Exolit AP For Polyolefins July 2013

Exolit ® AP 76x
EFFICIENT FLAME
RETARDANTS FOR
POLYOLEFINS
Public
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TM & RD Flame Retardants
15.07.2013
2 Public, Exolit AP Flame Retardants for Polyolefines
BU Additives, BL Flame Retardants, TM & RD Flame Retardants, 15.07.2013
Exolit AP 76x for Polyolefins
– Introduction – Intumescence in Polyolefins
– Product Portfolio
- Exolit AP 766 (TP)
- Exolit AP 765
- Exolit AP 760
- Exolit AP for Elastomers and WPC
– Processing
– Contacts Clariant BL Flame Retardants

Introduction
- INTUMESCENCE IN
POLYOLEFINS
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What is Intumescence ?
− Intumescence = swelling, foaming
− The thermoplastic material swells out (foams) on exposure to flame
− The carbon rich foam layer formed swollen

material
− has a heat-insulating effect specimen (carbon rich
foam layer)
− reduces further oxygen

access
− reduces fuel transport into
the flame
Intumescence at a PP specimen
− prevents dripping
Bunsen burner
Intumescent Action in Polymers (I)
Flame exposure causes decomposition to:
thermal feedback
→ phosphoric polyacids
oxygen
→ crosslinking materials
→ volatiles
heat
combustion
A solid carbonaceous char is formed products
by a sequence of chemical reactions combustible smoke
(step by step or simultaneously) heat gases
→ reactions need to take place at the right temperature Pyrolyse " foamed char "
and the correct sequence!
Char formation is driven by
→ IFR systems are sensitive to formulation modifications!
area of decomposition
synergism of phosphorus
and nitrogen components!
Char formation is driven by
synergism of phosphorus char formation
foaming
and nitrogen components!
©Clariant GmbH 2000
Intumescent Action in Polymers (II)
Chemical mechanism (schematic):
1. Partial decomposition of APP

heat
(NH4PO3)n n NH3 + (HPO3)n
> 250 °C
2. Crosslinking reactions
heat
(HPO3)n + N-synergist + polymer phosphate-bridged organic clusters
3. Char formation
heat
(HPO3)n + P-organic clusters H3PO4 + dehydrated char
Product Portfolio for
Polyolefins
Public
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Exolit® AP 76x Product Group -

Composition and physical properties
AP 760 AP 765* AP 766*

Phosphorus [% by wt.] 20.0 21.0 24.0
Nitrogen [% by wt.] 14.0 18.0 15.4
Density [g/ml] 1.8 1.7 1.7
Bulk density [g/ml] 0.4 0.6 0.6
Moisture content [% by wt.] < 0.5 < 0.5 < 0.5
Products are based on different synergist technology
* Registered in Europe only, not listed in TSCA (USA), METI (Japan) and IECSC (China) inventories
Exolit® AP 76x for Polyolefins

Typical dosages
Loading levels (% by wt.) for a UL 94 V-0 classification
at 1.6 mm material thickness:
AP 760 AP 765* AP 766*
PP homo (MFR 12) 30.0 25.0 22.0
PP copo (MFR 5) 32.0 28.0 24.0
Loading levels depend on MFI and copolymer content; typically, the higher
the MFI and the higher the copolymer content, the higher the loading
requirement for the FR.
Achievable Test Classifications with the

Exolit® AP 76x series (examples)
Electrical & Electronics Industry
Dosage
Polymer Standard Class (thickness)
[% by wt.]
PP-Homo 22 - 30 UL 94* V-0 (1.6/3.2 mm)
PP-Copo 24 - 32 UL 94* V-0 (1.6/3.2 mm)
PP-Copo 26 - 32 UL 94* 5-V (3.2 mm)
PP 20 - 30 IEC 60695-2-12 + 960°C (of part)
PE-HD (AP 760) 30 - 32 UL 94* V-0 (1.6/3.2 mm)
PE-LD (AP 760) 30 - 35 UL 94* V-0 (1.6/3.2 mm)
EVA (AP 760) 30 UL 94* V-0 (1.6/3.2 mm)
* Underwriters Laboratories (vertical burn test) 94

+ Glow wire flammability index (GWFI)
Achievable Test Classifications with the

Exolit® AP 76x series (examples)
Building Industry
Dosage
Polymer Standard Class (thickness)
[% by wt.]
PP-Homo 20 DIN 4102* B2 (1 mm)
PP-Copo 27 - 30 NT Fire 006+ passed
PP approx. 20 Cal TB 133D (3/8‘‘)
PE-LD (AP 760) 35 DIN 4102* B2 (0.5 mm)
EVA (AP 760) 30 DIN 4102* B2 (1 mm)
* German Building Code

+ Scandinavian roofing test (fire spread)
D Test for seating furniture in public buildings (California Technical Bulletin)
Exolit® AP 76x Product Portfolio for Polyolefins

(PP, PE, EVA, and for PO and SEBS based elastomers)
− Intumescent systems based on ammonium polyphosphate
− Exolit AP 760
high flowability due to melting component
− Exolit AP 765*
better stability for PP extrusion, less water uptake
− Exolit AP 766*
higher efficiency and thermally stable,
very good efficiency in glass fiber reinforced PP
Typical dosage of products is in the range of 20 – 35 % depending on polyolefin type

Exolit® AP 76x – where to use?

General selection criteria
− Exolit AP 760
− Standard grade for injection molding applications
− Limited suitability for extrusion applications (LDPE/EVA, PP copolymers possible; not low MFI PP)
− Highest dosage requirements of product range
− Best flow properties due to melting synergist
− Lowest processing stability of product range in compounding (approx. 220 °C)
− Exolit AP 765
− Suitable for both injection molding and PP extrusion (e.g. pipes, conducts with low MFI) but not
HDPE extrusion applications
− Highest processing stability of product range in compounding (approx. 250 °C)
− Suitable for talc reinforced PP compounds with low to moderate levels of talc (max. 20 % talc)
− Exolit AP 766
− Suitable for both injection and extrusion applications (with non-demanding extrusion requirements
=> low temperature, low shear)
− Highest FR efficiency of product range
− Processing stability in compounding a little bit lower as with Exolit AP 765 (approx. 240 °C)
− Best efficiency in glass-fiber reinforced PP compounds
− Product of choice for development of TPE-S formulations
Exolit® AP 76x - Applications
– Electrical equipment
⇒Interior parts for consumer & technical electronics
⇒Fuse boxes
⇒Installation materials
– Construction engineering
⇒Cable ducts
⇒Roofing (extruded)
⇒Stadium seats
Flame retarded PP/PE can partially substitute engineering plastics!

Comparison to other Flame Retardants
− Advantages compared to − Advantages compared to

halogen FRs metal hydroxides
− Lower smoke density − Much lower dosage
− Less corrosive gases − Better mechanical properties
− High grade light stabilization possible − Lower compound density
− Lower compound density
Due to solid phase mechanism

⇑ ⇑
− Char formation
⇓ ⇓
Intumescent FR versus Halogen

Containing FR (Schematic)
UL 94 classification
V-0
V-1
Halogen containing FR
V-2
Intumescent FR
no
class
0 10 20 30
FR content [% by wt.]
Exolit AP 76x grades do not meet UL 94 V-1 or V-2 at lower loadings!

FR Effect in Polyolefins – LOI & UL 94 V
– UL 94 V-0 @ 20-25% dosage

– UL 94 V-2 from 15 to 20% dosage
45
40 UL 94 classification V-0 V-0

UL 94 Klasse
3.2 and 1.6 mm V-0
35
V-2 V-0
30 V-0
N.k.
25 V-2
LOI / %
N.k.
V-2
20
N.K.
15 N.K.
10 LOI 1,6 mm LOI 3,2 mm
0
0 5 10 15 20 25 30 35
Exolit AP 765 / [%]
Exolit® AP 76x – where to use?
− Compounding industry
- As the dosage of Exolit AP 76x in the final application is rather high, this product range is used almost
directly in the compounding industry for the production of ready-to-use compounds.
→ compounding industry is the target industry
– Masterbatch industry
- The masterbatch route is not favored due to cost (unattractive let-down ratio) and processing
difficulties encountered when trying to achieve high filling grades.
→ masterbatch industry is not a target industry
− Processing industry (injection molders; producers of extruded products)

- Processers typically can process only granules (polymers, masterbatches) on single screw
equipment; the dosage of powders is not possible.
→ processing industry is not a target industry
Exolit AP 76x for Polyolefins/Elastomers
Products are suitable for a wide variety of final applications but they are not
generally suitable for every application; so there are certain limitations:
Yes No
Injection moulded parts with thickness ≥ 1 mm Films with less than 0.5 mm thickness
(e.g. parts of electrical equipment, housings, seats)
→ major applications so far
Extruded products Very thin applications as fibers, tapes, foams
(e.g. cable ducts, corrugated pipes)
Cable insulations Cable insulations
(without water contact requirements) (with water contact requirements)
Cable sheathings Articles with a glossy surface (“ABS like”)
Parts with continuous water contact
(e.g. drain pipes, sewage pipes)
Exolit ® AP 766 (TP)
AN EFFICIENT FLAME
RETARDANT FOR
POLYOLEFINS
Public
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15.07.2013
Compounding Stability
Exolit AP 766 (TP):
– less water uptake during cooling

of polymer strands than
previous grades
– minimized sensitivity to
hydrolysis at the surface
Exolit® AP 766 (TP) -

Compound Properties of PP-Homopolymers
PP blank Exolit AP 766
MFR [g/10 min] 12.0 10.8
Tensile modulus [MPa] 1550 1870
Tensile yield stress [N/mm²] 35 25
Elongation at break [%] > 50 10.5
Impact str. (Charpy) [kJ/m²] 90 26
Notched impact str. [kJ/m²] 3.0 1.5

Exolit® AP 766 (TP) -

Compound Properties of PP- Copolymer
PP blank Exolit AP 766
UL 94 class [1.6 mm] n. c. V-0
GWIT [1 mm] 750 800
MFR [g/10 min] 4.4 3.1
Elongation at break [%] no br. no br.

Exolit® AP 766 (TP)-

Glass Fiber Reinforced PP-Homopolymer
Glass fiber content: 20 %
PP blank AP 766
UL 94 class [1.6 mm] n. c. V-0

GWIT [1 mm] 750 825
MFR [g/10 min] 6.0 4.4
Elongation at break [%] 2.4 2.7
→ V-0 with a flame retardant dosage of 22 % by weight !

Smoke Density (DS)

- PP-Copolymer
600
500
400
DS
300
200
100 Non-Flaming
without
0 24 % Exolit AP 766
DS (FL)
Flaming
0 5 10 15 20 25
without
Time [min]
24 % Exolit AP 766
NBS Smoke Box (ASTM-E 662-83)

Smoke Density (DS)

- PP-Homopolymer
Flaming Conditions
500
450
400
350
300
DS
250
200
150
100
50
0 without
0 1 2 3 4 5 6 22 % Exolit AP 766
26 % Exolit AP 760
Time [min]
NBS Smoke Box (ASTM-E 662-83)

Fire Gas Analysis

- PP-Homopolymers
Concentration after 4 min
< 150* < 1000* < 100*
250
200
Concentration [ppm]
150
100
50
0
Non Flaming Flaming Non Flaming Flaming Non Flaming Flaming
without
HCN CO NO-NO2
22 % Exolit AP 766
Airbus Directive ABD 0031-7.4 * Max. Concentration in ppm

Fire Gas Analysis

- PP-Copolymers
Concentration after 4 min
< 150* < 1000* < 100*
250
200
Concentration [ppm]
150
100
50
0
Non Flaming Flaming Non Flaming Flaming Non Flaming Flaming
HCN CO without
NO-NO2
22 % Exolit AP 766
Airbus Directive ABD 0031-7.4 * Max.

Concentration in ppm
Exolit AP 765
LOW MFI PP AND PP/TALC
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Exolit® AP 765 in Extrusion Application

Achievable Flame Retardant Efficiency in
Low MFI PP
PP homopolymer 100 75 72
[MVR 230/2,16 = 1,25 cm³/ 10 min]
Exolit AP 765 (TP) - 25 28
UL 94 (1.6 mm) n.c. V-0 V-0
UL 94 (0.8 mm) n.c. V-2 V-0
GWFI (1 mm) 650°C 960°C 960°C
− V-0 achievable also at 0.8 mm

− Exolit AP 760 and Exolit AP 766 cannot be used due to processing issues in low MFI PP
Exolit® AP 765 in Talc Reinforced PP

Flame Retardant Efficiency in a PP Homopolymer
PP homopolymer 80 65 60 50 45
(MFR 230/2.16 = 12 cm³/10 min)
Talkum Luzenac 1445 20 10 10 20 20
Exolit AP 765 (TP) - 25 30 30 35
UL 94 1.6 mm n.c.* V-2** V-0 V-2** V-0
UL 94 3.2 mm n.c.* V-0 V-0 V-0 V-0
GWIT (1 mm) 775 °C 800 °C 825 °C 825 °C 825 °C
GWFI (1mm) 750 °C 900 °C 960 °C 960 °C 960 °C
* no classification possible
** only one or two specimens showed burning dripping
Exolit AP for Elastomers
and WPC
Public
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Flame Retardants for Thermoplastic Elastomers

(TPEs)
Huge variety of TPEs:
TPEs
Block Elastomer
Copolymers Blends
PEBA/
TPE-S TPE-E TPU TPO/ R-TPO TPV
COPA TPE-A
Styrenic Polyether Polyurethane Polyolefin SUPER TPV
Polyether amide
based ester based based based Vulcanized
based
PO/EPDM
SBS – SIS – SEBS Ether based PO/EVA
PO/EVA/EPDM
Ester based
FR formulations with Exolit AP
FR formulations with Exolit OP
Main focus is the development of halogen-free cable compounds to replace PVC

Exolit AP for Elastomer Blends

- TPE-O, TPE-V and TPE-S
− Based on polyolefins or SEBS (SBS, SEPS . . .)
− Blended with EPDM and/or EVA and/or EVA/LLDPE
− Rubber phase might be cross linked
− Might contain highly flammable extender oils (almost anytime with SEBS elastomers)
− Quite high shear might be applied to realize proper blend morphology
Flame retardants for TPE-O, TPE-V and TPE-S

Intumescent flame retardants as Exolit AP 760/AP 765/Exolit AP 766 work but
typically (much) higher amounts of such flame retardants are needed as for
straight polypropylene, especially in TPE-S based elastomers.
→ dosage > 35 % of Exolit AP 76x might be necessary; Exolit AP 766 favored for TPE-S
Exolit AP 422 for WPC (wood plastic composites)
− Example: WPC based on PP with Exolit AP 422
− Specimen is self extinguishing after removal of burner after 15 s
− ⇒ Exolit AP 422 can be part of a FR formulation for polyolefin based WPCs
After 15 s 15 s 30 s
Formulation: 55 % wood
30 % PP
15 % Exolit AP 422 (test according to German standard DIN 4102 B2)
Processing
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Compounding of Exolit® AP 76x
Points to consider
− Machine design
− Handling
− Processing conditions
Machine design: Co-rotating twin screw extruder
− Adequate processing length (30 - 40 D)
− Side feeding of the flame retardant is recommended
− Low number of kneading blocks in the FR processing zone
− Low shear mixing elements for a good dispersion
− Air knife and strand pelletizer preferred
− Fast and effective drying of granules after pelletizing recommended
− It is always helpful to check humidity levels of granules after production

Typical screw design and temperature setting for PP compounding (Exolit AP 760)
(Berstorff ZE 25 / 40 D, co-rotating twin screw extruder)
temp.
water- settings
170 170 175 175 180 185 180 175 170 cooled [°C]
nozzle
screw
flights
process
stages
Note: after the side feed of flame retardant some kneading blocks can be inserted, especially for the proper dispersion
of Exolit AP 765/AP 766 (non-melting); for Exolit AP 760 (melting component) kneading blocks are not “a must”.
Typical screw design and temperature setting for PP compounding (Exolit AP 765/AP 766)
(Berstorff ZE 25 / 40 D, co-rotating twin screw extruder)
temp.
water- settings
170 170 175 175 180 185 180 175 170 cooled [°C]
nozzle
screw
flights
process
stages
Note: after the side feed of flame retardant some kneading blocks have been inserted for the proper dispersion
of Exolit AP 765/AP 766 (non-melting); for Exolit AP 760 (melting component) kneading blocks are not “a must”.
Handling
− Dry storage and handling of the product necessary

− Immediate processing of the powder after bags have been opened
− No storage of open containers or bags
− Avoid condensation of humidity at cold equipment parts
Processing conditions: example PP, injection moulding grade
− Mass temperature of 200 - 230 °C (392 - 446 °F) recommen ded

− Temperature range of heating units: approx. 170 - 200 °C (338 - 392 °F)
− Cooling of side feeder can be helpful
− Use the full capacity of the screw (no underfeeding)
− Optimize screw speed and dosage according to temperature limit
Effects of higher processing temperature or too much shear:
Partial decomposition of the flame retardant can lead to
⇒ soapy surface of polymer strands after going through the water bath
⇒ high water uptake from the cooling bath
⇒ sticky granules that are hard to dry
⇒ gas bubbles in the compound granules
Note: as Exolit AP 76x are polar substances the surface of a polyolefin strand gets more polar as well;
so the strands are wetted better in general with water leading to a certain water-carry-over (WCO) effect.
Compounding of Exolit® AP 760
Formation of screw deposits possible with Exolit AP 760
A layer of high viscosity liquid is formed at hot metal parts during compounding
due to the chemical nature of the synergist in the AP 760 formulation.
When the compounding machine is cooled down after a campaign a thin

hard deposit (thermoset) remains on the surface of screws and cylinder and is
difficult to remove.
Compounding of Exolit® AP 760
Cleaning of the compounding machine
− Tough purging compounds are good for a coarse clean-up before the machine is
cooled down.
− A purging compound wetted with a sodium carbonate (soda) solution (approx. 10 %
soda) is more efficient (foams!).
− After cooling down the machine commercial alkaline or acidic cleansers can be used
for clean-up.
− A wire brush is always an alternative but time consuming!
Exolit AP 765/766 do not generate screw deposits.

Defining the processing window for a sensitive product (schematic)

Throughput [kg/h]
processing
window
Screw speed [rpm]
© cpm GmbH, Georgsmarienhütte / Germany

Maximum output with a mass temperature of 210 °C (4 10 °F)

Throughput [kg/h]
Screw speed [rpm]

Maximum output without decomposition

Throughput [kg/h]
Increasing decomposition
by
shear and residence time
Screw speed [rpm]

Injection Moulding of Exolit® AP 76x
Processing conditions
− Temperatures up to 250 °C (482 °F) can be applied (ma ximum!)

− Minimize residence times of the compounds in hot zones
− Lower temperatures cause less mold deposits and lead to better material properties
(e.g. blooming)
− Empty machine and run purging polymer, if process is interrupted for some reason
Contacts
- Marketing
- KAM
- Technical Marketing
Public
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BL Flame Retardants
15.07.2013
Contact List of BL Flame Retardants

Marketing
− Head of Marketing and Advocacy Flame Retardants: Dr. Adrian Beard, global (tel. +49(0)2233/48-6114, Adrian.Beard@clariant.com )
Flame Retardants for Thermoplastics

− KAM: Mr. Elmar Schmitt, global (tel. +49(0)6196/757-6617, Elmar.Schmitt@clariant.com )
− Technical Marketing: Dr. Sebastian Hörold, Germany (partly), Italy, Spain, Switzerland, selected key accounts
(tel. +49(0)821/479-2506, Sebastian.Hoerold@clariant.com )
Bernd Naß , Asia, Austria, France, Greece, Nordics, Eastern Europe, UK
(tel. +49(0)821/479-2343, Bernd.Nass@clariant.com )
Elke Schlosser, Germany (partly), Benelux, Israel, LATAM, USA
(tel. +49(0)821/479-2445, Elke.Schlosser@clariant.com )
Flame Retardants for Thermosets

− KAM: Stefanie Fuge, global (tel. +49(0)6196/757-6621, Stefanie.Fuge@clariant.com )
− Technical Marketing: Dr. Frank Osterod, global (tel. +49(0)2233/48-6512, Frank.Osterod@clariant.com )
Intumescent Coatings
− KAM: Achim Hennemann, global (tel. +49(0)6196/757-6611, Achim.Hennemann@clariant.com )
− Technical Marketing: Dr. Klaus Bender, global (tel. +49(0)2233/48-6743, Klaus.Bender@clariant.com )
Phosphorus Chemicals and Polyurethanes

− KAM: Stefanie Fuge, global (tel. +49(0)6196/757-6621, Stefanie.Fuge@clariant.com )
− Technical Marketing: Dr. Achim Kruckenberg, global (tel. +49(0)2233/48-6174, Achim.Kruckenberg@clariant.com )

Exolit AP For Polyolefins July 2013

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Exolit ® AP 76x

Exolit AP 76x for Polyolefins

– Introduction – Intumescence in Polyolefins

– Contacts Clariant BL Flame Retardants

− Intumescence = swelling, foaming

− The thermoplastic material swells out (foams) on exposure to flame

− The carbon rich foam layer formed swollen

− reduces further oxygen

Intumescent Action in Polymers (I)

Flame exposure causes decomposition to:

Intumescent Action in Polymers (II)

Chemical mechanism (schematic):

1. Partial decomposition of APP

Exolit® AP 76x Product Group -

AP 760 AP 765* AP 766*

Products are based on different synergist technology

Exolit® AP 76x for Polyolefins

AP 760 AP 765* AP 766*

PP homo (MFR 12) 30.0 25.0 22.0

PP copo (MFR 5) 32.0 28.0 24.0

Achievable Test Classifications with the

PP-Homo 22 - 30 UL 94* V-0 (1.6/3.2 mm)

PP-Copo 24 - 32 UL 94* V-0 (1.6/3.2 mm)

PP-Copo 26 - 32 UL 94* 5-V (3.2 mm)

PP 20 - 30 IEC 60695-2-12 + 960°C (of part)

PE-HD (AP 760) 30 - 32 UL 94* V-0 (1.6/3.2 mm)

PE-LD (AP 760) 30 - 35 UL 94* V-0 (1.6/3.2 mm)

EVA (AP 760) 30 UL 94* V-0 (1.6/3.2 mm)

* Underwriters Laboratories (vertical burn test) 94

Achievable Test Classifications with the

PP-Homo 20 DIN 4102* B2 (1 mm)

PP-Copo 27 - 30 NT Fire 006+ passed

PP approx. 20 Cal TB 133D (3/8‘‘)

PE-LD (AP 760) 35 DIN 4102* B2 (0.5 mm)

EVA (AP 760) 30 DIN 4102* B2 (1 mm)

* German Building Code

Exolit® AP 76x Product Portfolio for Polyolefins

− Intumescent systems based on ammonium polyphosphate

Typical dosage of products is in the range of 20 – 35 % depending on polyolefin type

Exolit® AP 76x – where to use?

Exolit® AP 76x - Applications

Flame retarded PP/PE can partially substitute engineering plastics!

Comparison to other Flame Retardants

− Advantages compared to − Advantages compared to

Due to solid phase mechanism

Intumescent FR versus Halogen

Exolit AP 76x grades do not meet UL 94 V-1 or V-2 at lower loadings!

FR Effect in Polyolefins – LOI & UL 94 V

– UL 94 V-0 @ 20-25% dosage

40 UL 94 classification V-0 V-0

10 LOI 1,6 mm LOI 3,2 mm

Exolit® AP 76x – where to use?

− Processing industry (injection molders; producers of extruded products)

Exolit AP 76x for Polyolefins/Elastomers

Exolit AP 766 (TP):

– less water uptake during cooling

Exolit® AP 766 (TP) -

PP blank Exolit AP 766

MFR [g/10 min] 12.0 10.8

Tensile modulus [MPa] 1550 1870

Tensile yield stress [N/mm²] 35 25

Elongation at break [%] > 50 10.5

Impact str. (Charpy) [kJ/m²] 90 26

UL 94 1.6 mm n.c.* V-2 V-0 V-2 V-0