Great Lakes Chemical Corporation Technical Service EMEA

Chain Scission FR Mechanism of aliphatic bromine compounds in PS and PP

Jelle H.Kaspersma FR Technical Service Herentals, Belgium

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FR Technical Service

Help FR customers with solutions Correlation between UL V2 and Glow Wire? FR compounds in HIPS and PP for E&E applications Project . FR Mechanisms for explanation

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Flame Poisoning Mechanism

aromatic bromine, Sb2O3 synergist gas phase mechanism, polymer unspecific

Br FR + Sb2O3 SbBr3 + H HBr

High energy H and OH are generated in the partial oxidation cycle of hydrocarbons: start: growth: branching:

RH R + H

R + O2 ROO + RH ROOH ROOH RO + OH

+ R

High energy radicals are removed by HBr and SbBr3 , the flame is extinguished:

HBr +

H H2 +

Br

HBr + OH H2O +

Br

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Chain Scission Mechanism

aliphatic bromine, in polymer melt polymers with tertiary carbon FR + Br
H H H C H C C H C H HCH HCH H H

Br FR

H abstraction

Br

HBr

H H C H C C H C H HCH HCH H H

H H C H C C H C H HCH HCH H H

scission

H CH + C H CH H

H H C C H H CH H

H C H H C

. .
+

HC H H

H H C C H HC H H

termination

H C H H CH H CH H

H C HC H CH H

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Br FR additives
Br Br Br Br

Fully aliphatic bromine FR compound Hexabromo cyclo dodecane Commercial name CD-75P used in PS CD-75Pstab contains 5% acid scavenger

Br

Br

Br Br Br CH3 C CH3 Br CH2 CH CH2 O

Br Br Br O CH2 CH CH2 Br

Mixed aliphatic/aromatic bromine FR compound Tetrabromo bisphenol A bis (2,3-dibromopropyl ether) Commercial name PE-68 used in PP

Br Br Br

Br O Br

Br

Br Br

Br

Br

Aromatic bromine FR compound Decabromo diphenyl oxide Commercial name DE-83R used in HIPS and PP

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FR test methods

UL94 V2:

2 times flame application for 10 seconds Average burn time less than 25 seconds Burning drips are allowed

Glow Wire:

Application of hot wire at 960, 850 or 750oC On most critical area of molded part Contact for 30 seconds Additional burn time less than 30 seconds (60 in total) Burning drips are not allowed

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Results of CD-75Pstab in HIPS

HIPS with 6.5% rubber FR loading for Glow Wire 960oC vs. UL94 V2

Glow Wire 960oC thickness CD-75Pstab content Av.burn time 1 mm 2.1 % 10 20 sec

UL 94 V2 thickness CD-75stab content Av.burn time 0.8 mm 1.6 % 2 sec

1.5 mm

4.2 % 10 20 sec

1.6 mm

1.6 %

5 sec

3 mm

2.1 % 10 20 sec

3.2 mm

1.6 %

2 sec

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Result of CD-75Pstab in HIPS

Effect of rubber and mineral oil

CD-75Pstab in 1.5 mm Glow Wire plaque at 960oC HIPS with 6.5 % rubber HIPS MFI 7 with 1.8 % mineral oil Mineral oil Result Rubber Result CD-75Pstab Av.burn time CD-75Pstab Av.burn time 1.8 % 4.2 % Pass 39 sec 6.5 % 4.2 % Pass 10 20 sec

0.9 %

4.2 %

Pass

5 sec

9.5 %

6.0 %

Pass

10 20 sec

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Results of CD-75Pstab + Dicumene in HIPS

H HC H C HC H H H HC H C HC H H 2 H HC H C HC H H

HIPS with 6.5% rubber

Glow Wire 960oC on 1.5 mm CD-75Pstab Result Dicumene Av. burn time 4.2 % Pass 16 sec UL94 V2 on 1.6 mm CD-75Pstab Dicumene 1.6 % Result Av. burn time Pass 3 sec

3.0 %

0.3 %

Pass

12 sec

1.6 %

1.6 %

Pass

1 sec

4.0 %

Fail

> 60 sec

1.6 %

Fail

> 30 sec

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Results of CD-75Pstab + Sb2O3 in HIPS

HIPS with 6.5% rubber

Glow Wire 960oC on 1.5 mm CD-75Pstab Sb2O3 Result Av.burn time 4.2 % Pass 16 sec

UL94 V2 on 1.6 mm CD-75Pstab Sb2O3

Result Av.burn time Pass 5 sec

1.6 %

4.2 %

1.4 %

Pass

14 sec

1.0 %

0.33 %

Fail

> 30 sec

3.5 %

1.2 %

Pass

12 sec

2.0 %

0.67 %

Fail

> 30 sec

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Conclusions for CD-75Pstab in HIPS

Additive effects indicate: Chain Scission is the main mechanism for V2: - Sb2O3 removes Br radicals from the melt, fails V2 - Dicumene enhances Chain Scission, a real synergist A mixed Chain Scission/Flame Poisoning Mechanism for Glow Wire: - Both Sb2O3 and Dicumene are synergists - Strong effect of rubber on FR loading by counteracting flow UL V2 easier to pass than Glow Wire in HIPS - No Sb2O3 for Flame Poisoning, needed more for Glow Wire

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Results of PE-68 + Sb2O3 in PP

PP homopolymer MFI 11

FR/Sb2O3 PE-68 % Sb2O3 % UL94 V2 0.8 mm

1.0 2.0 3.0 1.5 % 1.5 % 1.5 % 1.5 % 0.75 % 0.5 % Result / Av. burn time Pass Pass Pass 4 sec Pass Pass 5 sec 3 sec Fail (1/10 fail) Pass 2 sec 4 sec Pass 3 sec 2 sec

6.0 1.5 % 0.25 % No result

1.6 mm Fail (4/10 fail)

Fail (1/10 fail) Fail (3/10 fail)

3.2 mm

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Results of PE-68 in PP
PP homopolymer MFI 11 Glow Wire 960oC vs UL94 V2 loading

Glow Wire 960oC gage PE-68 Sb2O3 1.0 % 1.0 mm 0.33 % 1.0 % 1.5 mm 0.33 % 1.0 % 3.0 mm 0.33 %

Result Av.burn time Pass 21 sec Pass 25 sec Pass 31 sec

UL 94 V2 gage PE-68 Sb2O3 1.5 % 0.8 mm 0.5 % 1.5 % 1.6 mm 0.5 % 1.5 % 3.2 mm 0.5 %

Result Av.burn time Pass 2 sec Pass 3 sec Pass 6 sec

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Conclusions for PE-68 in PP

Additive effects indicate: A mixed Chain Scission/FlamePoisoning Mechanism for V2 and Glow Wire - Aliphatic Br sustains the Chain Scission mechanism - Aromatic Br sustains Flame Poisoning with Sb2O3 synergist - Lower FR loading for Glow Wire vs V2: Flame Poisoning more important for Glow Wire than for V2

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Comparison of Br FR load levels for V2 and V0

Aliphatic or mixed Aliphatic/Aromatic vs fully Aromatic Br
HIPS 6.5% rubber CD-75Pstab Sb2O3 DE-83R Sb2O3 Aliphatic Br Aromatic Br

UL94 V2 1.6 mm UL94 V0 1.6 mm PP homopol MFI 11 UL94 V2 1.6 mm UL94 V0 1.6 mm

1.6 %

6.0 % 2.0 %

1.1 %

5.0 %

8.0 %

3.0 %

11.5 % 3.5 %

5.7 %

9.5 %

PE-68

Sb2O3

DE-83R Sb2O3

Mixed Br

Aromatic Br

1.5 %

0.5 %

unknown

1.0 %

10.0 %

3.0 %

23.0 % 10.0 %

6.8 %

19.1 %

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Conclusions on Chain Scission in V2/V0 in PS and PP

Comparison of Aliphatic and Aromatic Br in V2 and V0 in HIPS: - For V2 Aliphatic Br is 450% more effective than Aromatic Br - For V0 Aliphatic Br is 60% more effective than Aromatic Br Comparison of mixed Aliphatic/Aromatic and Aromatic Br in V0 in PP: - For V0 mixed Aliphatic/Aromatic Br is 280% more effective than Aromatic Br

The Chain Scission Mechanism is more effective

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Results of Mixed Br FR vs Non Hal FR in PP

V2 and V0 in 1.6 mm

HO CH2

CH2 O P C CH2 O CH2 O

NH-1197

NH-1197, Pentaerithritol phosphate NH-1511, blend of NH-1197 with phosphate synergist

PE-68 vs Non Hal NH-1511 in PP homopolymer MFI =11 FR additive FR loading for FR loading for UL94 V0 in 1.6 mm UL94 V2 in 1.6 mm PE-68 + Sb2O3 NH-1511 10% PE-68 + 3.3% Sb2O3 28 % 1.5% PE-68 + 0.5% Sb2O3 23 %

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Final Conclusions
Relative importance of Chain Scission vs. Flame Poisoning: - for V2 Chain Scission is most important - for Glow WireChain Scission and Flame Poisoning are equally important - for V0 Flame Poisoning is most important, but Chain Scission contributes a lot Aliphatic Br FR`s are very effective for European FR ratings in PS and PP Non-Halogen FR`s can be effective for V0 by a Charring Mechanism Non-Halogen FR`s are not effective for V2/Glow Wire: no Chain Scission