wax 2

Waxes for pigment dispersion in
polar and non polar plastics
1st International Conference
on Masterbatch & Compound
15th/16th of February 2016 - Tehran
1
Classification of PE-waxes and effects in colour MB
=> PE-waxes can be produced in different ways:
1.
Polymerisation process e.g. by metallocene or
Ziegler-Natta-catalysts starting from Ethylene
2.
Thermal degradation of polyethylen in a batch process
using e.g. peroxides and / or paraffin
3.
Using low molecular waste wax from HDPE manufacturers
by removing hexene or heptane sometimes destillation
and removing the catalyst
4.
Depolymerisation process of polyethylen in a reactor
2
What are the differences / advantages / disadvantages?
1.
Polymerisation process:
+ typically high quality waxes
+ low amount of low molecular weight by-products
+ good dispersing properties / color yield
+ very low migration
- price level
- polymerisation reactor with high throughput of
typically ~ 15000 – 40000 t/a; reduced flexibility in
production and shortage in case of force majeur
or maintanance of the plant
3
What are the differences / advantages / disadvantages?
2.
Thermal degradation:
+ low price
- insufficiant process control
- low molecular weight by-products
- broad / non stable molecular weight distribution
- yellowish color
- batchwise changing of dispersing properties
- migration
- smell due to peroxide decomposites
4
What are the differences / advantages / disadvantages?
3.
By-product wax from HDPE production:
+
+
-
low price
good wetting due to very low viscosity
low molecular weight
not constant molecular weight distribution
depending on manufactured HDPE
not constant availability
sometimes yellowish colour (catalyser residues)
low dispersing properties due to low viscosity
and linear structure
migration
sometimes spots / agglomerates from catalyser
5
What are the differences / advantages / disadvantages?
4.
Depolymerisation process developed by EUROCERAS:
+
+
+
+
+
+
+
-
high quality comparable with polymerisation process
reasonable price
very stable parameters and quality
flexible production due to medium sized reactors
of 3000 – 8000 t/a
low amount of molecular weight by-products
very low migration
good dispersing properties / color yield
polydispersibility < 2 difficult to achieve
6
Fast laboratory tests to characterise the wax quality (low MW content)
(2.) waxes made by
thermal degradation:
wax #A: penetration into filter paper
wax #B: strong penetration
wax #E: penetration
(3.) by-product wax from HDPE:
wax #C: slight penetration
wax #D: extreme penetration
(4.) depolimerisation process:
CERALENE® 2T: no penetration
CERALENE® 1X: no penetration
7
Example of migration after storage in a warehouse (3 month)
Black masterbatch
produced with wax from
depolimerisation
process (4.):
CERALENE® 2T:
Black masterbatch
produced with
by-product wax (3.):
strong migration
no migration
8
DSC of a by-product wax from HDPE (3.)
9
DSC of a wax from depolimerisation process (4.)
10
TGA measurement of high quality waxes:
1203xxx T240 - Vergleich PE W achs- 03/12
method:
%
20 – 240°C with 30K/min
240°C isotherm 60min
(4.) wax from depolymerisation
process:
CERALENE® 2T:
26.03.2012 11:01:14
- 0.421%
(1.) waxes from polymerisation
process:
PE-Wax
TGA - 60 min. at 240 °C
101,5
!120372 T240 - Ceralene 2T - 03/12
120372 T240 - Ceralene 2T - 03/12, 12,5013 mg
101,0
!120374 T 240-Licowax PE520 Piv- 03/12
wax#1
120374 T 240-Licowax PE520 Piv- 03/12, 11,4 090 mg
100,5
100,0
99,5
!120371 T240 - Honeywell
wax#2AC 6A - 03/12
120371 T240 - Honeywell AC 6A - 03/12, 13,7410 mg
99,0
!120373 T 240-Luwax
A - 03/12
wax#3
120373 T 240-Luwax A - 03/12, 11,2 553 mg
98,5
98,0
wax#1: - 0.667%
97,5
wax#2: - 0.482%
wax#3:
- 0.905%
method: 30-240/30K - Iso 60 min - BK - N2
97,0
96,5
96,0
0
100
200
5
M ETTLER TO LED O
240
10
15
20
25
30
35
°C
40
45
50
55
60
STAR e
11
min
SW 10.00
Application tests with high quality waxes
from polymerisation and depolymerisation process:
Ramafast blue (Pigment blue 15:3 from India): 40% P.B. 15:3 + 40% PP
Test number
Wax
A.1
20% wax 1 (polymerisation process)
A.3
20% wax 2 (polymerisation process)
A.4
20% CERALENE 2T (depolymerisation)
=> Pressure filter test according to DIN EN 13900-5
=> Colour measurement according to EN ISO11664-4
12
Pressure filter test according to DIN EN 13900-5: screenshot CERALENE 2T (A.4)
13
Pressure filter test according to DIN EN 13900-5:
results (with 40 mm sieve)
P
start (bar)
P end (bar)
∆P (bar)
P max (bar)
FPV end (bar/g)
V A.1 (wax 1)
19,02
117,40
98,38
123,90
2,46
V A.3 (wax 2)
20,19
80,50
60,31
112,60
1,51
V A.4 CERALENE 2T
19,60
73,50
53,90
94,00
1,35
14
Colour measurement according to EN ISO11664-4
Test number
Colour yield
(BASF method)
V A.1 (wax 1)
100,0%
V A.3 (wax 2)
98,9%
V A.4 CERALENE 2T
106,2%
15
Application tests with high quality waxes
Heliogen Blue K 6902 – P.B.15:1
Chromophtal Yellow HRPN – P.Y.191:1
Chromophtal Red 2030 – P.R. 254
Comparison of waxes from polymerisation and depolimerisation
process and combination with polar Polyesterwaxes
Chromophtal Yellow HRPN – P.Y.191:1
(14mm filter)
Formulation
Wax:
Pigment yellow 191:1:
PP powder:
20 %
40 %
40 %
Filter pressure value [bar/g]
2,0
20
110
1,5
1,0
100
104
105
1,1
90
70
0,7
50
Colour yield (BASF method) [%]
130
30
Wax 2
polymerisation
process
Ceralene 2 T
Ceralene 2 T / Ceralene 694 = 3:1
17
Heliogen Blue K 6902 – P.B.15:1
(40mm filter)
Wax 2
polymerisation
process
Formulation
Wax:
Pigment blue 15:1:
PP powder:
Ceralene 2 T
20 %
40 %
40 %
Ceralene 2 T / Ceralene 694 = 3:1
18
Chromophtal Red 2030 – P.R. 254
(14mm filter)
Formulation
Wax:
Pigment Red 254:
PP powder:
20 %
40 %
40 %
1,0
20
114
110
110
100
0,5
90
70
50
0,2
0
0,1
Wax 2
polymerisation
process
0,1
Ceralene 2T
Colour yield (BASF method) [%]
Filter pressure [bar/g] / filter 14mm
130
30
Ceralene 2T / Ceralene 694 = 3:1
19
Conclusions:
- it is possible to produce high quality waxes by using a
polymerisation process (starting with ethylene) as well
as by using a depolimerisation process (starting with polyethylene)
- dispersing properties and content of by-products of waxes
from depolimerisation (CERALENE® wax) and polymerisation
are comparable
- waxes made from polyethylene by a not proper controlled thermal
degradation as well as from HDPE by-products can cause
strong migration effects due to low molecular weight content
- a combination of PE-wax and polar Polyester wax can increase
the pigment dispersion and color yield
Unique synthetic polyester for pigment dispersion in
masterbatches for polar and non polar plastics

The new developed CERALENE® polyester waxes are synthetic
origin, this assures a reliable supply and constant quality.

The chemical structure of the new CERALENE® polyester waxes
as a synthetic product is more uniform in comparison to a natural
wax which contains several fractions.

CERALENE® polyester waxes are available in free flowing prills
with a typical particle size between 0.2 – 1.0 mm. The prills
assure easy and accurate dosing as well as uniform mixing.
22
 Properties of CERALENE® POLYESTER WAXES:

Polymer with a molecular weight Mw > 2000
=> no migration / no plate out

Very low volatility
=> important for high temperature processing

Good compatibility
=> grades with different polarity adjustable to the resin and application

Excellent temperature stability
=> no yellowishing / no influence on the resin colour

Excellent surface quality / gloss
 White colour of all grades
23
Polyolefine colour masterbatches (PE and PP)
+ colour yield
+ easier incorporation of pigments in polymers
+ strongly improved pigment wetting and dispersion
+ highly temperature resistant, suitable for fibres
+ no migration and plate out
+ no yellowishing
Technical plastics (e.g. PA, PS, PA, ABS, POM, PET)
+ stable at high process temperatures
+ improved flow
+ improved release (reduced demoulding forces)
+ surface gloss
24
 Overview about CERALENE® polyester waxes:
 Structure
polar functional groups
unpolar C-chain
drop point
acid number
viscosity (120°C)
[°C]
[mg(KOH)/g]
[mPa*s]
CERALENE® 691
~ 70
~10
~ 130
CERALENE® 693
~ 70
~16
~ 400
CERALENE® 694
~ 70
~19
~ 170
25
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 Excellent temperature stability:
CERALENE ®
CERALENE ®
CERALENE ®
Montan wax
ester
Air draft oven at 160°C, 24 hours)
Montan wax
ester
CERALENE ®
27
 Surface Quality/Gloss:
CERALENE ® 691
(after heating in an air draft
oven at 160°C for 24 hours)
28
 Application Fields:
 Usage in pigment dispersion
1. Pigment wetting
•
•
•
drop point
polarity
viscosity
2. Dispersion
•
•
•
viscosity
thermal stabilty
colour stability
3. Stabilisation
•
•
•
polarity
compatibility
viscosity
29
 Very good compatibilty with different technical resins:
Resin
Dosage
CERALENE 691 [%]
Visual
Polycarbonate
0.4
+, slightly opaque
Polystyrene
0.5
+, slightly opaque
Polyamide
0.3
++
Polyamide
5.0
++
ABS
0.4
++
POM
0.3
++
PET
0.3
++
PP
0.3
++
30
 Improved surface gloss (example polyamide):
31
 New CERALENE® copolymer waxes:
drop point
acid number
viscosity (120°C)
[°C]
[mg(KOH)/g]
[mPa*s]
CERALENE® CP15M
~ 103
~17
~ 500
CERALENE® CP30M
~ 99
~ 28
~ 600
CERALENE® CP45M
~ 97
~ 38
~ 600
 New CERALENE® PP homopolymer wax:
CERALENE® 850
drop point
acid number
viscosity (170°C)
[°C]
[mg(KOH)/g]
[mPa*s]
~ 150
0
~ 80
32