability
The indications are clear that there is a growing interest in bio-based plastics and composites with
halogen-free flame retardants. However, there is a need for more investment into the development
The acceptance
of new solutions.ofThe
halogen-free
highlighted flame retardant
benefits solutions
and the within
feasibility the focus industries
of compounding of E&E and
bio-polymer
Building
materials & Construction
with is not yet
non-halogenated widely
flame known.will
retardants Theencourage
presence further
of commercially available
manufacturers to become
compounds incorporating more environmentally-compatible
more environmentally-conscious in their product offerings. flame retardants shows that there is a
demand for such materials. However, availability is currently limited, with only a few compounders
advancing into this area. The following examples provide a selection of halogen-free flame
***
retardant bio-based plastics currently available. EuroStar Engineering Plastics has introduced flame
retarded thermoplastic compounds based on a renewable oyster shell filler using Clariant’s Exolit®
® Trademark
AP of Clariant
non-halogenated flameregistered in many
retardants. countries
[11] DSM’s EcoPaXX® development is a polyamide 410 that
not only derives3rd
®* Registered from 70%
party renewable materials but is also proven to be 100% carbon neutral from
trademark
cradle-to-gate. One halogen-free grade reaches UL94V-0 classification and is promoted for E&E
applications. [12] In addition, under the general term GreenLine, EMS-GRIVORY®* markets a
wideAuthors
The range of bio-based polyamides which are partially or wholly manufactured from renewable
raw materials. [13] GreenLine includes two halogen-free flame retarded grades of a bio-based PPA
EMG
dr. | Clariant
that muriel
achieve | Feature
raKotomalala
UL94 Article
V-0 rating. on FR formarketing
is technical Biobasedmanager,
Plastics/Composites Pagein 4this
Flame retardants, and at Clariant of 5
position since 2011.
muriel.rakotomalala@clariant.com
The indications are clear that there is a growing interest in bio-based plastics and composites with
elKe sCHlosser is technical marketing manager, Flame retardants, and at Clariant in this position
halogen-free
since 1995. flame retardants. However, there is a need for more investment into the development
of new solutions. The highlighted benefits and the feasibility of compounding bio-polymer
elke.schlosser@clariant.com
materials with non-halogenated flame retardants will encourage further manufacturers to become
dr. seBastian HÖrold is Head of development & application technology Plastics, Flame retardants,
more environmentally-conscious in their product offerings.
and at Clariant in this position since 2001
sebastian.hoerold@clariant com
***
Figure Captions
® Trademark of Clariant registered in many countries
Figure 1. Fire behavior of 70% wood-filled polypropylene without flame retardant
®* Registered 3rd party
DIN 4102 trademark
B2 test passed, specimen (shown after 60 s) burns off completely

Figure 2. Fire performance of 55% wood-filled polypropylene


®
with 15% Exolit AP 422: Self-extinguishing after 30 s
The Authors
Figure 3. Cone calorimetric data of PHBV with Exolit OP 1240 (designated as AlPi)
dr. muriel raKotomalala is technical marketing manager, Flame retardants, and at Clariant in this
and iron oxide as flame retardant additives
position since 2011.
muriel.rakotomalala@clariant.com
Figure
®
4. The non-halogenated flame retardants of Clariant’s Exolit brand
are ideal for use in combination with bio-based plastics and renewable fillers,
elKe sCHlosser is technical marketing manager, Flame retardants, and at Clariant in this position
such as wood, lignin, starch and even ground oyster shell
since 1995.
elke.schlosser@clariant.com
Note: All figures and table courtesy Clariant
dr. seBastian HÖrold is Head of development & application technology Plastics, Flame retardants,
and at Clariant in this position since 2001
sebastian.hoerold@clariant com

Figure Captions

Figure 1. Fire behavior of 70% wood-filled polypropylene without flame retardant


DIN 4102 B2 test passed, specimen (shown after 60 s) burns off completely

Figure 2. Fire performance of 55% wood-filled polypropylene


®
with 15% Exolit AP 422: Self-extinguishing after 30 s

Figure 3. Cone calorimetric data of PHBV with Exolit OP 1240 (designated as AlPi)
and iron oxide as flame retardant additives
®
materials with non-halogenated flame retardants will encourage further manufacturers to become
more environmentally-conscious in their product offerings.

***

® Trademark of Clariant registered in many countries


®* Registered
EMG | Clariant3rd party trademark
| Feature Article on FR for Biobased Plastics/Composites Page 5 of 5

The Authors
literature

dr.
[1] muriel raKotomalala
market Based is technical
study on Bio-based Polymersmarketing
in europe,manager, Flame
© nova-institut retardants,
GmbH, and at Clariant in this
version 2013-07
position since 2011.
[2] the state-of-the-art on Bioplastics: Jan Th. J. Ravenstijn, 2010, Polymedia Publisher GmbH
muriel.rakotomalala@clariant.com
[3] market developments of and opportunities for biobased products and chemicals. Final report december 2013.
authors: dammer,
elKe sCHlosser m. Carus, a.
is technical raschka, manager,
marketing l. scholz, © nova-institut
Flame GmbHand at Clariant in this position
retardants,
since 1995.
[4] inorganic compound, causes no biological oxygen depletion, rapidly decomposes to ammonium and phosphate in
elke.schlosser@clariant.com
ground and sludge. source: uBa research report, december 2000, pp 112.
[5] seBastian
dr. Biopolymers:HÖrold
Polylactic acid and flame
is Head retardancy, www.flameretardants-online.com/web/en/news/?showid=267
of development & application technology Plastics, Flame retardants,
and at Clariant in this position since 2001
[6] evonik industries © 2012 vestamid Ht plus m3000 datasheet
sebastian.hoerold@clariant com
[7] evonik industries © 2012 vestamid Ht plus m3033 datasheet
[8] Clariant’s new development with clearly higher thermal stability and reduced plate-out
Figure Captions
[9] datasheet dsm ecoPaXX
[10] study
Figure by dr
1. Fire e Gallo with
behavior exolit
of 70% oP 1240 (aka
wood-filled aiPi) published
polypropylene in eur.
without Pol.J.47(7)
flame 1390-1401.
retardant
DIN 4102 B2 test passed, specimen (shown after 60 s) burns off completely
[11] http://www.plastics-u.com/2014/02/07/renewable-flame-retarded-polymers-filled-based-on-oyster-shell-filler-2/
[12] http://www.dsm.com/content/products/ecopaxx/en_us/markets/electrical-electronics.html
Figure 2. Fire performance of 55% wood-filled polypropylene
®
with 15% Exolit AP 422: Self-extinguishing after 30 s
[13] http://www.emsgrivory.com/en/products-markets/products/greenline/
Figure 3. Cone calorimetric data of PHBV with Exolit OP 1240 (designated as AlPi)
and iron oxide as flame retardant additives
[Ends]
®
Figure 4. The non-halogenated flame retardants of Clariant’s Exolit brand
are ideal for use in combination with bio-based plastics and renewable fillers,
such as wood, lignin, starch and even ground oyster shell

Note: All figures and table courtesy Clariant


EMG | Clariant | Feature Article on FR for Biobased Plastics/Composites Page 5 of 5

literature

[1] market Based study on Bio-based Polymers in europe, © nova-institut GmbH, version 2013-07
[2] the state-of-the-art on Bioplastics: Jan Th. J. Ravenstijn, 2010, Polymedia Publisher GmbH
[3] market developments of and opportunities for biobased products and chemicals. Final report december 2013.
authors: dammer, m. Carus, a. raschka, l. scholz, © nova-institut GmbH
[4] inorganic compound, causes no biological oxygen depletion, rapidly decomposes to ammonium and phosphate in
ground and sludge. source: uBa research report, december 2000, pp 112.
[5] Biopolymers: Polylactic acid and flame retardancy, www.flameretardants-online.com/web/en/news/?showid=267
[6] evonik industries © 2012 vestamid Ht plus m3000 datasheet
[7] evonik industries © 2012 vestamid Ht plus m3033 datasheet
[8] Clariant’s new development with clearly higher thermal stability and reduced plate-out
[9] datasheet dsm ecoPaXX
[10] study by dr e Gallo with exolit oP 1240 (aka aiPi) published in eur. Pol.J.47(7) 1390-1401.
[11] http://www.plastics-u.com/2014/02/07/renewable-flame-retarded-polymers-filled-based-on-oyster-shell-filler-2/
[12] http://www.dsm.com/content/products/ecopaxx/en_us/markets/electrical-electronics.html
[13] http://www.emsgrivory.com/en/products-markets/products/greenline/

[Ends]

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