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Presentation by
Michael Kearns, Technical Business Support EMEA
Great Lakes Solutions, a Chemtura business
May 22, 2013
Agenda
How flame retardants work
Great Lakes Solutions products by application/polymer
Emerald InnovationTM
Gas phase,
Free radical
quenching
Condensed
phase, Char
forming
Endothermic
5
Halogenated Flame
Retardants
Brominated FRs
Chlorinated FRs
Halogenated polymers
Antimony Synergists
Metal Hydrates
Aluminum Trihydrate
Magnesium Hydroxide
thermosets
Less use in engineered plastics
Technology
Firemaster CP44-HF
Firemaster PBS64-HW, PDBS-80
Polyamides
Polybromostyrene
Polycarbonate, PBT
Brominated Oligomer
Polybromostyrene
Unsaturated Polyesters
Reactive Intermediate
PHT-4 , BA-59P
Polyurethane
Reactive Intermediate
Proprietary Polymeric
Polyolefins, HDPE, PP
Styrenics, PS, HIPS, ABS
Epoxy
Products
Reactive Intermediates
BA-59P
Polyolefins
TPO
EPDM
Bromine-based FR
Phosphorus-based
FR
Firemaster 2100R
Emerald Innovation 1000
Firemaster 2100R
Emerald Innovation 1000
DP 45
Firemaster 2100R
Emerald Innovation 1000
Synergists,
Smoke Suppressants
Reofos 95
Reofos RDP
Reofos BAPP
PVC
DP 45
Firemaster 2100R
Emerald Innovation 1000
Phosphorus based FR
Reofos 35, 50, 65 95,
Kronitex CD, TCP
Rigid PU
PHT 4 Diol
PHT 4 Diol LV
Firemaster 508
Flexible
PU
DP 45
Firemaster BZ 54
Firemaster 550
Firemaster 600
PDBS 80
DE-83R
Firemaster BZ 54
Firemaster 2100R
Emerald Innovation 1000
TPU
Bromine
based FR
Synergists,
Smoke Suppressants
Timonox /TMSBlue Star
Ultrafine Blue Star
ZB 223, ZB 467, Smokebloc
Ongard 2, LSFR
Theromoguard CPA
Phosphorus
based FR
Synergists,
Smoke Suppressants
SP 75
Firemaster 2100R
Emerald Innovation 1000
ABS
BA-59P
BC-52, BC-58
Firemaster 2100R
Emerald Innovation 1000
Reofos RDP
Reofos BAPP
PC/ABS
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW
BC-52 , BC-58
Firemaster 2100R
Emerald Innovation 1000
PDBS 80
Emerald Innovation 1000
Reofos RDP,
Reofos BAPP
HIPS
PPE/HIPS
Bromine
based FR
Polymer type
10
Bromine-based FR
EPS
XPS
Bromine-based FR
UPES
(unsaturated
polyester)
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW *PHT 4
*BA-59P
Firemaster BZ-54
Firemaster 2100R
Emerald Innovation 1000
Epoxy
Phenolic
*BA-59P
Firemaster BZ-54
Firemaster 2100R
Emerald Innovation 1000
DP 45
Firemaster BZ-54
Firemaster 550
Firemaster 552
DE-83R
Firemaster 2100R
Emerald Innovation 1000
* Reactive FR
11
Phosphorusbased FR
Synergists,
Smoke Suppressants
Timonox /TMSBlue Star
Ultrafine Blue Star
ZB 223, ZB 467, Smokebloc
Ongard 2, LSFR
Theromoguard CPA
Polymer type
PA 6
PA 66
HTPA
12
Bromine-based FR
Synergists,
Smoke Suppressants
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW
Firemaster 2100R
Timonox/TMSBlue Star
Ultrafine Blue Star
ZB 467
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW
Timonox/TMSBlue Star
Ultrafine Blue Star
ZB 467
Polymer type
PBT
PET
PC
13
Bromine-based FR
Synergists,
Smoke Suppressants
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW BC-52
BC-58
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW
Firemaster PBS-64 HW
BC-52
BC-58
ZB 467
Developing Sustainable
Flame Retardant Solutions
14
16
Property
Appearance
Off-white
powder
Bromine, %
78
5-6
5% wt loss, 0C
(Thermogravimetric Analysis (@ 10 0C/min under N2)
Emerald
Innovation
1000
4100C
IN
FR-1
FR-2 FR-3
FR-4
FR Load, %
19.0
19.0
19.0 21.0
22.3
UL-94, at 1.6 mm
V-0
V-0
V-0
V-0
V-0
Gardner Impact, J
17.8
17.1
17.7
1.5
15.2
Elongation at Yield, %
8.5
10.1
8.7
5.6
6.9
49.7
55.8
49.5 61.3
46.6
Property
LABEL
FR-1
FR-2
FR-3
FR-4
DESCRIPTION
DECABROMODIPHENYL OXIDE (DE-83R)
BIS (PENTABROMOPHENYL) ETHANE (2FIREMASTER 2100R)
POLY(PENTABROMOBENZYL) ACRYLATE (FR-1025)
ETHYLENEBIS(TETRABROMOPHTHALIMIDE) (SAYTEX BT-93)
Emerald1000
Innovation 1000
Emerald
FR1
FR2
FR3
1000
FR4
Viscosity, Pa-sec
100
10
10
100
1000
Shear Rate, 1/sec
10000
Ductile yield
03/30/2012 V1.0
FR-1
FR-2
FR Load, %
21.0
21.0
21.0
UL-94, 1.6 mm
V-0
V-0
V-0
11.4
12.8
11.9
33.6
35.8
41.1
Elongation at Yield, %
2.29
2.42
2.38
Property
LABEL DESCRIPTION
FR-1
FR-2
FR-3
2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE
170
160
150
140
130
Emerald
Emerald
1000
Innovation
1000
120
Firemaster
Firemaster2100R
2100R
110
100
Same impact strength
at over 40% lower
impact modifier load
90
80
1
3
% Kraton D1101
220 0C
1000
Emerald
Emerald
10001000
Innovation
FR-1
FR-2
100
FR-3
10
10
LABEL DESCRIPTION
FR-1
FR-2
FR-3
2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE
100
1000
10000
FR 2
FR 3
FR 4
13.0
13.0
16.2
21.7
V0
V0
V0
V0
47.9
46.2
50.1
51.2
Strain at yield, %
3.02
2.66
2.86
2.53
Strain at break, %
15.3
15.1
7.1
3.02
75.2
72.9
78.6
72.5
2437
2594
258
3
2777
107.3
55.0
83.8
41.1
29
21
43
73
FR, %
UL-94 @ 1.6 mm
HDT, C, , 1.8MPa
75.2
76.5
73.8
73.2
107
84
55
41
Joules/Meter
Emerald
Emerald
1000
Innovation
1000
FR 2
FR 3
FR 4
26
27
v.2.0
ATO functions via the formation of flame quenching antimony trihalides through a gas-phase mechanism. It is not absolutely
necessary but makes the system more cost effective
Alternatives to ATO are sought due to:
28
I.
II.
29
METAL SALTS
21
21
21
21
21
ATO TMS, %
Zn Borate, %
3.5
3.5
3.5
Ca/Zn molybdate, %
3.5
Zn molybdate, %
3.5
Zn phosphate, %
3.5
UL-94 @ 1.6 mm
V-0
V-0
V-0
V-0
V-0
2.9
3.0
3.4
2.6
3.5
ZB 467
= Zn Borate
Kemgard 981 = Zn phosphate
Kemgard 911A = Ca/Zn molybdate
Kemgard 911B = Zn molybdate
MODIFIED CLAYS
UNFILLED PP HOMOPOLYMER
PROFAX 6323
Emerald InnovationTM 1000, %
30
27
27
27
27
ATO, %
10
4.25
4.0
4.0
3.0
4.25
4.0
4.5
4.5
4.2/1.8
4.2/1.8
1.8/3.0
3.4/4.2
Modified clay* %
Avg. Burn time, sec
Total Burn time, sec
39
30
30
24
38
UL-94 @1.6 mm
V-0
V-0
V-0
V-0
V-0
*Modified clay:
quaternary ammonium and siloxane treated
montmorillonite clay.
Charex 44PSS
Amcol/Nanocor
MODIFIED CLAYS
UNFILLED PP COPOLYMER
SG702 18MFI
26
26
26
26
26
26
ATO, %
8.7
7.7
6.7
5.7
4.7
3.7
0.8/1
2/0.8
2/5.2
Modified clay*, %
Avg. Burn time, sec
15
12
18
18
36
UL-94 @ 1.6 mm
V-0
V-0
V-0
V-0
V-0
V-0
MFI, g/10min
20.0
21.2
20.7
21.0
22.08
19.19
Amcol/Nanocor
Notched Izod
impact (J/m)
Modulus (MPa)
Strain @ Break,
%
100
90
80
70
60
50
40
30
20
10
0
FR/ATO/Nanoclay
FR/ATO
Tensile Strength,
MPa
Strain @ Yield,
%
FR, %
ATO , %
Modified clay, %
26
8.7
26
6.7
2
118
135.2
18.2
2.5
4.8
1588.0
17.0
2.5
6.1
1623.4
FR2
FR3
FR, %
12.0
12.0
12.0
12.0
12.0
15.0
PPE, %
8.0
10.0
15.0
20.0
20.0
20.0
HIPS, %
74.8
72.8
67.8
62.8
62.7
59.7
Kraton D1101
5.0
5.0
5.0
5.0
5.0
5.0
Alkanox 240, %
0.2
0.2
0.2
0.2
0.2
0.2
UL-94 1/16
Fail
Fail
Fail
V-0
Fail
Fail
>30
>30
>30
2.0
>30
>30
34
PPE/HIPS
PPE/HIPS (1:1)
wt % FR-1
3
4
5
6
Flammability
time, seconds
13.5
8.2
4.8
2.5
PPE/HIPS (1:3)
UL94V
Rating
V-2
V-1
V-0
V-0
wt % FR-1
8
9
10
11
16
14
V-2
V-1
12
10
V-1
8
6
V-0
V-1
V-0
4
V-0
V-0
2
3
3.5
35 35
Flammability UL94V
time, seconds Rating
5.8
V-1
5.3
V-1
4.2
V-0
3.3
V-0
4.5
FR-1, wt %
5.5
6.5
8
35
10
FR-1, wt %
11
12
1:1 PPE/HIPS
No FR
5% FR-1
Fail
V-0
>30
4.6
141
118
Capillary Rheology
10000
Property
1000
710.8
885.4
114.1
115.0
58.2
57.1
Elongation at Yield, %
9.0
8.8
Elongation at Break, %
18.7
21.9
100.1
100.5
2571.0
2659.3
16.2
20.0
100
10
100
1000
PPE/HIPS
PPE/HIPS/Emerald 1000
10000
FR-3
FR-4
FR, %
12.0
12.0
12.0
15.0
PPE, %
20.0
20.0
20.0
20.0
HIPS, %
62.7
62.7
62.7
59.7
Kraton D1101, %
5.0
5.0
5.0
5.0
Alkanox 240, %
0.2
0.2
0.2
0.2
PETS wax, %
0.1
0.1
0.1
0.1
UL-94 1/16
V-0
Fail
Fail
Fail
2.6
>30
>30
>30
FR %
PPE, %
ATO, %
HIPS, %
Kraton D1101, %
UL-94 1/16
Average Burn time, secs
Notched Izod Impact Strength, 1/8 J/m
Gardner Impact, J
HDT, C @ 1.8 MPa
Vicat softening temperature, C
Tensile Strength, MPa
Elongation at Yield, %
Elongation at Break, %
Flexural Strength, MPa
Flexural Modulus, MPa
Melt flow index, 200 C/5kg; g/10mins
38
Emerald
InnovationTM
1000
12.0
20.0
62.7
5.0
V-0
2.0
235.0
6.98
89.5
121.3
39.8
2.43
27.8
69.5
2310.3
0.60
FR-2
12.0
4.0
78.7
5.0
V-0
0.2
101.5
6.16
70.1
97.6
24.2
1.49
36.0
37.5
2068.9
8.38
Flexural Modulus
Gardner Impact
Elongation at Yield
FR-2
HDT
Vicat softening
temperature
Flexural Strength
39
FR-1
Tensile Strength
MFI, g/10mins
PPO 640
PPO 630
FR2/ATO
8890C
190
200
210
220
230
Temperature, C
240
250
260
PC/ABS (80/20)
% Emerald
Burn Time,
InnovationTM 1000 seconds
14
0
12
0
10
0
9
0.9
8
2.1
7
3.3
41
UL-94
V-0
V-0
V-0
V-0
V-0
V-0
FR-5
FR-6
FR-7
FR %
8.0
10.5
8.6
13.0
UL-94, 1.6 mm
V-0
V-2
V-2
V-0
1.7
1.6
2.6
0.6
9.4
8.6
9.7
33.9
111.8
115.2
112.5
81.7
656.3
208.3
592.7
52.3
64.6
67.4
64.7
69.8
Elongation at Yield, %
5.3
5.6
5.5
4.4
Elongation at Break, %
40.3
31.7
38.0
23.1
104.7
108.7
106.6
113.0
2675.9
2692.4
2691.0
3003.4
42
Flexural Strength,
MPa
100
90
80
70
60
50
40
30
20
10
0
Elongation at
Break, %
Emerald Innovation 1000 does not plasticize the resin unlike FR-7
Improved overall HDT, impact and mechanical properties
FR-1
FR-7
HDT, C
Tensile Strength
MPa
Elongation at
Yield, %
43
Izod Impact
Strength
FR-1 in PC-ABS
% FR-1
%PC
80
70
60
50
45
40
30
23
21
19
17
15
13
11
9
7
5
10
30
50
% PC in PC-ABS
70
90
CONCLUSIONS
Performance comparisons for Emerald Innovation 1000 in polyolefins and
styrenics demonstrate comparable efficiency at similar load levels over DE83R and Firemaster 2100R
Emerald Innovation 1000 provides higher multi-axial impact strength than
other polymeric brominated flame retardants tested
Evaluation of metal salts and modified clays show great potential to
significantly reduce the use of high cost ATO in polyolefins whilst maintaining
flammability performance
HIPS formulations containing Emerald Innovation 1000 & PPE exhibits V-0
performance without ATO
In PC/ABS blends Emerald Innovation 1000 exhibits V-0 without ATO over a
wide range
45
46
47
EN ISO 11925-2
Property
Appearance
white powder
Bromine, %
64
Softening point, 0C
120
5% wt loss, 0C
(Thermogravimetric Analysis (@ 10
52
0C/min
under N2)
2620C
Emerald Innovation
3000
HBCD
White powder
White powder
64
75
0.5/0.7
1.2/1.5
262
238
>20/100
2/100
100,000 160,000
642
under N2)
Solubility in Styrene
g/100g styrene @ 25o C
Flammability Performance
56
polystyrene foam (XPS) and like HBCD will require stabilization during extrusion.
A stabilizer formula consisting of hindered phenol (AO1), a high performance
phosphite (P1), and an epoxy novalac resin (E1) provides the most effective
stabilization package for Emerald 3000 in XPS foam.
This stabilizer system provides an excellent balance of color and molecular weight
retention in XPS foam formulated with Emerald Innovation 3000.
A01
P1
E1
Anox 20
Ultranox 626
Epon 164 OR Equivalent
Experimental Approach
Several combinations of primary and secondary antioxidants in combination
with an epoxy novolac resin were evaluated.
All formulations were run on a single screw extruder for multi-pass evaluation in
Polystyrene Nova PS1600 @ 200C.
Pellets from extrusion pass 1, 3 & 5 were set aside for melt flow and color
determination on molded plaques.
The results show that a combination of AO1, P1 and E1 gives the best color and
molecular weight retention in XPS foam.
This optimized formulation is available from Chemtura as a non-dust blend (NDB1).
A01
P1
E1
NDB1
Anox 20
Ultranox 626
Epon 164 OR Equivalent
Lowinox XPS 162
Emerald
Emerald
PS + Innovation 3000 PS + Innovation 3000
AO1/P1/E1
+ AO1/P1/E1
A01
P1
E1
Anox 20
Ultranox 626
Epon 164 OR Equivalent
Emerald
PS + Innovation 3000
+ alternative AO
Yellowness Index
Emerald
Emerald
PS + Innovation 3000 PS + Innovation 3000
AO1/P1/E1
+ AO1/P1/E1
A01
P1
E1
Anox 20
Ultranox 626
Epon 164 OR Equivalent
Emerald
PS + Innovation 3000
+ alternative AO
61
62
63