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TRANSCRIPT
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Polyphosphazenes as halogen free flameretardants for textiles
33rd Cotton Conference
retardants for textiles
Thomas Mayer-Gall, Ralf Kappes, Torsten Textor, Klaus Opwis, Jochen S. Gutmann
DTNWDeutsches Textilforschungszentrum Nord‐West
Krefeld‐ Research institute‐ Associated Member:
‐ Hochschule Niederrhein‐ Universität Duisburg‐Essen
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DTNW, Krefeld
FiberFiber
Surface
modification
Function
Methods
• thermal
• wet chemical• wet chemical
• sol‐gel process
• super‐critical fluids
• physical
• photo‐chemical
• laser
• …
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Wettability, adhesion
hydrophil
hydrophob
oleophob
Barrier‐layers
Protection againts:
‐chemistry
‐abrasion/wear
‐light (UV or IR)
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New green dyeing solvents
~ 3.0 m
Ionic LiquidsscCO2
Conductive Texiles
Spannungsquelle
PEDOT:PTSA‐Ausrüstung
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Antimicrobial TextilesAntifouling Textiles
Silver, Copper, Zinc
Biopolymere
Photo‐catalytic surfaces
Organotextile Catalysis
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Environmental Remediation ‐Urban‐Mining
Flammschutz
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Why flame retardants?Why halogene free?
• World: 300.000 dead by firei b /d f i+ serious burns/deformation
• Europe: 25.000 dead at 2.5 million fire
• 1 % economical damage
• 80 % dead at house fire
Why no halogens?Why no halogens?
• Environmental problem
• Toxicity, persistent, bioaccumulation, cancerogenice
• REACH / Ban of use
Why flame retardant textiles?
Cotton Cotton/PETCotton Cotton/PET50:50
PETCotton/PET
50:50
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Why flame retardant textiles?
Cotton Cotton/PETCotton Cotton/PET50:50
PETCotton/PET
50:50
Task of a flame retardant
US National Fire Protection Association
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Functions of Flame retardants
• Dilution of the gas phase by• Nitrogen• Nitrogen• Water
• Radical Scavenger• Bromine or Chlorine compounds
• Formation of a barrier layer • Char formation (phosphor compounds/nanoclays)Char formation (phosphor compounds/nanoclays)• Intumescent layer
Why polyphosphazenes?
Nitrogen: • dilution of gas phase
• Anchor Groups• properties
modification• further flame
retardant function
g p
Phosphor:• Char and
• Barrier layer formation
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Solvent-based synthesis of polyphosphazenes
N P
Cl
N NP
ClCl
∆
Linear Chloro-PPZ
ClnP
NP
Cl
ClCl
Cl
cat.
ClONa
O
AllyPPZ
N P
Cln
+ N P
On
Mujumdar, A. N.; Young, S. G.; Merker, R. L.; Magill, J. H. Macromolecules 1990, 23, 14–21., DOI: 10.1021/ma00203a004
Next step: Photo-induced immobilization
PET
N P N P N P N P N P N P N P
UV
PET
N P
R
N P N P N P N P N P N P
R R R
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CharacterizationCotton/PET (50/50)
FT-IR (ATR)
0,03
0,04 PET/BW (Huntsman, orange) unbehandelt PET/BW (Huntsman, orange) allyl-oxy-PPZ-modifiziert
blank
4000 3500 3000 2500 2000 1500 1000
0,00
0,01
0,02
Abso
rptio
n
Wellenzahl [cm-1]
Analyses
SEM
yAdd-on 22.3 wt.-%
P-content (ICP-OES) 3.06 wt-%
EDX (surfacecomposition)
C O P
Blank 50.2 % 49.8 % 0
Allyl-oxy-PPZ modified 49.9 % 31.6 % 18.5 %
PPZ‐modified
Flame retardant performancepre-testing by TGA
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Flame retardant performancePre-testing by TGA
LOI: LOI:LOI:17.5 23.0
LOI:18.5 26.5
LOI:31.5 19.5
LOI:16.5 24.0
Flame retardant performance“DIN EN ISO 15025”
Cotton Cotton/PETCotton Cotton/PET50:50
PETCotton/PET
50:50
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Flame retardant performance“DIN EN ISO 15025”
Mechanism: Char Analysis ‐Thermal decomposition
IR – thermal decomp.
IR ‐ Char
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Washing resistanceExample: Cotton/PET Blend (50/50)
1 Washing CycleAdd-on 26.7 %
2 Washing CyclesAdd-on 26.7 %
6 Washing CyclesAdd-on 25.8 %
No significant loss of weightNo significant loss of flame retardant performance
untreated
Abrasion resistanceExample: Cotton/PET Blend (50/50)
No significant loss of weightNo significant loss of flame retardant performance
5 k rounds 10 k rounds 50 k rounds
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Summary
• polyphosphazenes are suitable halogen-free flame
retardants
• permanent and resistant finishing of textiles
• curing of AllylPPZ by UV-irradiation
• Adjustable loading in the range of 10 - 50 wt.-%
• Ideal flame retardant for Cotton/PET blends and pure
cotton
• Significantly change in melting behavior of PET by PPZ
finishing
Outlook – Sol‐Gel
N‐P‐Silane – Flame retardant test
+14.5 %
30
+6.3 %
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Thank you for your attention!!!Financial Support
AcknowledgementThe authors wish to acknowledge financial support by the Forschungskuratorium Textil e.V. for the project IGF 16780 N. The support was granted within the
contact: mayer‐[email protected]
IGF 16780 N. The support was granted within the program Industrielle Gemeinschaftsforschung (IGF)
from resources of the Bundesministerium fürWirtschaft und Technologie (BMWi) via a
supplementary contribution by the Arbeitsgemeinschaft IndustriellerForschungsvereinigungen e.V. (AiF).