9. CLARIANT CORP., BU ADDITIVES-Tim Reilly

Additives BL-FRs T. Reilly New formulations with organic phosphinate flame retardants for plastics Fire Retardants in Plastics Conference 2011 Organized by: Applied Market Information LLC. June 17, 2011 Denver,Colorado, USA 09.05.2011 Tim Reilly Clariant Corporation BU Additives USA Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 2 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Presentation Outline Definition of Flame Retardant Synergism Organic Phosphinate Application Areas & formulations: - polyamides - thermoplastic polyesters - elastomers - epoxies Summary Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 3 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates Synergism “Synergism, as currently used in FR terminology is a poorly defined term. Strictly speaking, it refers to the combined effect of two or more additives, which is greater than that predicted on the basis of the additivity of the effect of the components”1). A B A + B Le Bras, Camino, Bourbigot and Delobel (Eds.), Fire Retardancy of Polymers. The Use of Intumescence. Royal Soc. of Chemistry (1998). Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 4 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Examples of Well Known FR Synergies Main goals:  Meet Fire Test Performance  Lowest possible FR loading  Less influence on physical properties  Less impact on the environment  Lower costs Antimony oxide Halogens Nitrogen Phosporus Hydroxides Nanoclays Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 5 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Comments concerning Nitrogen/Phosphorus Synergism)  Nitrogen/phosphorus systems in cellulosics: Since the 1960s and possibly earlier, a flame retardant effect was observed when using nitrogen compounds (urea, melamine) in combination with ammonium phosphates in cotton finishing operations.  In cellulosics, It has been found that there is not a “general synergist” that can be used in combination with phosphorus flame retardants. Some N-compounds can interfere with the phosphorus action (i.e. antagonistic effect).  Fire Resistant Intumescent coatings contain an acid source or catalyst for char formation (e.g. ammonium polyphosphate), a carbon donor (e.g. pentaerythritol) and nitrogen containing blowing agent (e.g. melamine). This formulation concept has been extended to other non-coating applications (e.g. FR plastics). Source: E. Weil, “Synergists, Adjuvants and Antagonists in Flame Retardant Systems”, Fire Retardancy of Polymeric Materials, Marcel Dekker, 2000 FR PP Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 6 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Organophosphorus Flame Retardant Chemistry from Clariant Based on Metal Phosphinate Pigments & Additives Division White Powder, Additive FR , Non-Toxic, High P Content(~24%), Does NOT absorb Water, Good Thermal Stability, registered globally in key markets Exolit® OP 1230 M = Al, Zn R1, R2 ≠ H Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 7 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Commerically Available Products Neat Aluminum Phosphinate Exolit®OP 1230: epoxies, aromatic polyamides (d95<50um) Exolit® OP 930: epoxy laminates (d95<20um) Exolit® OP 935: adhesives, flexible laminates, TPEs (d95<10um) Exolit® OP 1240: filled/unfilled thermoplastic polyesters (d95<75um) Formulated Aluminum Phosphinate (plus N-synergist) Exolit® OP 1311: TPEs, PA 6 GF Exolit® OP 1312: PA 6 GF, PA 66 GF Exolit® OP 1314: PA 6 GF, PA 66 GF Neat Zinc Phosphinate* Exolit® OP 950: melt soluble FR for polyesters *(limited supply at this time). Registered only in USA and Europe to date. Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) 1. Polyamides 1. Polyamides Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 9 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Flame Retardancy of Neat Phosphinate in PA Exolit® OP 1230 (20 % by weight) * 15% FR loading **V-0 achievable at 10 % loading n.c. = not classified UL 94 (0.8 mm) UL 94 (1.6 mm) GWIT (1mm) LOI PA 6 V-0 V-0 725 32 PA 6 GF 25 V-1 V-0 / V-1 750 PA 66 V-0 V-0** 725 36* PA 66 GF 30 V-1 / V-2 n.c. 750 PPA GF 30* V-0 V-0 800 40 (partially aromatic polyamide) Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 10 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Search for Synergies in Reinforced PA The Classic Combination: P and N !  Melamine products  Triazine or piperazine derivatives  Isocyanurates  Polyurea  etc. However: The number of thermally stable organic N-synerists is limited ! Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 11 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Best Choice for Glass Reinforced PAs Melamine polyphosphate (MPP) Melem O H P O P O O O P O O O H O O n N N N N H 2 N H 2 N H 3 + N N N N H 2 N H 2 N H 3 + N N N N H 2 N H 2 N H 3 + N N N N H 2 N N H 2 N N N N H 2 Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 12 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Positive UL 94 Results with P/N Synergistic Blends ! 16% 18% 19% 15% 16% 18% 19% PA 66 GF 30% Exolit OP 1312 16% 18% 20% PA 6 GF 30% Exolit OP 1311 3.2mm 1.6mm 0.8mm 3.2mm 1.6mm 0.8mm 0.4mm UL 94 5VA UL 94 V-0 Well investigated synergism with AL phosphinate & melamine polyphosphate in PA 6 GR and PA 66 GR: Clariant: EP 1070754 and EP 1386942 --- --- --- --- Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 13 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates Thermal Stability  Sufficient thermal stability of Exolit OP 1230 + MPP for some Polyamide 6 applications  Discoloration is observed in Polyamide 66 applications  With zinc borate no discoloration and better char is observed Exolit OP 1230 MPP in PA6 GR Exolit OP 1230 MPP in PA66 GR Exolit OP 1230 MPP ZB in PA66 GR Injection moulded PA 6&66 GR parts Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 14 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates UL 94 of PA 66 GR with Phosphinate – MPP & ZB PA 66 55 55 54 Glass fibres 25 25 25 Exolit OP 1230 20 13 MPP 20 6,5 Zinc borate 0,5 UL 94 (0.8 mm) V-1/V-2 N.c. V-0 UL 94 (1,6 mm) N.c. V-1/V-2 V-0  Total FR content: 20 % by wt.  V-0 @ 0,8 mm with Phosphinate + MPP only Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 15 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates FR Mechanism of the Phosphinate/MPP- Synergy  Shift from high gas phase contribution (neat phosphinate) to more solid phase interaction (FR blend)  Phosphinate reacts with the synergist before acid is released  Barrier formation by Al-phosphate is intensified  Stability of barrier is increased with zinc borate Braun, Schartel et. al., Polym. Degr. Stab. 92, 1528 ff. (2007) Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 16 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates FR Mechanism Shifts in PA 66 GF dependent upon Synergists PA 66 GF + AL Phosphinate PA 66 GF + AL Phosphinate + MPP PA 66 GF + AL Phosphinate + MPP + Zn Borate Flame Inhibition + + + Carbonaceous Char + + + + + + + Inorganic Barrier + + + + + + . Braun , Schartel, ‚“ Flame Retardancy of Aluminum Phosphinate in Glass Reinforced Thermoplastics“, BCC Conference 2008. Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 17 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Glow Wire Test IEC 60695 Pigments & Additives Division 1N specimen glow wire (max. 960°C) sled  Glow Wire Ignition Temperature (GWIT): Maximum Temperature Level with ignition time < 5 seconds.  Glow Wire Flammability Index (GWFI): Maximum Temperature Level with an after flame < 30 seconds.  Purpose of Test: Determination of fire hazard by bringing specimen in contact with an electrically heated wire at a specific temperatures. Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 18 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates GWIT improvement of PA 66 GR PA 66 49 48 49 Glass fibres 30 30 30 Exolit OP 1230 13.8 8.0 8.0 MPP 6.7 12.0 8.0 Melem* 4.0 Zinc borate 0.5 2.0 1.0 GWIT (1 mm) [°C] 750 800 775 UL 94 (0.8 mm) V-0 V-0 V-0 * Result by Clariant lab refering to US 2007299171 by Rhodia  Total FR content: 21 or 22 % by wt. Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 19 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates Phosphinate plus Carbon Nanotubes in PA 66 GR  Improved GWIT performance, but reduced mechanical properties PA 66 52 51,8 51 Glass fibres 30 30 30 Exolit OP 1312* 18 18 18 Carbon Nanotubes** 0,2 1 UL 94 (0.8 mm) V-0 V-0 V-0 GWIT (0,75 mm) [°C] 750 775 775 Impact Strength 63 58 53 Elongation at break 2,6 2,3 1,9 * blend of phosphinate, MPP, ZB ** Nancyl 7000 Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 20 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Nanoclays as Synergists Example: PA 11 PA 11 100 70 72.5 Exolit OP 1230 30 20 Nanoclay 7.5 PHRR [kW/m2] 1589 887 480 PHRR reduction [%] 44 70 UL 94 class n.c. V-0 V-0 Lao,Wu, Moon, Koo, Morgan, Pilato and Wissler, J. Comp. Mat. 43, 1803-1818 (2009) Remarkable reduction in peak heat release (PHRR) at lower total loading ! n.c. = no class Peak Heat Release Rate (cone calorimetry) = peak energy evolved Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 21 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Boehmite Mineral – A synergistic component ?  Boehmite grades can partially substitute a Phosphinate/MPP-blend in PA 6/66 GR (more a cost issue, not performance driven) Berneck, J. Proceedings of „Fire Resictance in Plastics“, Dec 2009 (Nabaltec).  Boehmite as a co-additive to Phosphinates in high temperature polyamides Martens, M. Saga, Y. WO 2005_033192 (DuPont de Nemours) AlO(OH) Source: Nabaltec, Germany Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 22 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates Phosphinate plus Boehmite in PA 66 GR  Exolit OP 1312 can be partly replaced by Boehmite, reduced mechanical properties PA 66 50 48 49 Glass fibres 30 30 30 Exolit OP 1312* 20 15 13 Boehmite** 5 7 UL 94 (0.8 mm) V-0 V-0 V-1 GWIT (0,75 mm) [°C] 750 775 750 Impact Strength 63 48 45 Elongation at break 2,6 2,1 1,9 Tensile Strength 146 130 126 * blend of phosphinate, MPP, ZB ** Apyral AOH 180E Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) 2. Thermoplastic Polyesters Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Main Decomposition Pathway of PBT/GF- aluminum phosphinate-melamine cyanurate Slide 24 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates Source: Braun, Schartel, Macromolecular Materials Engineering, 2008, 293, 206-217 Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 25 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Neat Phosphinate grade for PBT / PET Exolit OP 1240 (neat phosphinate) Ingredients PBT (non- reinforced) PBT GF 30% PET (non- reinforced) PET GF 30% PET 84.7 54.7 PBT 79.7 49.7 Glass fibers 30 30 Exolit OP 1240 20 20 15 15 Licowax E 0.3 0.3 0.3 0.3 UL 94 (0.8mm) V-0 V-0 V-2 V-0 GWIT [°C] 725 750 700 725  AL-phosphinate has more FR efficacy in PET GF v. PBT GF  Glass fibers do not influence UL94 rating in PBT, while there appears to be an influence in PET Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 26 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Best choice for PBT / PET Melamine cyanurate N N N N H 2 N H 2 N H 2 N H N H N H O O O Melamine polyphosphate (MPP) O H P O P O O O P O O O H O O n N N N N H 2 N H 2 N H 3 + N N N N H 2 N H 2 N H 3 + N N N N H 2 N H 2 N H 3 + Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 27 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates No Real FR synergy in PBT GF 30% Choice of FR blend by other criteria PBT 49.7 49.7 49.7 Glass fibres 30 30 30 Exolit OP 1240 20 13.3 13.3 MPP 6.7 MC 6.7 Licowax E 0.3 0.3 0.3 UL 94 (0.8 mm) V-0 V-0 V-0 MPP = melamine polyphosphate MC = melamine cyanurate VN 97644;97947-950  UL 94 V-0 with 20% total flame retardant Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 28 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Polymer degradation during processing Solution Viscosity of PBT Reinforced 127 99 105 112 0 20 40 60 80 100 120 140 without FR OP 1240 OP 1240/MC OP 1240/MPP S o lu ti o n v is c o s it y [ c m ³/ g ] Highest SV-level retained with MPP as a synergist MC has a cost advantage 30% glass fibers, 20% total flame retardant Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 29 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates FR Synergy with Neat Phosphinate & PTFE in PBT (non-reinforced) PBT 79.7 84.4 79.4 Exolit OP 1240 20 15 13.3 PTFE 0.3 0.3 MC 6.7 Licowax E 0.3 0.3 0.3 UL 94 (0.8 mm) V-0 V-0 V-0 GWIT 1 mm 725°C 800°C 825°C  UL 94 V-0 with a total FR loading of 15.3 %  GWIT significantly increased Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 30 08.11.2010 Confidential: Exolit OP 1240 + Phosphazene Phosphazene Products  Otsuka SPB 100  Fushimi Rabitle FP 110 – Melting point 110°C (Rabitle) – Phosphorus content 13,4%  Registration in EU, US, China, Japan, Taiwan, Korea  Raw materials are PCl3 und NH3 Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 31 08.11.2010 Confidential: Exolit OP 1240 + Phosphazene Thermal Stability  Rabitle (Fushimi Phamaceuticals, JP): 2% @ 308°C  SPB 100 (Otsuka Chemicals, JP) : 2% @ 322°C Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 32 25.11.2010 Public: Flame Retardant Synergies with Organic Phosphinates UL 94 PBT – Phosphinate + Phosphazene  UL 94 V-0 and improved mechanical properties with phosphinate + phopshazene PBT 79,7 79,7 79,7 Exolit OP 1240 20 15 Phosphazene 20 5 Licowax E 0,3 0,3 0,3 UL 94 (0.8 mm) V-0 N.c. V-0 Elongation at break / % 2,5 17 7 Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 33 08.11.2010 Confidential: Exolit OP 1240 + Phosphazene PBT reinforced  No V-0 with Exolit OP 1240 + Phosphazene  V-0 and better elongation with Exolit OP 1240 +MPP+ Phosphazene VN 105089 105090 105091 105092 PBT Ultradur B 4500 Natur 50 50 50 50 Vetrotex EC 10 4,5MM 952 30 30 30 30 Exolit OP 1240 13,3 10 13,3 13,3 Phosphazen SPB 100 6,7 3,3 3,3 Melapur 200/70 6,7 3,4 6,7 UL 94 0,8 mm V-1 V-0 V-0 V-0 Burning time s 110 27 47 28 UL 94 1,6 mm V-1 V-0 V-0 V-0 Burning time s 115 24 23 17 E-Modulus Mpa 8882 10076 9984 11333 Tensile strength Mpa 101 111 108 110 Elongation at break % 3 2,4 2,4 1,9 Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) 3. Thermoplastic Elastomers Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 35 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Polyester Elastomers – Performance synergies with new Polyphosphonate P R 1 R 2 O O n _ M n+ n O O P O CH3 CH3 CH3 Metal phosphinate (®Exolit OP 1240) Polyphosphonate (®FRX 100) Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 36 29.04.2010 Public: Flame Retardant Synergies with Organic Phosphinates Extrusion grade TPE-E for W+C Results with specific Exolit/FRX combination  VW 1 test passed  Safe UL 94 V-0 with 20 % total FR loading  GWIT 850°C (not required for W+C but tested for evaluation of FR effects)  Easy processing on small scale tube extrusion line, good melt strength  Smooth surface appearance  Higher elongation at unchanged shore hardness US patent application pending Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) 4. Epoxies Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 38 29.04.2010 Confidential Synergism with metal phosphinates- epoxies Possible combinations of Exolit ® OP 930/935 with other FR Metal phosphinate P R 1 R 2 O O n _ M n+ DOPO based EP resins Al(OH)3 (HO)n O P O CH3 O O P O O CH3 (OH)m p m,n = 0 or 1 MPP ATN-hardener Fyrol PMP O O H R1 " O O N N O R N O H N O H O R O O H R1 " O O n Benzoxazine/epoxy Dr. S. Hörold, BU Additives, ATPG - Flame Retardants (Copyright Clariant. All rights reserved.) Slide 39 29.04.2010 Confidential Improvement of Glass Transition Temperature (Tg): Aluminum phosphinate plus melamine polyphosphate in Epoxy Laminate for Printed Wiring Board Performance: Glass transition temperature (Tg) Method DSC, prepreg pdr flame retarder ratio Tg (°C) DSC OP 930 132 OP 930/MPP 3:1 140 OP 930/MPP 1:1 156 OP 930/MPP 1:3 160 MPP 167  MPP increases Tg level and lowers formulation costs  Exolit OP 930 improves electrical properties and resistance against water