HALOGEN-FREE FR

1. Ammonium Polyphosphate (APP) : [NH4 PO3]n ; n= chain length

-an inorganic salt of polyphosphoric acid and ammonia.
-Crystal phase I APP (APP I) is characterized by a variable linear chain length, showing a
lower decomposition temperature (aprox 150°C) and a higher water solubility
-Crystal phase II APP (APP II) APP II structure is cross linked/branched. The molecular
weight is much higher than APP I with "n" value higher than 1000. APP II has a higher
thermal stability (decomposition starts at approximately 300°C) and lower water solubility
- The maximum processing temperature is 230°C. Also the APP should not be processed
under pH >7, because ammonia will be released.
- most important inorganic nitrogen – phosphorus compound used as a flame retardant
- (flame-retard paper, canvas, cotton batting, draperies, fiberboard, or other cellulosic
materials =ammonium phosphates)
- intumescent
APPLICATION: Polyamides, Polyesters, Polyolefins,rigid Polyurethanes

2. . Bisphenol A bis(diphenylphosphate) (BDP) : C39H34O8P2

- Colourless Thick Oil
- Can be stored in a refrigerator
- used in electrical wire covering
- High hydrolytic stability and heat resistance
- brings high insulation property, due to its condensed structure.
- TPP Content % ≦1.00
- Soluble in the following materials: DMSO Ethyl Acetate
APPLICATION: PC / ABS, Polycarbonate, Polyurethanes

3. Dicumene : C18H22 (Flame Retardant Synergic)

- 2,3-Dimethyl-2,3-diphenylbutane
- an environment friendly replacement for Antimony Tri-oxide (Sb2O3) and is
commonly used as a flame retardant (FR) synergist for polypropylene and
polystyrene, especially in expandable polystyrene (EPS).
- White to light yellow powder
- can be used with brominated flame retardants for preparation of polymers
- can reduce the dosing levels of brominated compounds used.
- a radical initiator for the crosslinking of polymers at high temperature.
- High thermal stability and does not contain any peroxide
- dosage is only 30% of traditional Sb2O3
APPLICATION: Polyolefins, XPS

4. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) : C12H9O2P

- White crystal or powders or granules
- mainly used for Flame retardant epoxy resin for PCB, Color protector for plastics, Fire
Retardant Polyester Fiber Fabrics
- Non- toxic flame retardant
- the first efficient halogen free flame retardant for novolac-based epoxy systems with
low phosphorus content
- more likely to act in the gas-phase
- foam material containing this flame retardant satisfies the highest flame retardant
classification (UL 94 HB).
 - mechanism is that the phosphorus containing compound is converted by thermal
decomposition to phosphoric acid. The phosphoric acid then dehydrates the oxygen
containing polymer and causes charring.
APPLICATION : Polyamides, Polyesthers, Polyurethanes

5. Triarylphosphate Isopropylated (IPPP)

- Isopropylate Triphenyl Phosphate/TIPP
- Colorless or light yellow transparent liquid
- Widely used for fabric coating, circuit boards, flooring, textiles, PVC, phenolic resin
and other fields.
- a fireproof plasticizer with excellent hydrolysis stability, oil resistance and electric
insulativity, high fungus resistance, good mutual solubility, excellent fireproof and
plasticization property.
- PVC, Phenolic, PU, Epoxy resins
APPLICATION: Polyurethanes,PPO

6. Triphenyl Phosphate (TPP) : (C6H5)3PO4 or C18H15O4P

-an aryl phosphate resulting from the formal condensation of phosphoric acid with 3 mol
eq. of phenol
-a solid; flame retardant and a plasticizer for cellulose acetate and nitrocellulose.
-derived from phenol.
-organophosphate FR
- volatile
- Not classifiable as a human carcinogen.
- permits lower levels of bromine (combination of bromine with phosphorus in PS)
*note: In recent years several companies have started labeling nail polish as "3-free,"
meaning the products do not contain the toxic chemicals toluene, formaldehyde or
dibutyl phthalate, the compound that triphenyl phosphate replaced in some product lines.
APPLICATION: electronic equipment, PVC, hydraulic fluids, lubricating oil, glues, in nail
polishes, casting resins, lacquers and varnishes. PC / ABS, PPO/HIPS, RUBBER,
Epoxy Resin, Phenolic Resin, Acetalic Resin

7. Hexaphenoxycyclotriphosphazene Oligomer (HPCTP): (C12H10NPO2)n

-white powder
- addition- type flame retardant
- PC, PC / ABS, PA, PBT, PET
APPLICATION: epoxy resin, copper clad laminate, LED light-emitting diode,
encapsulating materials and polymer materials.

8. Phenoxycyclotriphosphazene : C36H30N3O6P3
- excellent thermal stability, corrosion resistance, water resistance, chemical
resistance, and good material compatibility, minimal influence on the material
properties
- Hexaphenoxycyclotriphosphazene(HPCTP); Phenoxycyclotriphosphazene (PCPZ)
- flame retardancy is better than Brominated flame retardant, can reach UL-94V0
grade.
- Good retardancy on Epoxy Resin
- After using the HPCTP, the PC has great water proof, Oil proof and will not be
eroded by organic solvent.
- white crystal
 APPLICATION: LED, powder coating, potting material and polymers, PC and
PC/ABS resins
9. Cyclic Phosphonate
- high phosphorus containing material is suited for applications in both thermosoling of
polyester fabric for wash durability
- demonstrates excellent flame improvement with many textile back coatings.
- suited for acrylic based latices and other oxygen containing polymers
- has excellent water solubility and can be added directly to the latex without the
addition of an emulsifier.
- Excellent thermal stability
- Low volatility
- Low acidity
- Clear, viscous liquid
- Nonionic
- Melamine powder or various bromine compounds may be added to further enhance
flame-resistant properties.
APPLICATION: Textiles, Carpet, Back coatings, Non- wovens, polyesters, PC / ABS,
Polycarbonate , Polyurethanes

10. Potassiumdiphenylsulfonesulfonate (KSS) : C12H9KO5S2

- extremely effective as a flame retardant additive with premium performance in
polycarbonate at very low additive levels
- white crystalline powder, potassium salt of a complex of diphenyl sulfone sulfonate
and diphenyl sulfone disulfonate
- note: For most effective incorporation it is recommended that the additive be initially
dispersed Into a 10% or more masterbatch and then compounded into the final
plastic blend
- polycarbonate resin
- No characteristic odor
- Decomposition products are toxic. (NOx and SOx type,CO, CO2)
APPLICATION: transparent PC at very low dosage,polycarbonates

11. Melamine : C3H6N6 or C3N3(NH2)3

- cyanuramide or triaminotriazine
- rich in nitrogen 66% (fire retardancy)
- an organic compound that is often combined with formaldehyde to form…
- Melamine resin: a synthetic polymer which is fire resistant and heat tolerant. It is a
very versatile material with a highly stable structure; a thermoset plastic
- can be easily molded while warm, but will set into a fixed form.
- manufactured by mixing urea with formaldehyde under heat and pressure (Melamine
resin) ; difficult to recycle
- releases water under pressure, which will make the plastic unstable if not removed.
- can be made into a foam product; Melamine foam has a distinctive structure
composed of stacked bubble shapes, which are extremely hard and therefore can
easily clean a wide variety of substances. (Magic Eraser)
- textiles used in upholstery and the uniforms worn by firemen; Thermal liners, heat
resistant gloves, and aprons to protect from splashback of hot substances are made
using melamine
- help to resist the spread of fire in aircraft and buses by providing a fire blocker.
 - also used in the manufacture of some filters; Melamine filters are capable of handling
a high capacity and can be used in hot environments due to the heat resistance of
melamine.
- intumescent flame retardant
*note: A copolymer containing melamine, formaldehyde, and sodium bisulfite
produces a foam with sound-absorbing and flame-retardant properties. The foam has
a notably hard microbubble structure, which gives it an abrasive quality that has
been utilized in the development of cleaning products.
APPLICATION: Adhesives and sealant chemicals, Pigments, Building/construction
materials - wood and engineered wood products, Foam seating and bedding products,
Polyamides, Polyesthers, Polyolefins, Polyurethanes
12. Melamine Cyanurate : C6H9N9O3
- fine, white, crystalline powder, nontoxic, odourless
- for polyamide/ nylons(unreinforced)
- intumescent flame retardant
- low toxicity in case of fire, the absence of dioxin and halogen acids as well as their
low evolution of smoke. (melamine compounds)
- salt of melamine and cyanuric acid
- Melamine Cyanurate has a higher thermal stability than pure melamine, remaining
stable upto about 320 °C
- Aromatics, Inhibitors
APPLICATION: Polyamides, Polyesthers, Polyurethanes

13. Melamine Pyrophosphate : C3H10N6O7P2

- fabrics, nylons, paint, paper and plastics
- electronic industry when incorporated in the manufacturing of circuit boards and
other equipment
- can be used with epoxy and other adhesive compositions to achieve fire retardant
barriers in gluelines in wood and plastic laminates
- Due to acidic catalysis, inert gas formation and foaming, flames are retarded or
eliminated.
- does not contribute to the formation of toxic gases.
- Fine white powder , no moisture absorption
- Fire proof coatings, thermosetting and thermoplastics
- PA, Epoxy Resins, PU, Polyesters, PP
APPLICATION: Polyamides, Polyesthers, Polyolefins, Polyurethanes

14. Melamine Polyphosphate (MPP): HO(C3H7N6PO3)nH

- Specially used for glass-fiber reinforced nylon, thermoplastics, thermosetting
plastics, rubber, and fiber
- very high thermal stability
- White powder
- slightly soluble in water, slight smockingness, no moisture absorption
APPLICATION: Polyamides, Polyesthers

15. Pentaerytritol: C(CH2OH)4

- odorless white solid
- Sinks and mixes slowly with water.
- a primary alcohol.
  Note : The synthesis of pentaerythritol involves reacting four moles of
formaldehyde and one mole of acetaldehyde in two differentiated steps.
- Adhesives and sealant chemicals
- Fuels and fuel additives
- Lubricants and lubricant additives
- Paint additives and coating additives
- Plasticizers
- Viscosity adjustors
APPLICATION: Polyamides, Polyurethanes

16. Tetraphenyl Resorcinol Diphosphate (RDP): C30H24O8P2

- Colourless to Pale Yellow Oil
- Aromatics, Phosphorylating and Phosphitylating Agents
- Moisture Sensitive
- low volatility and high heat resistance.
- Resorcinol bis(diphenyl phosphate)
- engineering thermoplastics such as phenylene oxide blends, thermoplastic polyesters,
polyamides, vinyls and polycarbonates
- primary flame retardants for polycarbonate and acrylonitrile-butadiene-styrene (ABS)
copolymers. (aromatic phosphates)
APPLICATION: PC / ABS, Polycarbonate, Polyurethanes, HIPS PPO

17. 2-(6-Oxide-6H-dibenz,c-e, 1,2 oxaphosphorin-6-y) methyl – Butandioic acid (DDP):

- heterocyclic phosphorus flame retardant
- White solid
- Excellent thermal stability, Good water resistance, Anti-oxidation ability
- reactive and additive flame retardant
- hardener agent of the epoxy resin
 NOTE: In polyester, Copolymerization reaction can happen between DDP and PET、
PEN and PBN, the flame retardant effect will increase with the increase of the
component of phosphor.
- can be used in the textile coating of PU.
APPLICATION: Polyamides, Polyesthers, Polyurethanes
18. Tricresyl Phosphate (TCP): C21H21O4P
- colorless,odorless liquid.
- Insoluble in water and slightly denser than water.
- Toxic by ingestion and skin absorption
- Non-combustible, substance itself does not burn but may decompose upon heating to
produce corrosive and/or toxic fumes. Containers may explode when heated. Runoff may
pollute waterways.
- are susceptible to formation of highly toxic and flammable phosphine gas in the
presence of strong reducing agents such as hydrides. Partial oxidation by oxidizing
agents may result in the release of toxic phosphorus oxides.
 - Organophosphate
- PE, PVC, Rubber, Wire & cables
- stable in neutral and acidic media at normal temperatures. But it is readily hydrolysed in
an alkaline medium, producing dicresyl phosphate and cresol
- as a solvent and thinner for nitrocellulose, paints acrylate lacquers, and varnishes, as a
plasticizer for PVC processing, a heat exchange media, an additive in high-pressure
cooling lubricants, a lead scavenger in gasoline.
- exhibit the properties of anti-wear and corrosion inhibition either as free esters or in the
forms of metal and amine salts
APPLICATION: Polyurethanes, adhesives
19. Triethyl Phosphate (TEP): C6H15O4P or (C2H5)3PO4
- colorless, corrosive liquid
- Combustible. Slowly dissolves in water and sinks in water
- trialkyl phosphate that is the triethy ester derivative of phosphoric acid. It derives from an
ethanol.
- mild pleasant odor
- useful as a solvent in many applications, as a plasticizer for tough, fire-resistant plastics,
and as an agricultural chemical as an intermediate in preparing tetraethyl pyrophosphate
(TEPP).
- Process solvents, industrial catalyst
APPLICATION: Intermediate for agriculture insecticides; floor polishes; lubricants;
hydraulic fluids; aprotic solvent. Polyurethanes
20. Aluminum Trihydrate (ATH): (AI2O3•3H2O)
- non-toxic, halogen-free, chemically inert, and has low abrasiveness.
- Extends titanium dioxide (TiO2) and colors without darkening
- Stain, scrub and water resistant; UV transparent
- Dehydration mechanism: under flame, it forms 2 non- toxic ingredients aluminum oxide
(forms inert residue/char) and water which dilutes the smoke.
- Obtained from Bauxite(a mixture of hydrous aluminum oxides, aluminum hydroxides,
clay minerals, and insoluble materials such as quartz, hematite, magnetite,)
- used as an inert filler in paints and tends to increase the transparency of colors when
dispersed in oils.
- Also used for waterproofing, tapestry and furniture.
- Maybe coated with Zin Hydroxy stannate or Zinc Stannate
APPLICATION: polyester, polymer resins as low-smoke, non-toxic replacement for latex,
rubber, wires & cables and floorings. Plastics, paper, paints & coatings, adhesives,
chemicals, and pharmaceuticals.
21. Magnesium Hydroxide (MDH) : Mg(OH)2 or H2MgO2
- an inorganic compound that occurs in nature as the mineral brucite. It acts as an antacid
with cathartic effects .
- Solution of antacid and laxative with magnesium hydroxide
- An additive type of FR
- Non-corrosive
 - May be combined with ATH
- low and non-toxic smoke
- high thermal and long term heat-aging stabilities
- dimensional stability after injection molding
- acid scavenger and heat stabilizer
- reinforcing filler
- high thermal stability up to 340C and is recommended where ATH is not sufficiently
stable
- Mg(OH)2 MgO + H2O (endothermic decomposition)
- Produces MgO which is alkaline, reducing the chances of appearance of acidic, corrosive
gases
- May be coated with Zinc Hydroxy Stannate or Zinc Stannate
- More basic than ATH, neutralizes HCl better
22. Zinc borate : B2O6Zn3
- white powder
- (typically 45% ZnO, 34% B2O3 and 20% H2O).
- Slightly soluble in water.
- used as a fungus and mildew inhibitor, to fire proof textiles
- Effective in enhancing the flame-inhibiting powers of chlorine
- May be combined with ZHS and ZS,ATH
- Low toxicity
- Acid suppressant
- Char promoter(forms glassy layer)
- Low tint strength ( allows lower pigment loading vs antimony oxide, retains translucence)
- For protection of plastics, a rate range of 3-30 parts product per hundred parts resin is
used. For coatings, rates range from 1.25 to 3.0 lb/gal.
23. Zinc Stannate : ZnSnO3 or O3SnZn
- Tin zinc oxide
- Inorganic
- may be used as synergists with halogenated flame retardants and halogen-
containing polymers as partial or complete substitutes for antimony III oxide

- Zinc Stannate vs. Zinc Hydroxy Stannate

properties ZINC HYDROXY STANNATE ZINC STANNATE
CHEMICAL FORMULA ZHS/ ZnSn(𝑂𝐻) 6 or ZnSn𝑂3
ZnO.𝑆𝑛𝑂3 𝐻2 𝑂
PHYSICAL FORM White powder White powder
MEDIAN PARTICLE SIZE, 1 µm 1 µm
𝐷50
PARTICLE SIZE, 𝐷90 10 µm 10 µm
SURFACE AREA 7 𝑐𝑚2 /gm 7 𝑐𝑚2 /gm
SPECIFIC GRAVITY 3.3 3.9
BULK DENSITY 0.6 gm/ 𝑐𝑚3 0.8 gm/ 𝑐𝑚3
REFRACTIVE INDEX 1.9 1.9
pH (5% aqueous slurry) 10 10
 FREE MOISTURE 0.5% 0.5%
TIN 41.5- 43% 51-52%
ZINC 22-24% 28-29%
LOSS ON IGNITION 17-19% 2%
DECOMPOSITION 200°C 400°C
TEMPERATURE
- Zinc stannate is preferred on polymers that are processed above 200°C. almost all
temperature ranges
- ZHS is recommended for use in formulations that are processed below 180’C