waxes for engineering plastics

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BU AdditivesTechnical Marketing Waxes08.05.2013

Specialty Waxes for the Processingof Engineering Resins

BU Additives, Technical Marketing Waxes, 08.05.2013

Content

– Lubricants for engineering resins - demands and effects – Clariant lubricant portfolio– Methods for internal and external lubrication measurement– Results in styrenics and engineering resins

- Lubricants for PS and PS -Copolymers- Lubricants for PC- Lubricants for PET / PBT- Lubricants for POM- Lubricants for TPU- Lubricants for PMMA- Lubricants and nucleating agents for PA- Lubricants for thermosets- Specialities

Public, Waxes for Engineering Plastics

® Trademark registered by Clariant in numerous countries®* Trademark licensed to Clariant in numerous countries

2


Demands on Lubricants for Engineering Resins

Challenges Requirements on Lubricants

1. High processing temperatures ⇒ Low volatility, high thermal stability

2. Complicated moulded parts ⇒ Enhancing Melt Flow (internal lubricant)

3. Sticky polymer grades ⇒ Release/slip effect (external lubricant)

4. Optimised/maximum colour yield ⇒ Dispersing aid for pigments / fillers

5. Short cycle times ⇒ large numbers ⇒ Nucleating effect

Public, Waxes for Engineering Plastics3


Nucleation

Flow Promotion

Mold Release

Pigment/AdditiveDispersion

Coupling Effect

Adhesion Promotion /Compatibilisation

Licowax, Licomont and Licolub in PlasticsThe Main Effects



Waxes for Engineering Resins IStructures and Properties of Main Products


Drop point [°C]

Acid value[mg KOH/g]

Licowax E / Ceridust 5551 ~ 82 ~ 17

Licowax OP ~ 100 ~ 12

Licolub WE 4 ~ 80 ~ 25

Licolub WM 31 ~ 72 ~ 10

Licolub WE 40 ~ 74 ~ 17

Licowax CLicolub FA 1 powder vegetable based ~ 142 ~ 7

+Ca

n

COOH = Fatty acid~ C18 = CO-function (polar)COOH = Montanic acid

~ C30

5

= Amide group


Waxes for Engineering Resins IIStructures and Properties of Main Products

Drop point [°C]

Acid value[mg KOH/g]

Licomont NaV 101 ~210 < 5

Licomont CaV 102 ~85 ~10

Licowax PE 520 ~118 0

Licowax PED 191 ~123 ~ 17

Licolub H 12 ~106 ~ 17

Licocene PE MA 4221 ~ 123 ~ 18

Na+ [– ]

Ca2+ [– ]

6 Public, Waxes for Engineering Plastics

Na = metal soap


Method for External LubricationRelease Force Measurement

– Force being necessary to remove the molded part from the injection mold (tool).

– Evaluation of force which has to be applied at ejection of molded articles during injection molding process.

– This force is influenced by additives remarkably.

– In general it is advantageous to keep that force as low as possible.



Molding unit for release force measurement

Release Force Measurement


Cylindrical sleeves (molds)


Method for Internal LubricationSpiral Length Test - Injection Molding of Sprials


The longer the spiral, the better is the melt flow

Public


Results with Clariant Waxes in Styrenics& Engineering Resins

POLYSTYRENE AND PS-COPOLYMERSPOLYCARBONATEPOLYESTERPOLYACETALTHERMOPLASTIC POLYURETHANEPOLYMETHYL METHACRYLATEPOLYAMIDESPECIALITIES


Flow improvement: Licowax E, Licolub WE 4 0,3 - 1,0Licowax C / Licolub FA 1 pwd. veg. based

Release: Licowax C / Licolub FA 1 pwd. veg. based 0,3 - 1,0Licowax E, Licowax OPLicowax PE 520, Licolub WE 4

Dispersion: Licowax E, Licowax OP 0,5 - 7,0

Nucleation of EPS: Licocene PE 4201 0,05 - 0,3Ceridust 3620

Slip and antiblocking Licowax C / Licolub FA 1 pwd. veg. based 0,1 - 0,5properties:

[%]*)

*) = concentration by weight in the end article

PS and PS-Copolymers (incl. ABS, SAN etc.) Effects, Products and Dosage



Waxes for PS and PS-CopolymersRelease Effect in PS-HI


0

100

200

300

400

500

600

Without Licowax OP Licowax C Licowax E LicolubWE 40

LicolubWE 4

Rel

ease

forc

e [N

]

Formulation:Polystyrene (S 6600)+ 0,5 % Test product

12


Waxes for PS and PS-CopolymersFlow Improvement of PS-HI (Spiral Length Test)

58

59

60

61

62

63

Without Licowax OP Licowax E

Spira

l len

gth

[cm

]

Lubricant dosage: 0,5 %Mass temperature: 240°CMold temperature: 20 °C



Waxes for PS and PS-CopolymersRelease Effect in GP-PS

0

20

40

60

80

100

0

100

200

300

400

500

600

Without Licowax C Licowax E Licolub H 12 LicowaxPE 520

Tran

spar

ency

[%]

Rel

ease

forc

e [N

]

Release forceTransparency

Lubricant dosage: 0,5 %



0

20

40

60

80

100

0

5

10

15

20

25Corr. Haze [%] Transparency [%]

Colorimetry settings -transmission measurement:Haze: Spectrophotometer (Minolta CM 3600d),Light source: C,2° Standard observer;

Transparency: LT 12 (Dr. Lange),Light source: C

Samples:1 mm injection moulded plaques

Formulation:Polystyrene (N 2000)+ 1 % WaxExtrusion:Temp.: 180 -> 230 °C,Screw rotation: 40 rpm,Extruder: Leistritz LSM 30.34(23 x D)

=> the lower corr. haze the higher transparency !

Waxes for PS and PS-CopolymersTransparency



100

105

110

115

Licowax E Licowax OP Licowax C

rel.

colo

r yie

ld [%

] @ 5

10 n

m

Formulation: Processing: Colorimetric test:30% Pigment Green 7 cold mixture, 4 min. at 600 rpm Minolta CM-3600d5% wax Berstorff ZE 25 x 40D, 8 kg/h, 300 rpm full shade, 1% MB

65% Polystyrene N 2000 200-185-170-160-175-190-200 °C 510 nm,

Waxes for PS and PS-CopolymersPigment Dispersion



90

100

110

120

Licowax E Licowax C

rel.

colo

r yie

ld [%

] at 5

10 n

m

3% wax5% wax7% wax

Formulation: Processing: Colorimetric test:30% Pigment Green 7 cold mixture, 4 min. at 600 rpm Minolta CM-3600dx% wax Berstorff ZE 25 x 40D, 8 kg/h, 300 rpm full shade, 1% MB

63-67% Polystyrene N 2000 200-185-170-160-175-190-200 °C 510 nm, transmission

Waxes for PS and PS-CopolymersPigment Dispersion



1200

1400

1600

1800

2000

2200

Without Licowax OP Licowax E LicolubWE 4

Licowax C

Rel

ease

forc

e [N

]

Lubricant dosage: 0,5 %

Waxes for PS and PS-CopolymersRelease Effect in ABS



44

45

46

47

48

49

Without Licowax C Licowax E Licowax OP Licolub WE 4

Spira

l len

gth

[cm

]

Injection molding: 220-220-230-240°CMold temperature 50°CLubricants dosage: 0,2 %

Waxes for PS and PS-CopolymersFlow Improvement of SAN


Public


Results with Clariant Waxes in Styrenics& Engineering Resins




[ % ] *)

Flow improvement: Licowax E, Licowax OP 0,1 - 0,5Licowax C / Licolub FA 1 pow. veg. based

Dispersion: Licowax E, Licowax OP 0,1 - 1,0Licowax C / Licolub FA 1 pow. veg. based

Release: Licowax E, Licowax OP 0,1 - 1,0Licowax PED 191Licolub WE 4

Polycarbonate (PC)Effects, Products and Dosage



Waxes in PCRelease Effect

1000

2000

3000

4000

5000

6000

7000

Rel

ease

forc

e[N

]


VN 110543-557Lubricant dosage: 0,3 %


Waxes in PCFlow Improvement / Melt Flow Rate (1,2 kg, 300 °C)

0

2

4

6

8

10

12

14

Without PETS Licowax E Licowax OP Licolub WE 4 Polyesterwax

MFR

[g/1

0 m

in]




Waxes in PCTransparency

60

65

70

75

80

85

90

Tran

spar

ency

[%]




0

25

50

75

100

900

1200

1500

1800

2100

2400

2700

3000

3300

without lubricant + 0,3 % PETS + 0,3 %Licowax E

+ 0,3 %Licowax PED 191

Tran

spar

ency

[%]

Rel

ease

For

ce [N

]

Release forceTransparency

(Pentaerythritoltetrastearate)

Waxes in PCRelease Effect and Transparency (1 mm Plates)



.

Formulation: 17 % Pigment Green 7, 3 % montan wax, 80 % Polycarbonate (Blendex HPP 806, GE Plastics)Extrusion: Co-rotating twinscrew extruder Ø 25 mm, L/D= 40, screw speed 300 rpm, barrel 260 240 °C,

throughput 7 kg/hSample preparation: Ultrafine sections of granules, thickness 60-80 nm; Cutter type Ultracut E

(manufacturer Reichert+Jung, Germany)Microscopy: Transmission electron microscopy (TEM), Microscope type ZEISS EM 10B

Magnification: 4000x

No wax 3 % Licowax® E 2 % Licowax E1 % Ceridust® 5551

(colour yield = 100 %) (colour yield =117 %) (colour yield = 131 %)

Improved Dispersion through CeridustTEM Photographs of Polycarbonate Samples



Advantages of Licowax E in Polycarbonate

– Customer statements:

- No reaction of the metal-ion - sensitive PC with Montan waxes

- Almost no effect on transparency

- No safety problems at high processing temperatures (up to 300 °C)like burning of the lubricant

- Excellent thermal stability


Public


Some Results with Clariant Waxes in Styrenics& Engineering Resins



Flow improvement: Licowax E, Licowax OP 0,1 - 1,0Licolub WE 4, Licolub WE 40Licocene PE MA 4221

Dispersion: Licowax E, Licowax OP 0,1 - 1,0Licolub WE 4

Release: Licowax E, Licowax OP 0,1 - 1,0Licolub WE 4, Licolub WE 40Licocene PE MA 4221

Nucleating: Licomont NaV 101 0,1 - 0,3

Slip antiblocking: Licowax C / Licolub FA 1 pwd. veg. based 0,1 - 0,5

[%] *)


Polyester (PET/PBT)Effects, Products and Dosage


For more detailed information on our lubricants for Polyester, please refer to our separate Polyester presentation


Montan Waxes in PBTRelease Effect

1000

2000

3000

4000

5000

6000

7000

Without Licowax E Licowax OP PETS

Rel

ease

forc

e[N

]


VN 109995-110012

FormulationPBT + 0,3 % Test product

30


0

1000

2000

3000

4000

5000

6000

7000

8000

without Licowax E Licowax OP Licolub WE 4 Licolub WE 40

Rel

ease

forc

e[N

]

Formulation:PET T 86+ 0,3 % Test product

Montan Waxes in PETRelease Effect



Montan Waxes in PBTFlow Improvement / Melt Flow Rate (2,16 kg, 250 °C)

22

23

24

25

26

27

28

29

30

Without Licowax E Licowax OP Licolub WE 4

MFR

[g/1

0 m

in]


FormulationPBT + 0,3 % Test product

VN 109995-110012

32


Effects of Montan Waxes in Polyester

- EU approval for Montan Waxes like Licowax E, Licowax OP and Licolub WE 4in PBT / PET

– Due to long unpolar carbon chains and polar ester groups:- Excellent release properties - Flow improvement- Dispersion of fillers and pigments- Almost no effect on transparency for PET- No degradation of the polyester

– Due to the high molecular weight:- Low volatility- High thermal stability- Low migration



Licocenen PE MA 4221 in PBTColor Influence & Release Forces


0

1

2

3

4

5

6

7

8

Without Wax 0.3 %Licowax E

0.3 %Licocene

PE MA 4221

Yello

wne

ss In

dex

– No yellowish discoloration with Licocene PE MA 4221– Acceptable effect of reduction of release forces compared to Licowax E

0

200

400

600

800

1000

1200

1400

Without Wax 0.3 %Licowax E

0.3 %Licocene

PE MA 4221

Rel

ease

forc

e [N

]

> 6700


Licomont NaV 101 as an Effective and UniqueNucleating and Lubricating Agent for Polyesters

All advantages for the processing of polyester combined in one additive:

– Increased mechanical properties

– Higher degree of cristallisation

– Higher output in injection molding up to 35 %

– Faster nucleation, therefore decreased cycle time

– Easier demolding

– Improved flow

– EU approval in Polyester



Licomont NaV 101 in PETNucleation Properties / DSC

1. Cooling cycle

+ 0,2 % Licomont NaV 101



0,5 Wg-1

°C300 260 220 180 140 100 60

without

36





0,5 Wg-1

°C300 260 220 180 140 100 60

without

Licomont NaV 101 in PETNucleation Properties / DSC

1. Cooling cycle

Without 0,1 % Licomont NaV 101

0,2 % Licomont NaV 101

0,4 % Licomont Nav 101

Peak of Crystallisation[°C]

187,5 200,0 203,0 204,9

Heat of Crystallisation[J/g]

36,9 37,9 39,5 41,5

37


Licomont NaV 101 in PETNucleation Properties Leading to Cycle Time Reduction

20

25

30

35

40

45

without 0,10% 0,20% 0,40%

Cyc

le ti

me

[s]

Injection molding machine:Arburg Allrounder 320 CFormulation:Polyester (IV = 0,811) Samples:Standard tensile barsMold temperature:15°C


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[ % ] *)

Flow improvement: Licowax E 0,2 - 0,5Licowax OPLicowax C / Licolub FA 1 pwd. veg. based

Dispersion: Licowax E 0,2 - 0,5Licowax OPLicowax C / Licolub FA 1 pwd. veg. based

Release: Licowax E 0,2 - 1,0Licowax OPLicowax PED 191Licowax C / Licolub FA 1 pwd. veg. based

Polyacetal / Polyoxymethylene (POM)Effects, Products and Dosage



0

500

1000

1500

2000

2500

3000

without Licowax E Licowax OP Licolub WE 4 Licomont CaV 102

Rel

ease

For

ce [N

]

Formulation:Hostaform C 9021 99,7 %Test product 0,3 %

Waxes for Polyacetal (POM)Release Effect


Public





[ % ]*)

Flow improvement: Licowax E 0,3 - 0,8Licowax OPLicowax C / Licolub FA 1 pwd. veg. based

Release: Licowax E 0,3 - 1,0Licowax OPLicowax C / Licolub FA 1 pwd. veg. based


Thermoplastic Polyurethane (TPU)Effects, Products and Dosage



0

10

20

30

40

50

60

70

without Licowax E Licowax OP LicolubWE 4

LicolubWE 40

Licowax C LicomontCaV 102

Tack

free

tim

e [m

in.]

> 75 > 75 > 75

Formulation:Elastollan C85A10

0,2 % lubricant (tumbled onto TPU granules)

1,0 % lubricant (tumbled and extruded togetherwith TPU prior to two-roll milling)

Determination of Tack-free Time (two-roll Mill (stainless steel); 185 °C; 16,7 / 20 rpm)

Waxes for TPU (Polyester-based Polyurethane Elastomer)Release Effect


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[ % ] *)

Flow improvement: Licowax E 0,1 - 0,5Licowax C / Licolub FA 1 pwd. veg. basedLicolub WE 40

Dispersion: Licowax E 0,1 - 0,5Licowax C / Licolub FA 1 pwd. veg. basedLicolub WE 40

Release effect: Licowax E 0,1 - 0,5Licolub WE 40Licowax C / Licolub FA 1 pwd. veg. based

Polymethyl Methacrylate (PMMA)Effects, Products and Dosage



0

200

400

600

800

1000

1200

without Licowax E Licolub WE 40 Licowax C

Rel

ease

forc

e[N

]

Formulation:Diakon CLG 502+ 0,2 % Test product

Waxes for Polymethyl Methacrylate (PMMA) Release Effect



0 4 8 12 16

no wax

LicowaxE

LicowaxOP

LicowaxC

LicolubWE 4

LicolubWE 40

Correlated Haze [%]

2,5%1,0%0,5%

Licowax C: No influence on transparency, even in high concentrations

Licolub WE 40: Best Montanwax with regard to transparency. No influence on transparency in low to medium concentrations, less in high concentrations

Licolub WE 4: No influence on transparency in low to medium concentrations, unsuitable for high concentrations

Licowax E and OP: Suitable for low concentrations, less influence on transparency in medium concentrations.

Conclusion:

Licowax C for highest demands on transparency

Licolub WE 40 for high demands on transparency if a Montanwax is preferred

Waxes for PMMAInfluence of Waxes on Transparency


Public





[ % ] *)

Flow improvement: Licowax E, Licowax OP 0,1 - 1,0Licomont CaV 102, Licolub WE 40Licowax C / Licolub FA 1 pwd. veg. based

Dispersion: Licowax E, Licowax OP 0,1 - 1,0Licowax C / Licolub FA 1 pwd. veg. based

Release: Licowax E, Licowax OP 0,1 - 1,0Licomont CaV 102, Licolub WE 40

Nucleating: Licomont CaV 102 0,1 - 0,3


Polyamide (PA)Effects, Products and Dosage


For more detailed information on our lubricants for Polyester, please refer to our separate Polyester presentation


Waxes for Polyamide 6Release Effect

400

600

800

1000

1200

1400

1600

Without Calciumstearat PETS Licowax E Licowax OP Polyesterwax

Rel

ase

forc

e [N

]

Formulation:PA + 0,3 % Test product


VN 109971-980 u. VN 109981-991

> 8000


Waxes for Polyamide 6Flow Improvement / Spiral Flow Test

39

40

41

42

43

44

45

Spira

l len

gth

[cm

]


VN 109971-980 u. VN 109981-991

Formulation:PA 6 + 0,3 % Test product


Waxes for Polyamide 6.6Release Effect

600

800

1000

1200

1400

1600

1800

Rel

ease

forc

e [N

]


VN 109935-944 u. VN 109945-955

Formulation:PA 6.6 + 0,3 Test product


Waxes for Polyamide 6.6Flow Improvement / Spiral Flow Test

40

45

50

55

60

65

70

Spira

l len

gth

[cm

]


VN 109935-944 u. VN 109945-955

Formulation:PA 6.6 + 0,3 % Test product


40

45

50

55

60

Without Licowax E Licowax OP LicomontCaV 102

Spira

l len

gth

[cm

]

(Spiral test of PA 6.6, 45% GF; Temperature: 320°C; Dosage: 0,5 %)

Waxes for Polyamide 6.6 / GF reinforcedFlow Improvement / Spiral Flow Test



0

100

200

300

400

500

600

700

800

900

1000

without 0,05% 0,10% 0,30% 0,50% 0,80%

Rel

ease

For

ce [N

]

Concentration Licowax E

Waxes for Polyamide 6.6 / GF reinforcedRelease Effect / Optimum Concentration



Licocene PE MA 4221 in PA 6 / GF reinforced (30%)Color Influence & Release Effect


12

13

14

15

16

17

18

19

20

Without Wax 0,3 %Licowax E

0,3 %Licocene

PE MA 4221

Yello

wne

ss In

dex

– Almost no yellowish discoloration with Licocene PE MA 4221– Montan Waxes provide better release

0

500

1000

1500

2000

2500

Without Wax 0,3 %Licowax E

0,3 %Licocene

PE MA 4221

Rel

ease

forc

e [N

]


Properties of Montan Waxes in Polyamides

- EU food-approval in PA

– Due to long unpolar carbon chains and polar ester groups

- Excellent release properties

- Flow improvement

- Dispersion of fillers and pigments

- Almost no effect on transparency

– Due to the high molecular weight

- Low volatility

- High thermal stability

- Low migration



Properties of Licowax C and Licolub FA 1 pwd. veg. based in Polyamides


– Flow improvement

– FDA approval for all polymers according to „prior sanction status“

– Almost no effect on transparency and Yellowness Index

– Vegetable based source available: Licolub FA 1 pwd. veg. based

– Disadvantage: Tendency to migrate to the surface


Licomont CaV 102 for PolyamidesEffective Nucleating Agent and Lubricant for the Processing

Drop point[°C]

Acid value[ mg KOH/g ]

Licomont CaV 102 ~ 85* ~ 10Ca - salt of long chain carboxylic acids


Ca2+ [– ]2

= metal soap * DSC

All advantages for the processing of polyamides are combined in one additive:– Increased mechanical properties– Higher degree of crystallization– Faster nucleation, therefore decreased cycle time– Easier demolding– Improved flow– Higher output in injection molding up to 25 %


Polyamide Nucleating with Licomont CaV 102DSC: Isothermal Run at 200°C with PA 6 Compounds


5,8 15,3

0,5 % Licomont CaV 102

Without nucleating agent

Hea

t flo

w (e

xoth

erm

ic)

Time [min]T2 T1

=> The shorter time to crystallization -the shorter are cycle times for molding !

=> The higher the crystallization peak -the higher is mechanical strength of the final article !


Polyamide -Injection Molding-Cycle Time Reduction with Licomont CaV 102


15

20

25

30

without + 0,5 % Licomont CaV102

cycl

e tim

e [s

]

Injection molding machine:Arburg Allrounder 320 CFormulation:Polyamide 6.6 MVR 80 g/10min (275°C/5kg)+ 30 % glass fibersSamples:Standard tensile barsMold temperature:80°C

Investigation was done under supervision of Arburg

- 23 %

mold


Licomont CaV 102 fine grainThe Ultimative Additive for Injection Molded Polyamides

– Licomont CaV 102 fine grain provides a lot of advantages for polyamide processing:- Nucleating effect- Lubricating effect- Excellent release properties- Dispersion of fillers and pigments- High thermal stability- Low volatility- Low discoloration of the polymer- Easy handling (reduction of dust fumes, better metering properties compared to powder)- Sufficient melt strength- No polymer degradation- Almost no negative influence on transparency- No negative influence on mechanical properties ( e.g. impact strength)- Effective at low concentrations (~ 0,2 - 0,3 %)



Flow improvement:

Release effects:

Dispersion:

Wetting effect:

Moisture barrier:

Surface improvement:

Licowax E

Licowax OP 0,5 - 2,0 %

Licowax S

ThermosettingsEffects, Products and Dosage


Public





[ % ] *)

Anti-tack agent: Ceridust 3620 0,5 - 1,0 (TPE‘s, EPDM) Ceridust 5551

Ceridust 3910Coupling agents/Adhesion promoter: Licocene PE MA 4351 0,3 - 5,0(i.e. Glass and natural-fiber Licocene PP MA 7452 TPreinforced Polyolefins) Licocene PP MA 6452 TP

Compatibilizer: Licocene PE MA 4351 1,0 - 5,0(i.e. PP/PA-Blends) Licocene PP MA 7452 TP

Licocene PP MA 6452 TP


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