clariant waxes for pvc - general...better external release effect and fast geleation vs. fatty acid...

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Technical Marketing Waxes

22.07.2016

Clariant Waxes for PVC Processing GENERAL

Ing. Contreras Plata Enrique in representation of Clariant Division of Plastics additives

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22.07.2016

Clariant Waxes for PVC Processing CONTENT

PRODUCTS

APPLICATIONS

PERFORMANCE

BU Additives, Technical Marketing Waxes, 22.07.2016

Montan Waxes - Unique Lubricants for PVC Processing

Public, Clariant Waxes for PVC - General 3

Drop point

[°C]

Acid value

[mg KOH/g]

Licowax® E ~ 81 ~ 18

Licowax OP ~ 99 ~ 12

Licolub® WE 4 ~ 80 ~ 26

Licolub WM 31 ~ 74 ~ 12

Licolub WE 40 ~ 76 ~ 20

+

Ca

n

COOH = Fatty acid ~ C18

= CO-function (polar) COOH = Montanic acid ~ C30

® Trademark registered by Clariant in numerous countries


Polar Lubricants for PVC Processing

Drop point

[°C]

Viscosity

[mPa*s]

Acid value

[mg KOH/g]

Licowax PED 191 ~123 ~ 1800

(140 °C) ~ 17

Licolub H 12 /

Licowax PED 521 ~104

~ 350

(120 °C) ~ 17

Licowax C /

Licolub FA 1 veg. based ~ 142 - ~ 8

= Alkyl chain * Softening point

4 Public, Clariant Waxes for PVC - General


Non-Polar Lubricants for PVC Processing

Drop point

[°C]

Viscosity

[mPa*s]

Licowax PE 190 ~135* ~25.000

(140 °C)

Licowax PE 520 ~120 ~ 650 (140 °C)

Licolub H 4 ~111 < 10

(120 °C)

Licocene® PE 4201 ~ 128 ~ 60

(140 °C)

Licocene PP 6102 ~ 145 ~ 60

(170 °C)

= Alkyl chain * Softening point



Montan Waxes - Unique Lubricants for PVC Processing


Flow Promotion Broad lubricating

(internal and external)

Effects Benefits

High melt strength

Low volatility

High compatibility

Release Effect

Dimensional Stability

No Condensed Precipitates/no mold deposits

Surface Properties (smoothness, printability)

High Transparency

No plate out

High Vicat Value /Heat Distortion Temperature

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22.07.2016

Clariant Waxes for PVC Processing APPLICATIONS


Application & Effects of Clariant Waxes in PVC


Effects

Applications

Processing Surface

Shear dependent

viscosity control

Antisticking Slip Antiblock

1a) PVC Film Rigid

Calender

Sn-stab.; Ca/Zn-stab.

WE 4 / E / WM 31 WE 4 / E / WM 31 C/FA 1 veg.

Extrusion / Calendrette

Sn-stab.

WE 4 / E / WM 31 WE 4 / E / WM 31 C/FA 1 veg.

Extruded / blown film

Sn-stab.

E H 12 C/FA 1 veg.

Ca/Zn-stab. OP / E OP / E C/FA 1 veg.

1b) PVC Film Flexible WE 4 / H 12 C/FA 1 veg.

2) Non Food Applications WE 40 WE 40 C/FA 1 veg.

3) Injection Molding OP / E / WM 31 OP / E / WM 31


Effects of Clariant Waxes in PVC Extrusion


Effects

Applications

Processing Surface

Shear dependent

viscosity control

Antisticking / Gelation /

Machine load

Gloss

4) PVC Profile

Ca/Zn-stabilized WE 40 H 12

PED 191

PE 520

PP 6102 / PE 4201

PE 520

PP 6102 / PE 4201

OBS-stabilized WE 40 H 12

PED 191

PE 520

PP 6102 / PE 4201

PE 520

PP 6102 / PE 4201

5) PVC Pipe

Ca/Zn-stabilized H 12 PE 520

PP 6102 / PE 4201

PE 520

PP 6102 / PE 4201

Organic based

Stabilizer

H 12 PE 520

PP 6102 / PE 4201

PE 520

PP 6102 / PE 4201

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22.07.2016

Clariant Waxes for PVC Processing PERFORMANCE


Volatility (TGA) of Lubricants for PVC Lowest volatility with montanic esters compared to stearic esters


0

2

4

6

8

10

12

14

16

18

20

180 200 220 240 260 280

Vo

tality

[%

]

Temperatur [°C]

GMS (FAE)

FACE / FAE

FACE

Licowax E

Licolub WE 4

Licowax OP

Licolub WE 40

Weight: 500 mg

Surface: 3 cm²

Heating rate: 120 K/h

Atmosphere: 1 l air/min,


Influence of Lubricants on Melt Strength Highest melt Strength with montanic esters compared to stearic esters


0

30

60

90

120

150

180

210

0 2 4 6 8 10 12 14

F [

cN

]

v [cm/s]

Tensile Stress Capacity of a Ca/Zn-Stabilized PVC Melt

Licolub WE 4

Licolub WE 40

Licowax E

FAE

FACE

Göttfert ®Rheotens

(screw Ø 30 mm; gradient 4:2; die Ø 5 mm

temperature: 140/160/175/190 °C

acceleration 6 cm/s2)

Basic formulation:

S-PVC, k value 60 100,0 parts

Ca-12-Hydroxy Stearate 0,3 phr

Zn-Stearate 0,1 phr

Epoxidized Soyabean Oil 3,0 phr

ß-Diketone 0,3 phr

Lubricant 0,5 phr


Vicat Softening Point of Different Lubricants Highest Vicat values with Licowax E

74

75

76

77

78

79

80

without Glycerol dioleate Mixture of fattyacid complexesters (Gl 2)

Licowax E Licolub WM 31

Formulation:

Vinnolit S 3160 100 phr

Octyl tin stabilizer 1,5 phr

Processing Aid (Arcylate) 1 phr

Test product 1 phr

Parameters:

(according to DIN EN ISO 306)

Initial temp.: 30 °C

Heating rate: 50 K/h

Method: B (50 N)

VN 107078-080


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22.07.2016

Clariant Waxes for PVC Processing FILM COMPOUNDS


Release Effect in Sn-Stabilized PVC Film Compound

Licolub WM 31 shows excellent external lubrication and anti-sticking


0

5

10

15

20

25

30

800 900 1000 1100 1200 1300 1400

Sti

ck

ing

po

we

r

Time [sec.]

Licowax E

Licolub WE 4

Licolub WM 31

Formulation:

S-PVC, k value 60 100 phr

Sn-Octyl mercaptide 1,5 phr

MBS Impact modifier 5,0 phr

PMMA Processing aid 1,0 phr

GDO 0,3 phr

Lubricant 0,3 phr

Collin Two Roll Mill

220 g, 195 °C, 15/20 rpm


0

5

10

15

20

25

30

0 200 400 600 800 1000 1200 1400

Sti

ck

ing

po

we

r

Time [sec.] FACE / FAE

Licowax E

Release Effect in Sn-Stabilized PVC Film Compound

Licowax E show excellent anti-sticking


Formulation:





GDO 0,3 phr

Lubricant 0,3 phr


220 g, 195 °C, 15/20 rpm


17

Transparency in Sn-Stabilized PVC Film Compound

Higher transparency with all montanic acid esters vs. fatty acid esters

76

78

80

82

84

86

88

90

Licowax E Licolub WE 4 Licolub WM 31 FACE/FAE

Tra

ns

pa

ren

cy [

%]

0,5 mm 2 mm

Formulation:

100,0 parts M-PVC, k value 60

8,0 phr MBS Impact modifier

1,2 phr PMMA Processing aid

1,2 phr Sn-Octyl mercaptide

0,5 phr GDO

0,3 phr Lubricant

0,5 and 2 mm pressed plates


Release Effect and Gelation in Sn-Stab. PVC Film Compound

Better external release effect and fast geleation vs. fatty acid ester mix


0

4

8

12

16

20

FACE/FAE/Ca-Soap

Licowax OP

Tim

e t

o s

tic

kin

g [

min

.]

0

30

60

90

120

150

FACE/FAE/Ca-Soap

Licowax OP

Fu

sio

n t

ime

[s

ec

.]

Haake kneader (40 rpm, 140°C, 63 g)

Basic formulation:

S-PVC, k value 60 100,0 parts




GDO 0,6 phr

External lubricant 0,5 phr

Two roll mill (190 °C, 16,7/20 rpm)


Release Effect in Ca/Zn-Stabilized PVC Film Compound

Better anti-sticking/external lubrication of montanic esters vs. FACE/FAE


Formulation:


Ca/Zn Stabilizer 3,0 phr



GDO 0,3 phr

Lubricant 0,3 phr


220 g, 195 °C, 15/20 rpm

0

5

10

15

20

25

30

800 1000 1200 1400 1600

Sti

ck

ing

po

we

r

time [sec.]

Licowax E

FACE/FAE

Licolub WE 4


Clariant Waxes for PVC Processing Film Compounds - Summary

– All Montan Waxes provide better anti-sticking performance than fatty

acid complex ester mixtures

– Licolub WE 4 performs best

– Transparency is excellent


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22.07.2016

Clariant Waxes for PVC Processing PROFILE / PIPES

COMPOUNDS


PVC Pipes - Replacement of FT Paraffins, Ca/Zn-Stabilized

Lower pressure and torque vs. FT paraffins…


0

50

100

150

200

250

300

350

400

450

500

Pressure p1 Pressure p3 Pressure p4 Pressure p5

Pre

ss

ure

[b

ar]

Pressure along the barrel

0,3 / 0,05 phr FT80/FT1

0,35 phr Licocene PE 4201

0,35 phr Licocene PP 6102

Formulation: phr

S-PVC, k value 68 100,0

CaCO3 (90T) 15,0

Ca/Zn Core stabilizer 1,18

Test products 0,35

Extrusion Parameters:

Single Screw Laboratory Extruder: Collin E 30M, L/D= 25/1;

Round section Die; Temp.: 170-180-190-195-195 °C

Die : 195-195 °C; Speed: n= 60 rpm


PVC Pipes - Replacement of FT Paraffins, Ca/Zn-Stabilized

…and lower energy consumption of the extruder with Licocene


Formulation: phr

S-PVC, k value 68 100,0

CaCO3 (90T) 15,0

Ca/Zn Core stabilizer 1,18

Test products 0,35

Extrusion Parameters:

Single Screw Laboratory Extruder: Collin E 30M, L/D= 25/1;

Round section Die; Temp.: 170-180-190-195-195 °C

Die : 195-195 °C; Speed: n= 60/80/90 rpm

0.06

0.065

0.07

0.075

0.08

0.085

0.09

0.095

0.1

0.105

50 60 70 80 90 100

E-v

alu

e [

KW

h/k

g]

Screw Speed [1/min]

Energy consumption at different screw speeds

0,3 / 0,05 phr C80/H1




PVC Pipes - Replacement of Paraffins, Sn-Stabilized

Lower pressure with lower dosage of Licocene PP 6102 …

0

50

100

150

200

250

300

p1 p2 p3 p4 p5

Pre

ssu

re [b

ar]


1 phr Hydrocarbon wax 1 phr Licocene PP 6102

1 phr Licocene PE 4201 0,7 phr Licocene PP 6102

S-PVC k-value 57 100,0 phr

Sn-butyl-stabilizer 1,3 phr

TiO2 8,0 phr

Chalk 6,0 phr

Impact modifier 5,0 phr

Processing aid 1,0 phr

Ox. PE-wax 0,5 phr

Test products 1,0 – 0,7


Extrusiometer E 30 M

D= 30 mm, 25 L/D

n= 30 rpm,

180-185-190-200-210°C

round-section die: 215°C


PVC Pipes - Replacement of Paraffins, Sn-Stabilized

… and lower energy consumption/higher output

0

0.01

0.02

0.03

0.04

0.05

0

2

4

6

8

10

E-v

alu

e [

kW

h/k

g]

Ou

tpu

t [k

g/h

]

Energy consumption and Output

Output

E-value


Extrusiometer E 30 M

D= 30 mm, 25 L/D

n= 30 rpm,

180-185-190-200-210°C

round-section die: 215°C


PVC Profiles [Ca/Zn] – Metallocene vs. Standard PO Waxes

Lower pressure and torque with Licocene …


0

50

100

150

200

250

300

350

p1 p2 p3 p4 p5

Pre

ss

ure

[b

ar]


0,3 phr standard PE wax


0,2 phrLicocene PP 6102



Formulation:

S-PVC k-value 68 100 phr

Ca/Zn-Stabilizer compound 2,4 phr

Impact modifier 7 phr

Processing aid 1 phr

TiO2 4 phr

Chalk 6 phr

Di stearyl phthalate 0,5 phr

Calcium stearate 0,5 phr

Oxidized PE-wax 0,2 phr

Test product 0,2 - 0,3 phr

Extrusiometer E 30 M D= 30, 25 L/D, n= 30 rpm, Temp: 180-185-190-195-195°C, round-section die:195°C


PVC Profiles [Ca/Zn] – Metallocene vs. Standard PO Waxes

… and lower torque + similar output vs. standard PE wax


Formulation:





TiO2 4 phr

Chalk 6 phr


Calcium stearate 0,5 phr


Test product 0,2 - 0,3 phr

40

45

50

55

60

65

70

75

20

25

30

35

40

45

standard PEwax

Licocene PP6102

Licocene PE4201

Licocene PP6102

Licocene PE4201

To

rqu

e [

%]

Ou

tpu

t [k

g/h

]

Output

Torque

Dosage: 0,3 phr Dosage: 0,2 phr

Weber DS 48 190, D= 48 mm, 17 L/D, n= 25 rpm, Temperature: 190-194-195°C, profile die: 195°C


PVC Profiles [Ca/Zn] – Licolub WE 40 Performance

… and lower energy consumption with WE 40!


Formulation:





TiO2 4 phr

Chalk 5 phr



PE Wax 0,20 phr

Test product 0,3 phr

Weber CE 3Z, D= 52 – 24 mm, n= 30 rpm, Temperature: 185-185-185-185°C, flat die: 190 °C (VN99498ff)

0.08

0.085

0.09

0.095

0.1

without 30 rpm without 45 rpm Licolub WE 4030 rpm

Licolub WE 4045 rpm

e -

Va

lue

[k

Wh

/kg

]

Energy Consumption / Twin Screw


PVC Profiles [Ca/Zn] – Licolub WE 40 Performance

Higher output and faster gelation vs. fatty acid complex ester


0

2

4

6

8

10

12

14

16

18

0

50

100

150

200

250

300

0,3 phr FACE+ 0,2 phr Licowax PE 520

0,3 phr Licolub WE 40+ 0,2 phr Licowax PE 520

Fu

sio

n t

ime

[m

in]

Ou

tpu

t [g

/min

]

Output

Fusion timeExtrusiometer

(70-180-190-195°C,

screw 5/2, die 75/5, 60 rpm)

Basic formulation:

S-PVC, k value 64, impact mod, 100,0 phr

Ca-Stearate 0,5 phr

Zn-Stearate 1,0 phr

Hydrotalcit 1,0 phr

ß-Diketone 0,6 phr

Di-Trimethylol Propane 0,5 phr

Phenolic Antioxidant 0,1 phr

Brabender® Plastogram

(35 g, 150°C, 40 rpm)


Clariant Waxes for PVC Processing Profile / Pipes Compounds - Summary – Pipes:

Licocene PP 6102 is an excellent FT replacement with

room for dosage reduction and plate out minimizing

– Profiles:

- Licocene PP 6102 performs outstanding compared to standard PE

waxes with saving opportunities

- Licolub WE 40 shows lower energy consumption, fast gelation

combined with high Vicat Softening Temperature resp. Heat Distortion

Temperature.


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22.07.2016

Clariant Waxes for PVC Processing BACKUP

clariant waxes for pvc - general...better external release effect and fast geleation vs. fatty acid...

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