Commercial Alternatives to Deca BDE

S.V. Levchik, ICL-IP America, 430 Saw Mill Rriver Rd., Ardsley, NY, 10502, M. Leifer, S. Lifshitz and D. Pelah, ICL-IP, P. O. Box 180, Beer Sheva 84101, Israel

Decabromodiphenyl Oxide, Deca-BDE

Property Values Chemical formula

OBr

Br

Br

Br

Br

Br

Br

Br

Br

Br CAS number 1163-19-5 Bromine content, % 83 Molecular weight 959 Purity, assay % >97 Melting point, ºC 305 Thermal stability, 5 wt. % loss by TGA, ºC 360 Appearance White powder, often micronized Water solubility Insoluble Vapor pressure Not measurable

3

A decade ago Deca-BDE was the second after TBBA most widely used brominated commercial flame retardant.

Since Deca-BDE has a broad spectrum of application it has been a workhorse FR for over 30 years

Although more advanced FRs were in the market, low cost and availability ensured Deca-BDE deep penetration to all major sectors of the economy including aerospace industry

We believe that Deca-BDE helped to save many lives and millions of dollars in property damage

Background

Adhesives and Tapes Composites Ducting & Molded Parts Electrical/Electronics Emergency Equipment Fabrics & Films Insulation Interiors Sealants

Use of Deca-BDE in Airplanes

ICL-IP advocates broader use of polymeric or high molecular weight brominated and phosphorus FRs

Polymeric FRs have advantages:◦ Low water solubility, thus, not expected to be toxic to aquatic

organisms ◦ Not likely to be bioavailable, e.g. no bioaccumulation is expected◦ USA EPA- “Polymers are not readily absorbed by biological

species and thus are relatively non toxic”= low risk◦ EU REACH- “exemption for polymers” ◦ Leaching and migration is not likely◦ Due to high thermal stability polymer FRs show good

performance during recycling

Polymeric FRs

Brominated FRs Brominated FRs (BFRs) provide combination of gas phase and

condensed phase action via chemical and physical mechanisms.

BFRs are the most effective flame retardants and therefore they are used in highly flammable polymers

BFRs are typically used at relatively low loading, therefore impact on physical properties of the polymer is low

At present time there is no acceptable substitution for BFRs in ABS, HIPS and polyolefins

Halogen-free FRs are available for polyesters, nylons, epoxy resins and PU foams, ◦ Often they fall short on physical properties and price-performance

Brominated Epoxy, F-2000

F-2000 is a series of oligomers and polymers which differ by molecular weight and softening temperature◦ Low molecular weight products give good resin flow◦ High molecular weight products have good thermal stability◦ F-2000 series show good UV stability compare to other

aromatic BFRs

O C

CH3

CH3

O

Br

Br

Br

Br

CH2CHH2C

O

CH2 CH

OH

CH2 O C

CH3

CH3

O CH2 HC CH2

O

Br

Br

Br

Brn

Brominated Epoxy, F-2000 BFR Mw Br content

% Softening/

Glass transition*

Temperature °С

Main aoolication

F-2001 1000 49-51 60-70 UPE F-2200 HM 700 48 108-118 HIPS,

Stab. HBCD F-2016 1600 50 105-121 ABS F-2100L 10000 52 170-190 PBT, PC/ABS F-2100 20000 52 180-205 PBT, PC/ABS F-2300H 21500 52 130-150* PBT, PET,

PC/ABS F-2400 50000 53 145-155* PBT, PET,

polyamides

End-capped brominated epoxy, F-3000

Because of the presence of epoxy groups F-2000 series polymers tend to adhere to hot metal surfaces◦ This may cause appearance of black spots in extruded resin

End-capping eliminates problem of adhesion to the metals

Br content increases

n

O C

CH3

CH3

O

Br

Br

Br

Br

CH2CHCH2 CH2 CH

OH

CH2 O C

CH3

CH3

O CH2 CH CH2

Br

Br

Br

Br

OH

O O

Br

Br

Br

OHBr

Br

Br

End-capped brominated epoxy, F-3000

BFR Mw Br content,

% Softening

temperature °С

Main application

F-3014 1400 60 87-105 ABS, HIPS F-3020 2000 56 105-120 ABS, HIPS F-3516 1600 54 130-150 ABS, HIPS F-3100 15000 53 180-220 PBT, PET,

polyamides

V-0 ABS

FR type No FR F-2016 F-2400 F-3020 Composition, w%

ABS 100 74 74.8 76.2 FR - 20 19.2 17.8 Antimony trioxide - 6 6 6 Properties

MFI, g/10min (220°C, 5kg) 10 39 13 28

IZOD notched, J/m 211 63 82 92

HDT (1820 kPa), °C 93 91 90 91

Tensile: Strength, MPa 44 41 41 41

Elongation at break, % 19 2.5 4.1 3.5 Modulus, MPa 2300 2400 2200 2300 Blooming 7 days 65°C no no no no

Poly(pentabromobenzyl acrylate), FR-1025

Polymeric BFR with Br content 71% High thermal stability, 5% weight loss is

at 330°С◦ Softening temperature is relatively low, 190-

220°С Main application is in PP, PE, PBT and

polyamides Copolymerized with acrylates it is used

for finishing textiles Proprietary FR to ICL-IP

CH2 CH

C O

O

CH3

Br Br

Br

Br

Br

Glass-filled PBT, V-0, 0.8 mm

FR type No FR FR-1025 F-3100 F-2100 F-2400 Composition, w%

PBT 70 55.3 52.3 51.7 52.1 Glass fiber 30 30 30 30 30 FR

10 13 13.6 13.2

Antimony trioxide

4.5 4.5 4.5 4.5 PTFE (antidrip)

0.2 0.2 0.2 0.2

Properties MFI, g/10min (250°C,

2.16kg) 53 58 66 56 42

IZOD notched, J/m 92 114 88 83 58

HDT (1820 kPa), °C

200 204 202 200

Tensile:

Strength, MPa 121 122 123 116 121 Elongation at break, % 3.4 2.3 2.1 2.2 2.3 Modulus, MPa 9,300 10,600 10,400 10,500 10,000 CTI, V

250-300 200 200 200

with FR-1025

SEM of GF PBT+FR-1025 fracture

Ref. no FR

Thermal Aging at 1900C GFR PBT with FR-1025

Str

en

gth

rete

nti

on

, %

100

75

50

25

0 Time, h250 500 750 1000

Ref PBT No FR

FR-1025 in PBT

Brominated polystyrene, FR 803P

High molecular weight BFR, Mw = 600000. Br content 66% Very high thermal stability, 5% weight loss is at 360°С

◦ Very high softening temperature, 265-325°С Main application is in PBT, PET and polyamides

◦ ICL doesn’t sell FR-803P in the USA

CH2 CH

Brn

n = 2.7

Glass filled PA-6.6, V-0, 1.6 mm

FR type No FR

FR-803P FR-1025 F-3100 F-2400

Composition, w% Nylon 6,6 100 74.8 79.4 74.6 77.2

Glass fiber 30 30 30 30 30 FR

17.6 14.3 18.9 17.3

Antimony trioxide

7.6 6.3 6.5 5.5 Properties

Spiral flow, inch 35.3 36.7 49.3 41.2 29.5

IZOD notched, J/m 98 90 89 98 83

HDT (1820 kPa), °C 250 244 249 244 243

Tensile:

Strength, MPa 176 160 171 173 179

Elongation at break, % 3 2.3 2.2 2.1 2.5 Modulus, MPa 9,700 11,500 11,600 11,400 10,300 CTI, V 600 400 275 300 300

Nontoxic, not irritant to intact skin, not irritant or mild irritant to the eyes (below level of classification) and not skin sensitizers  

Not mutagenic Not classified by IARC (International Agency for Research on

Cancer) Not included in the NTP (National Toxicology Program) 12th

Report on Carcinogens  Based on products molecular weight, aquatic toxicity and

bioaccumulation potential are not expected◦ Not considered being PBT

HSE Profile of ICL-IP Polymeric FRs

Decabromodiphenyl Ethane, FR-1410 In many applications it is a drop in replacement of Deca-BDE

◦ Bromine content only slightly lower than Deca-BDE 82% It was developed in 90s as a Deca-BDE alternative which is not direct precursor

to dioxins Unless significant cost saving pressure, compounders are reluctant to use it

because of structural similarity with Deca-BDE HSE profile

◦ Nontoxic, non-irritating and not a skin sensitizer◦ Not mutagenic, no effect were found in developmental toxicity test◦ Nontoxic to aquatic organisms, not readily biodegradable and not bioaccumulative. Thus,

not considered being PBT. Br

Br

Br Br

Br

CH2 CH2

Br

Br Br

Br

Br

Tris(tribromoneopentyl phosphate), FR-370

Contains 70% Br and 3% P It melts at 180 С, and therefore promotes resin flow during compounding and molding Main use is in PP, especially in outdoor applications because FR-370 has very good UV

stability◦ Can be used in PP fibers

It is used in adhesives and pressure sensitive tapes It can be also used in HIPS and ABS for V-2 rating

BrCH2 C

CH2Br

CH2Br

CH2 O P

O

O

CH2

C

CH2Br

BrCH2 CH2Br

O CH2 C

CH2Br

CH2Br

CH2Br

FR-370

HSE Profile◦ Nontoxic, minimal irritant to eyes, not

irritant to intact skin and not a skin sensitizer. 

◦ No neurotoxic effects was found in a delayed neurotoxicity study with hens.

◦ Not mutagenic◦ Not classified by IARC and not included in

the NTP 12th Report on Carcinogens◦ Nontoxic to aquatic organisms, not readily

biodegradable, shows evidence of inherent biodegradability.

◦ Shows low potential for bioaccumulation in aquatic organisms. Not considered being PBT.

0

2

4

6

8

10

12

14

16

0 500 1000 1500 2000 2500 3000

Del

ta E

Hours of Exposure

Light Stability (Xenotest)

FR-370 Deca

Bis (2,3-dibromopropyl ether) of TBBA, FR-720

Contains 68 % Br, and half of Br is aliphatic It melts at about 113-117°С Main use is in V-2 PP It is very efficient and thermally stable.

◦ Because FR-720 tends to migrate to the surface “bloom”, is always used at low loading, typically below 5 wt. %

HSE profile◦ Nontoxic, minimal irritant to eyes, not irritant to intact skin and not a skin sensitizer. ◦ Not mutagenic ◦ Not classified by IARC and not included in the NTP 12th Report on Carcinogens◦ Nontoxic to aquatic organisms, not readily biodegradable, and shown to be not

bioaccumulative in earthworms. Thus, not considered being PBT.

O C

CH3

CH3

O

Br

Br

Br

Br

CH2CHCH2 CH2 CH CH2

Br Br Br Br

Tris(tribromophenoxy) triazine, FR-245

FR-245 was developed by ICL-IP in cooperation with DKS, Japan

It specifically targets HIPS and ABS◦ Bromine content (67 %) is lower than Deca-BDE◦ It melts at about 230°С which perfectly matches processing

temperatures of HIPS and ABS Very good melt resin flow

◦ Requires very little ATO HSE profile

◦ Nontoxic, not irritant to intact skin and eyes and not a skin sensitizer  

◦ Nontoxic in a repeated dose study◦ Not mutagenic◦ Not classified by IARC and not included in the NTP 12th Report on

Carcinogens◦ Not toxic to aquatic organisms, not readily biodegradable and not

bioaccumulative. Thus, not considered being PBT.

N N

NO O

O

Br

Br

Br

Br

Br

Br

Br Br

Br

Low ATO Systems, FR-245

FR type FR-245 FR-245 system FR-1410

Composition, w% Ref. 1

Ref. 2 HIPS Styron 1200 79.1 85 82 82.5 76.5 83.8 FR system* 16.4 13.5 16.5 16.5 22.5 12.2 Antimony trioxide 4.5 1.5 1.5 1 1 4 Total FR 20.9 15 18 17.5 23.5 16.2 Properties UL 94 (1.6mm) V-0 V-1 V-0 V-1 V-0 V-0 MFI, g/10min (200°C, 5kg)

14 9 11 11 19 6

Gardner impact, kg*cm 103 90 80 80 na 56

IZOD notched, J/m 107 105 93 93 78 89

HDT (1820 kPa), °C 70 72 72 72 72 71

Halogen-free FRs are mostly represented by phosphorus FRs, melamine or melamine salts, inorganic hydroxides

Mode of flame retardant action of non-halogen FRs is polymer specific◦ Therefore Deca-BDE replacement may require also

switch to different polymer associated with redesign and requalification

Organophosphates are specific to oxygen- or nitrogen-containing polymers.

Halogen-free alternatives

Resorcinol bis(diphenyl phosphate) Fyrolflex®RDP

Fyrolflex®RDP◦ P – 10.9 %

Very good thermal stability Main use in PC/ABS and

PPO/HIPS◦ Housings of business

machines and computers Limited application in HIPS and

ABS for V-2 rating Some applications in PWB Growing use in textiles Cannot be used in polyolefins

O P

O

O

O O P

O

O

On

Fyrolflex® Sol-DP

Fyrolflex® Sol-DP is a new addition to the bis-phosphates family.

Since Fyrolflex® Sol-DP is a free flowing powder there is no need for special metering equipment.

Applications are similar to Fyrolflex®RDP

Appearance White powder

Melting point, °C 101-108

Specific gravity 1.3

Phosphorus content, % 10.5

Acidity, mg KOH/g <0.1

Assay, wt. % >98

TGA,5% weight loss, °C 335

Water solubility Insoluble

Nontoxic, not irritant to intact skin, mild irritant to the eyes and not skin sensitizers  

Nontoxic in a repeated dose study Nontoxic in a reproductive study Not mutagenic Not classified by IARC and not included in the NTP 12th

Report on Carcinogens Nontoxic to aquatic organisms, can be not readily or

readily biodegradable, have low bioaccumulation potential.◦ Not considered being PBT.

HSE Profile of Bisphosphates

Fyrolflex® RDP, Sol-DP / PC/ABS

FR Type Sol-DP RDP BDP Composition, wt % PC 72.4 72.4 69.2 ABS 19.3 19.3 18.2 Flame Retardant 9.0 9.0 12.3 Anti-dripping agent 0.3 0.3 0.3 P content 1.0 1.0 1.1 Flame retardancy UL 94 class (1.6 mm) V-0 V-0 V-0 Physical properties Tensile strength, mPa 54 53 56 Flexural strength, mPa 78 81 85 Modulus, mPa 1520 1600 1660 IZOD notched impact, J/m 720 650 500 HDT (1.82 mPa), °C 88 83 81

FR-20-100 – untreated FR-20-200 (S7/S10) - stearic

acid surface treated FR-20-300 (S10) - vinyl

silane surface treated FR-20-400 (S5/S7) – amino

silane surface treated FR-20-500 – polysiloxane

coated (coming to the market in 2013)

It is used in polyolefins, elastomers, polyamides and PVC

Excellent smoke suppression properties in PVC

It is required > 50% FR-20 to achieve V-0 in polyamides

In halogen-free W&C formulations it required > 60 % to achieve VW-1

Magnesium hydroxide, FR-20

Because of the pressure of NGOs on OEMs Deca-BDE was withdrawn from the USA market

Depending on final applications there are many commercial Deca-BDE alternatives

Use of halogen-free alternatives is still limited to certain type of polymers.

ICL-IP and other FR producers strongly advocate use of polymeric FRs

All Deca-BDE alternatives have favorable human health and environmental profiles.

Conclusions

32

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