Organomodified Siloxanes for high filled HFFR ... - Plastic Additives

Platzhalter Titelbild
Organomodified H Siloxanes
F
for High Filled
F
HFFR Cable R Compounds
C
o
m
p
o

What are Organomodified
Siloxanes (OMS)?
Organomodified siloxanes (OMS) are performance
additives to improve surface and bulk properties
They overcome the disadvantages of silicone oil by
introduction of organic groups on the silicone
backbone
They generate a permanent functionalization of
thermoplastic polymers
Depending on the modification. OMS can orientate
to the surface (also internal surfaces) and/or to the
bulk phase of the polymer
OMS enhances processing. surface and material
properties
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Different Flame Retardants in
Thermoplastics and Mode of Action
Antimony trioxide +
brominated substances
Formation of radicals which block the
flame reaction
Organic or inorganic
phosphorous substances
Flame reaction is stopped by
formation of polyphosphoric acid
Metal hydroxides or
carbonates
Formation of not flammable gas
water or carbon dioxide
Nitrogen containing
substances
Formation of not flammable gas
nitrogen oxides
Plastics with inherent flame
retardant characteristics
Polysulfone. Polyether sulfones.
Polyaryl ether ketones
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Mechanism of HFFR Fillers
Thermal Dekomposition of MDH or ATH
2 Al(OH) 3 → Al 2 O 3 + 3H 2 O
Mg(OH) 2 → MgO + H 2 O
Source: Functional Fillers for Plastics. Marino Xanthos
Due to thermal decomposition MDH and ATH will form inorganic oxides and water.
The higher decomposition temperature of MDH easies the processing.
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Recommended Products
for HFFR Compounds
TEGOMER ® V-Si 4042
Liquid. solvent free organomodified siloxane
Reactive OMS therefore suitable for peroxide curing systems
Designed for high filled thermoplastic HFFR cable compounds
based on polyolefin. EVA. x-PP. x-PE as well as for EPDM
Recommended Dosage: 0.5 % - 2.0 % on compound
TEGOMER ® FR 100
Solid organomodified siloxane compound
Especially developed for HFFR Cable Compounder. which
prefer using non liquid additives
Suitable for polyolefin. EVA. x-PP. x-PE and EPDM
Recommended Dosage: 1.0 % - 3.0 % on compound
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Recommended Products
for HFFR Compounds
TEGOPREN ® 5885
Liquid. solvent free organomodified siloxane
Designed for high filled thermoplastic HFFR cable compounds
Also recommended for nano clay containing compounds
+ +
Clay
OMS
OMS coated
clay
Polymer
Exfoliated primary clay
particles in polymer
Suitable for polyolefin. EVA. x-PP. x-PE and EPDM
Recommended Dosage: 0.5 % - 2.0 % on compound
TEGOPREN ® 6875
Liquid organomodified siloxane
Used as post treatment for fillers to create easy to disperse grades of HFFR fillers
Used as an universal drawing oil for wire drawing and to reduce “peel off” forces in
cable insulating materials. e.g. CPE. Rubber. PVCC.
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Which Additive Meets which
Type of Customer
HFFR Producer
Production of inorganic
Fillers for flame retardant
application like ATH. AMH.
MDH. nano Clays.
CarbonatesC.
TEGOPREN ® 6875
TEGOPREN ® 6875-45
Used for the surface
treatment
HFFR
Compounder
Production and
development of
compounds
TEGOMER ® V-Si 4042
TEGOMER ® FR 100
TEGOMER ® 5885
Dispersing of filler with
high loadings.
Improvement of
mechanical. surface
and FR properties
HFFR Cable
Manufacture
Processing of cable
extrusion and or wire
drawing
TEGOPREN ® 6875
TEGOMER ® V-Si 4042
TEGOMER ® FR 100
TEGOMER ® 5885
Processing aid and
dispersant.
Lubricant for wire
drawing
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Additive Technologies used in HFFR
Cable Application
Silanes or maleinic acid
anhydride grafted polymers
are used to interact with
hydroxy functional
flame retardants
HO
Al(OH) 3
ATH or MDH
particles
O
Si
OR
OR
O
O
O
OH
OH
HO
Al(OH) 3
ATH or MDH
particles
OH
Silicone oil is an external
lubricant only
OMS can interact with
Polymers and FR. adjusted
functionalisation is possible
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How to Use TEGOMER ® in the
Processing
I. During compounding with
kneader or double screw extruders
II. During cable extrusion
Motor
1. Fast Wetting
Heating elements
Allows higher processing speed
Motor
Hopper
Allows higher loadings
2. Enhanced Grinding
Perfect distribution of HFFR fillers results in
enhanced FR classifications and mechanical
properties
3. Excellent Lubrification
Results in excellent smooth surfaces
No die drol
Depending on the chosen TEGOMER ®
additive. they can easily charged into the
main feeder or by direct injected into the
kneader
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Improvement of Processing Enables
Higher Out Put
Example: EVA Compound with 65 % Mg(OH) 2
80
70
Extrusion head pressure
[bar]
Torsional moment
[A%]
1.0 % Additiv
2.0% Additiv
60
50
40
without
additive
Competitor
Product
TEGOMER ®
V-Si 4042
(liquid)
TEGOMER ®
FR 100
(solid)
without
additive
Competitor
Product
TEGOMER ®
V-Si 4042
(liquid)
TEGOMER ®
FR 100
(solid)
TEGOMER grades for HFFR compounds lower the amperage use and the extruder
head pressure. They work as internal lubricant. give less abrasion and therefore
reduced maintenance costs.
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Influence of TEGOMER ® on the MFI in
HFFR/EVA Compounds
Example: EVA Compound with 65 % Mg(OH) 2
8.0
7.0
6.0
5.0
4.0
MFI 190°C/10 kg [g/10 min]
5.0 6.5 6.5 7.0 7.0
without
additive
Competitor
Product
TEGOMER ®
V-Si 4042
(liquid)
1.0 % Additiv 2.0% Additiv
6.8 7.0
TEGOMER ®
FR 100
(solid)
TEGOMER ® works as a
highly efficient dispersing
aid and internal lubricant.
not only as an external
lubricant as silicon oil.
Therefore. it enhances the
MFI of high filled HFFR
compounds and optimizes
the melt flow to receive
excellent cable surfaces.
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TEGOMER ® V-Si 4042 for HFFR Compounds
Treated and Untreated Mg(OH) 2 in EVA
2% TEGOMER ® V-Si 4042
120
100
114
108
103
extrusion head pressure (bar)
torsional moment A%
92
80
67
60
53 53
56
40
20
0
65% Mg(OH) 2 untreated
without Additive
65% Mg(OH) 2
untreated
65% Mg(OH) 2
amino silane treated
65% Mg(OH) 2
vinyl silane treated
TEGOMER ® V-Si 4042 improves machine parameters such as extrusion head pressure
and torsional moment significantly for a) untreated fillers and
b) even for silane treated grades
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Influence of OMS Additives on the Melt
Viscosity of HFFR/EVA Compounds
Mooney Mooney units [MU] [MU] 190 °C 190 °C
80
70
60
50
40
30
20
10
0
TEGOMER ® grades allow significant lowering of
the Mooney viscosity
TEGOMER ® grades enable to use cheaper
untreated filler grades
TEGOPREN ® 5885 can be used as well and might
create a higher gloss on the final cable surface
[Min]
Time [min]
1 2 3 4 5
65% Mg(OH) 2
untreated
65% Mg(OH) 2
untreated
65% Mg(OH) 2
untreated
65% Mg(OH) 2
amino silane treated
65% Mg(OH) 2
vinyl silane treated
no Additive
+ 2% TEGOPREN ® 5885
+ 2% TEGOMER ® V-Si 4042
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Standard Measurement Devices for
Flame Resistance
UL 94V
CC
(Cone Calorimeter)
Source: Nabaltec/Germany
LOI
(Lowes Oxygen Index)
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Char Formation
65% MDH in EVA
65% MDH in EVA without Additive
No
Additiv
TEGOMER ®
V-Si 4042
TEGOPREN ®
5885
Char Formation depends on the selection of the right
organomodified siloxane
TEGOMER ® V-Si 4042 is preferred for compounding
TEGOPREN ® 5885 is very efficient for surface treatment
65% MDH in EVA with TEGOPREN ® 5885
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Cone Calorimetry
EVA 19, 65 wt.-% MDH
Without
Additive
LOI: 38
+ 2 % TEGMER ®
V-Si 4042 comp.
LOI 43
+ 2% TEGOPREN ®
5885 comp.
LOI: 45
+ 1 % TEGOPREN ®
5885 treat.
LOI: 42
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Heat Release Rate
EVA 19, 65 wt.-%
350
MDH without Additive
MDH + 2% TEGOMER ® V-Si 4042 comp.
MDH + 2% TEGOPREN ® 5885 comp.
300
250
200
HRR [kW/qm]
150
100
50
0
0
50
100
150
200
250
300
Time [s]
350
400
450
500
550
600
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Heat Release Rate
EVA 19, 65 wt.-%
350
ATH without Additive
ATH + 2% TEGOMER ® V-Si 4042 comp.
ATH + 2% TEGOPREN ® 5885 comp.
300
250
200
HRR [kW/qm]
150
100
50
0
0
50
100
150
200
250
300
Time [s]
350
400
450
500
550
600
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Rate of Smoke Released
EVA 19, 65 wt.-%
6
MDH without Additive
MDH + 2% TEGOMER ® V-Si 4042 comp.
MDH + 2% TEGOPREN ® 5885 comp.
5
4
RSR [m²/s m²]
3
2
1
0
0
50
100
150
200
250
300
Time [s]
350
400
450
500
550
600
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Rate of Smoke Released
EVA 19, 65 wt.-%
6
ATH without Additive
ATH + 2% TEGOMER ® V-Si 4042 comp.
ATH + 2% TEGOPREN ® 5885 comp.
5
4
RSR [m²/s m²]
3
2
1
0
0
50
100
150
200
250
300
350
400
450
500
550
600
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Time [s]

Highest Flame Retardant Classification
Due to Efficient Filler Dispersion
Sample 126 mm
Distance
19 mm
Flame 38 mm
Compounds created by using
2% of TEGOMER ® Grades
result in better flame
resistance and LOI
Cotton
Burner
Material Classification according UL 94 V (Vertical Burning Test) V-0 V-1 V-2
Combustion time for each specimen. 1. treatment ≤10s ≤30s ≤30s
Flaming and glowing combustion for each specimen (1. + 2. treatment) ≤30s ≤60s ≤60s
Total flaming combustion for all 5 specimens of any set ≤50s ≤250s ≤250s
Cotton ignited by flaming drips no no yes
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Flame Retardancy UL94
EVA 19, 59-65 wt.-% ATH
ATH
content
without
additive
2%
V-Si 4042
compounding
1%
V-Si 4042
treatment
2%
TP 6875
compounding
1%
TP 6875
treatment
2%
TP 5885
compounding
1%
TP 5885
treatment
0.5%
TP 5885
compounding
59% failed failed failed V-1 ? ? ? ?
61% failed V-0 V-0 V-0 V-0 V-0 V-0 V-0
63% V-1 V-0 V-0 V-0 V-0 V-0 V-0 V-0
65% V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
A loading of 65% ATH is needed to receive the V0 classification. By using
organomodified Siloxanes. as processing and dispersing additives. the
loading could be reduced down to 61%.
? = not carried out so far
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Influence of OMS Additives on the
Dispersion of FR
The higher the loading with inorganic FR the more easy is
insufficient dispersion of the FR even visible at the exterior
roughness of the extruded material
The dispersion of FR in the inner bulk phase is influencing
mechanical properties
65% ATH in EVA without additive
E-Modulus has to be balanced with elongation and an
average tensile strength is considered as minimum
requirement
TEGOMER ® V-Si 4042 can be used in the compounding
with up to 2% addition for MDH and ATH whereas
TEGOPREN ® 5885 needs lower addition levels
TEGOPREN ® 5885 as well as TEGOPREN ® 6875 are
suitable substances for surface treatment of MDH and
ATH whereas TEGOMER ® V-Si 4042 is not suitable
65% ATH in EVA with
2% TEGOMER ® V-Si 4042
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Benefits of Organomodified Siloxanes in
HFFR Compounds
They act as internal lubricants and
dispersant to reduce abrasion and avoiding die drol
Higher output by optimized melt rheology
Less pressure built-up and amperage draw during
extrusion
Less maintenance costs
Better dispersion of fillers resulting in very good flame
resistant classification
Smooth cable surfaces with excellent printability
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Organomodified Siloxanes -
Outstanding Properties in Performance
Throughput / Lubrification
Melt flow / MFI
Filler distribution
Filler loading
Flame retardency classification
Surface smoothness
Migration
Printability
Low Oxygen Index (LOI)
Die drol
Gloss
Mech. properties
TEGOMER ®
TEGOPREN ®
Silicone oil
masterbatches
Silanes
Cable Compounding
MAA grafted
compatibilzer
+ +
O
-
+ +
O
-
+ O
+
+
+ +
O
-
Cable Extrusion
+ -
+
O
+ +
O
-
No
Yes
No
No
+ -
+
+
+ O
+
O
No
No
No
Yes
+ O
O
-
+ -
+
+
+ = good O = moderate - = bad
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