chain scission fr mechanism of aliphatic bromine compounds in ps an pp - j. kaspersma
TRANSCRIPT
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
Chain Scission FR Mechanism
of aliphatic bromine compounds in PS and PP
Jelle H.Kaspersma
FR Technical ServiceHerentals, Belgium
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
Flame Poisoning Mechanismaromatic 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: RH R
+ H
growth: R
+ O2 ROO
+ RH ROOH + R
branching: ROOH RO
+ OH
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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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
Chain Scission Mechanism
aliphatic bromine, in polymer meltpolymers with tertiary carbon
CH C
H
H
CHH
HCHH
H
CH C
H
H
Br FR FR
+ Br
Br +.C
H
CHHHCHHH
CH C
H
HCH
.C
H
CHHHCHHH
CH C
H
HCH
+ .CHH
H
CH C
H
H
CHHH
C
HCH
.CHH
H
CH C
H
H.CHH
H
CHC
H
H
+ CHH
H
CHC
H
H
+
CHH
H
CHC
H
H
scission
termination
H abstraction
HBr +
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
Br FR additives
BrBr
BrBr
Br Br
CH2 CH
Br Br
CH2 O O
Br
Br
Br
Br
CH3
CH3
C CH2 CH
Br
CH2
Br
Mixed aliphatic/aromatic bromine FR compoundTetrabromo bisphenol A bis (2,3-dibromopropyl ether)
Commercial name PE-68 used in PP
Fully aliphatic bromine FR compound Hexabromo cyclo dodecane
Commercial name CD-75P used in PSCD-75Pstab contains 5% acid scavenger
O
Br Br
Br Br
Br
Br
BrBr
Br
Br
Aromatic bromine FR compoundDecabromo diphenyl oxide
Commercial name DE-83R used in HIPS and PP
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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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 partContact for 30 seconds
Additional burn time less than 30 seconds (60 in total)
Burning drips are not allowed
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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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 UL 94 V2
thickness CD-75Pstab contentAv.burn time
thickness CD-75stab contentAv.burn time
1 mm 2.1 % 10 20 sec 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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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
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
CD-75Pstab
Result
Av.burn time
Rubber
CD-75Pstab
Result
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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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Results of CD-75Pstab + Dicumene in HIPS
HIPS with 6.5% rubber
H
C
C
C
H HH
HH
C
C
C
H
H
HH
HH
C
C
C
H
H
HH
HH
2.
Glow Wire 960oC on 1.5 mm UL94 V2 on 1.6 mm
CD-75Pstab Dicumene
ResultAv. burn time
CD-75PstabDicumene
ResultAv. burn time
4.2 % - Pass 16 sec 1.6 % - 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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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
Results of CD-75Pstab + Sb2O3 in HIPS
HIPS with 6.5% rubber
Glow Wire 960oC on 1.5 mm UL94 V2 on 1.6 mm
CD-75Pstab Sb2O3 Result
Av.burn time
CD-75Pstab Sb2O3 Result
Av.burn time
4.2 % - Pass 16 sec 1.6 % - Pass 5 sec
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
G L k Ch i l C i
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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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 Sb2
O3
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
G t L k Ch i l C ti
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Results of PE-68 + Sb2O3 in PP
PPhomopolymer MFI 11
FR/Sb2O3 1.0 2.0 3.0 6.0PE-68 % 1.5 % 1.5 % 1.5 % 1.5 %
Sb2O3 % 1.5 % 0.75 % 0.5 % 0.25 %
UL94 V2 Result / Av. burn time
0.8 mmPass
4 sec
Pass
4 sec
Pass
2 sec
No result
1.6 mm
Pass
5 sec
Pass
3 sec
Pass
3 sec
Fail
(1/10 fail)
3.2 mmFail(4/10 fail)
Fail(1/10 fail)
Pass
2 sec
Fail(3/10 fail)
Great Lakes Chemical Corporation
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
Results of PE-68 in PP
PPhomopolymer MFI 11Glow Wire 960oC vs UL94 V2 loading
Glow Wire 960oC UL 94 V2gage PE-68
Sb2O3
ResultAv.burn time
gage PE-68Sb2O3
ResultAv.burn time
1.0 mm
1.0 %
0.33 %
Pass
21 sec0.8 mm
1.5 %
0.5 %
Pass
2 sec
1.5 mm1.0 %
0.33 %
Pass
25 sec
1.6 mm1.5 %
0.5 %
Pass
3 sec
3.0 mm1.0 %
0.33 %
Pass
31 sec3.2 mm
1.5 %
0.5 %
Pass
6 sec
Great Lakes Chemical Corporation
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
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
Great Lakes Chemical Corporation
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Great Lakes Chemical CorporationTechnical Service EMEA
Comparison of Br FR load levels for V2 and V0
Aliphatic or mixed Aliphatic/Aromatic vs fully Aromatic Br
HIPS6.5% rubber CD-75Pstab Sb2O3 DE-83R Sb2O3
AliphaticBr
AromaticBr
UL94 V21.6 mm
1.6 % - 6.0 % 2.0 % 1.1 % 5.0 %
UL94 V01.6 mm
8.0 % 3.0 % 11.5 % 3.5 % 5.7 % 9.5 %
PP
homopolMFI 11
PE-68 Sb2O3 DE-83R Sb2O3
Mixed
Br
Aromatic
Br
UL94 V21.6 mm
1.5 % 0.5 % unknown 1.0 % -
UL94 V01.6 mm
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
Great Lakes Chemical Corporation
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7/30/2019 Chain Scission FR Mechanism of Aliphatic Bromine Compounds in PS an PP - J. Kaspersma
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Results of Mixed Br FR vs Non Hal FR in PPV2 and V0 in 1.6 mm
CH2HO CCH2
CH2
CH2
O
OO
P ONH-1197, Pentaerithritol phosphate
NH-1511, blend of NH-1197 withphosphate synergist
NH-1197
PE-68 vs Non Hal NH-1511 in PP homopolymer MFI =11
FR additive FR loading for UL94 V0 in 1.6 mm
FR loading forUL94 V2 in 1.6 mm
PE-68 + Sb2O3 10% PE-68 + 3.3% Sb2O3 1.5% PE-68 + 0.5% Sb2O3
NH-1511 28 % 23 %
Great Lakes Chemical Corporation
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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