Waxes for pigment dispersion in polar and non polar plastics

Transcription

1 Waxes for pigment dispersion in polar and non polar plastics 1st International Conference on Masterbatch & Compound 15th/16th of February Tehran 1

2 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

3 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 ~ t/a; reduced flexibility in production and shortage in case of force majeur or maintanance of the plant 3

4 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

5 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

6 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 t/a + low amount of molecular weight by-products + very low migration + good dispersing properties / color yield - polydispersibility < 2 difficult to achieve 6

7 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

8 Example of migration after storage in a warehouse (3 month) Black masterbatch produced with wax from depolimerisation process (4.): CERALENE 2T: no migration Black masterbatch produced with by-product wax (3.): strong migration 8

9 DSC of a by-product wax from HDPE (3.) 9

10 DSC of a wax from depolimerisation process (4.) 10

11 TGA measurement of high quality waxes: method: C with 30K/min 240 C isotherm 60min (4.) wax from depolymerisation process: CERALENE 2T: % (1.) waxes from polymerisation process: wax#1: % wax#2: % % 101,5 101,0 100,5 100,0 99,5 99,0 98,5 98,0 97,5 97,0! T240 - Ceralene 2T - 03/ T240 - Ceralene 2T - 03/12, 12,5013 mg! T240-Licowax PE520 Piv- 03/12 wax# T240-Licowax PE520 Piv- 03/12, 11,4090 mg! T240 - Honeywell wax#2ac 6A - 03/ T240 - Honeywell AC 6A - 03/12, 13,7410 mg wax#3! T240-Luwax A - 03/ T240-Luwax A - 03/12, 11,2553 mg 1203xxx T240 - Vergleich PE W achs- 03/ :01:14 PE-Wax TGA - 60 min. at 240 C method: /30K - Iso 60 min - BK - N2 wax#3: % 96, C 96, min M ETTLER TO LED O STAR e SW

12 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 => Colour measurement according to EN ISO

13 Pressure filter test according to DIN EN : screenshot CERALENE 2T (A.4) 13

14 Pressure filter test according to DIN EN : 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

15 Colour measurement according to EN ISO 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

16 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

17 Filter pressure value [bar/g] Colour yield (BASF method) [%] Chromophtal Yellow HRPN P.Y.191:1 (14mm filter) Formulation Wax: 20 % Pigment yellow 191:1: 40 % PP powder: 40 % 2, , ,0 1,1 70 0, Wax 2 polymerisation process Ceralene 2 T Ceralene 2 T / Ceralene 694 = 3:1 17

18 Heliogen Blue K 6902 P.B.15:1 (40mm filter) Formulation Wax: 20 % Pigment blue 15:1: 40 % PP powder: 40 % Wax 2 polymerisation process Ceralene 2 T Ceralene 2 T / Ceralene 694 = 3:1 18

19 Filter pressure [bar/g] / filter 14mm Colour yield (BASF method) [%] Chromophtal Red 2030 P.R. 254 (14mm filter) Formulation Wax: 20 % Pigment Red 254: 40 % PP powder: 40 % 1, , ,1 Wax 2 polymerisation process 0,2 0,1 Ceralene 2T Ceralene 2T / Ceralene 694 = 3:

20 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

21 Unique synthetic polyester for pigment dispersion in masterbatches for polar and non polar plastics

22 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 mm. The prills assure easy and accurate dosing as well as uniform mixing. 22

23 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

24 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

25 Overview about CERALENE polyester waxes: Structure polar functional groups unpolar C-chain drop point [ C] acid number [mg(koh)/g] viscosity (120 C) [mpa*s] CERALENE 691 ~ 70 ~10 ~ 130 CERALENE 693 ~ 70 ~16 ~ 400 CERALENE 694 ~ 70 ~19 ~

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27 Excellent temperature stability: CERALENE CERALENE Montan wax ester CERALENE Air draft oven at 160 C, 24 hours) Montan wax ester CERALENE 27

28 Surface Quality/Gloss: CERALENE 691 (after heating in an air draft oven at 160 C for 24 hours) 28

29 Application Fields: Usage in pigment dispersion 1. Pigment wetting 2. Dispersion 3. Stabilisation drop point polarity viscosity viscosity thermal stabilty colour stability polarity compatibility viscosity 29

30 Very good compatibilty with different technical resins: Resin Dosage CERALENE 691 [%] Visual Polycarbonate 0.4 +, slightly opaque Polystyrene 0.5 +, slightly opaque Polyamide Polyamide ABS POM PET PP

31 Improved surface gloss (example polyamide): 31

32 New CERALENE copolymer waxes: drop point [ C] acid number [mg(koh)/g] viscosity (120 C) [mpa*s] CERALENE CP15M ~ 103 ~17 ~ 500 CERALENE CP30M ~ 99 ~ 28 ~ 600 CERALENE CP45M ~ 97 ~ 38 ~ 600 New CERALENE PP homopolymer wax: drop point [ C] acid number [mg(koh)/g] viscosity (170 C) [mpa*s] CERALENE 850 ~ ~ 80 32