T. Neuner; R. Josten; N. Sary, H. Stange - SGF[Kirk-Othmer Encyclopedia of Chemical Technology] Neutralization Coagulation Freeze roll Washing Drying Roping Chopping Coagulation Dewatering

New options with Baypren ® K. Varnhorn T. Neuner; R. Josten; N. Sary, H. Stange

Sveriges Gummitekniska Förenings vårkonferens

2 Baypren Kay Varnhorn Malmö, 2013-04-11

Introduction:

Lanxess offers a broad range of

Polychloroprene rubbers.

Baypren® is a commonly used

elastomer due to it´s multi-purpose

properties.

A new finishing line offers new

options and keep the establish

properties of Baypren ®.


Agenda

Introduction, Polychloroprene

New products by new technology

New finishing – new possibilities

Summary

New products in compound studies


b) linear, non-uniform configuration

c) linear, reactive endgroups

Cl

Cl

n

Cl

Cl

Cl

Cl

X

Cl Cl Cl Cl

X

n

R S S R

d) precrosslinked

R R

R

R RR

R RR

R R

R

R

e) sulphur modified

comonomer

a) linear, uniform configuration

variations in MW and MW-distribution

Ve

Cl Cl Cl Cl

n

determines Mooney viscosity

What is Polychlorprene - Baypren® ?

Low crystallization tendency

XD types

determines gel content

S types


Conventional Lanxess CR products

30

40

50

60

70

80

90

100

110

120

General purpose grades

non precrosslinked

116

226

110

126

112

230

210

211

216

Mo

on

ey v

isc

os

ity *

M L

1+

4/1

00

°C

Pre-

crosslinked

types

214

215

Sulphur modified

grades

510 611

114

711 712

110

Adhesive

grades Latex grades


The first new grades:

Baypren® 100 A VP

Baypren® 200 A VP

Baypren® 110 A VP

Baypren® 210 A VP

Baypren® 126 A VP

Baypren® 216 A VP

Baypren® 110 A VP

110 crystallization, slow

210 cryst. medium

110 Mooney range

100 low Mooney

110 mercaptane

116 xanthogene

disulfid

A VP new, trial product Improved

Performance

Alternative

Performance

Special

Performance

Three groups of new Baypren® ‘s Nomenclature

Reduced marching modus

Low Mooney

grades,

better

extrusion

performance

Improved vulcanization

characteristics with MTT


Standard and new process

„…in that connection, freeze roll isolation of very low Mooney viscosity polymers or fluid polymers is

difficult or virtually impossible.“

[Kirk-Othmer Encyclopedia of Chemical Technology]

Neutralization Coagulation

Freeze roll Washing Drying Roping Chopping

Coagulation Dewatering Drying Chopping

Standard process

New (alternative) process

Standard New

Lowest

Mooney

37 28

Resources consumption

Ammonia -

Steam

Water

Natural gas -

Electricity


Focus of the presentation

Baypren®

Standard Mooney

Low Mooney

Mercaptane Xantogene Disulfide

Standard Mooney

ETU MTT

ETU MTT ETU MTT

Fast cure regular cure


Low Mooney grade B200A VP - Extrusion

Baypren® 210 Standard 100 50

Baypren® 200A VP 100 50

REGAL® SRF / N772 30 30 30

EDENOR® C 18 98-100 0,5 0,5 0,5

Scorchguard® O 5,3 5,3 5,3

ZINKWEISS ROTSIEGEL® 5 5 5

Edenol® 888 8 8 8

MTT based Crosslinking x x x

0

5

10

15

20

25

30

35

40

45

0 100 200 300 400

Mo

one

y-V

isco

sity

[MU

]Time [s]

Mooney viscosity compound

B210

B210-B200 50/50

B200A VP


B210 - B200A VP – Extrusion Die swelling

Lower die swell for low

Mooney B200 compared to

B210

Significant reduced die

swell for blend of

B210: B200 (50:50)

Less nerve

Advantages in calandering


B210 - B200A VP – Extrusion Volume output

Higher Volume output for

low Mooney B200

compared to B210

Significant increased

output for blend of

B210: B200 (50:50)

Higher output, higher

production rate

Advantage also for semi-

finished products


B210 - B200A VP – Extrusion Energy consumption

Lower Energy consumption

for low Mooney B200

compared to B210

Significant reduced

Energy consumption for

blend of

B210: B200 (50:50)

Safe energy cost

Less compound

temperature


B210 - B200A VP Mechanical properties

Stress strain curve for

standard and low Mooney

material comparable

No lack of mechanical

properties if low Mooney

material is used


B210 - B200A VP Compression set - hardness

22

29

2427

3028

53 53 54

0

10

20

30

40

50

60

B210 Standard B200A VP B210-200

Co

mp

ressio

n s

et (%

)H

ard

ne

ss (

ShA

)

CS 70h /22°C

CS 70h /70°C

Hardness(ShA)

Compression set at

evaluated temperatures for

a blend of low Mooney/

standard material is

comparable to standard

Low Mooney material

slightly increase

compression set

No influence on hardness

with low Mooney material

and blend of thereof


B110 – B100A VP Injection moulding

Injection moulding

formulation possible

Investigate the influence of

low Mooney CR on flow

behaviour and filling

degree of injection

moulding cavity

BAYPREN® 110 100 70 50

BAYPREN® 100A VP 30 50

SCORCHGUARD® O 5,3 5,3 5,3

ZINKWEISS ROTSIEGEL 5 5 5

EDENOR® C 18 98-100 1 1 1

CORAX® N 330 15 15 15

REGAL® SRF / N772 35 35 35

EDENOL® 888 10 10 10

TUDALEN® 1849-TE 10 10 10

RHENOFIT® DDA-70 1,5 1,5 1,5

RHENOGRAN® MBTS-80 1,25 1,25 1,25

RHENOGRAN® MTT-80 1 1 1

Injection moulding formulation

MTT based curing system

Blends of Baypren ® 110 Standard (40 MU)

and Baypren ® 100A VP low Mooney (34 MU)


B110 – B100A VP Compound Mooney – Filling degree

Compound Mooney

decrease with the addition

of 30 and 50 parts low

Mooney CR

Degree of filling increase

with the addition of 30 and

50 parts low Mooney CR

Better filling of IM cavity


Summary I: Low Mooney grades

Summary low Mooney grades

Baypren ® A VP low Mooney grades offer low Mooney viscosity about 28 MU

Baypren ® A VP low Mooney grades have comparable mechanical properties to standard grades despite lower Mooney viscosity

Baypren ® A VP low Mooney grades offer

better flowing

lower die swell

higher out put

lower energy consumption

Baypren ® A VP low Mooney grades offer new compounding option combinations of high and low Mooney polymers e.g. B230 / B200

Baypren ® A VP low Mooney grades can support to optimize processing


Curatives ETU and MTT

Most vulcanization systems for CR contain either ETU or MTT as curative.

“US Environmental Protection Agency” (EPA) has classified ethylene thiourea as a group B2, probable human carcinogen.

Therefore ETU is restricted in many countries. Customers looking for alternatives like MTT.

ETU Ethylene thiourea (Imidazolidin-2-thion) Trade names (Rheinchemie) Rhenogran® ETU 80 Rhenocure® NPV/C former Vulkacit® NPV/V

MTT N-Methyl-thiazolidin-2-thion Trade names (Rheinchemie) Rhenogran® MTT 80, Rhenocure® CRV/LG former Vulkacit® CRV


B110 - MTT curing - MDR

Temperature and level of

curative influence the cure

rate (and the maximum

torque)

Baypren® 110 100 100 100

REGAL® SRF / N772 30 30 30

EDENOR® C 18 98-100 0,5 0,5 0,5



RHENOGRAN® MTT 0,5 0,5 1

Rhenofit® DDA 70 1,5 1,5 1,5

Variation in temperature and MTT level


B110 – B110A VP MTT curing – MDR – Part I

0

2

4

6

8

10

12

14

16

18

20

0 300 600 900 1200 1500 1800 2100 2400

S' [

dN

m]

Time [s]

B110 MTT 0,5 180°C

B110 MTT 0,5 160°C

B110 MTT 1,0 160°C

B110 (ref.) MTT 0,5 160°C

B110A VP (fast) MTT 0,5 160°C

B110A VP (regular) MTT 0,5 160°C

1 phr

New, regular

New, fast

180°C

Temperature and level of

curative influence the cure

rate (and the maximum

torque)

Cure rate of new B110A VP

(fast) only be achieved with

the new material not with

variation of temperature or

curative level

B110 MTT

0,5 180°C

B110 MTT

0,5 160°C

B110 MTT

1,0 160°C

B110 (Ref.) MTT

0,5 160°C

B110 (fast) MTT

0,5 160°C

B110 (regular) MTT

0,5 160°C

Polymer B110 B110 B110 B110 B110A VP fast B110A VP regular

RHENOGRAN® MTT-80 0,5 0,5 1 0,5 0,5 0,5

Rhenofit® DDA 1,5 1,5 1,5 - - -


B110 – B110A VP MTT curing – MDR - Part II 160°C

Baypren® 110 100

Baypren® 110A VP (fast) 100

Baypren® 110A VP (regular) 100



EDENOR® C 18 98-100 1 1 1

REGAL® SRF / N772 30 30 30

RHENOGRAN® MTT-80 1 1 1

MBTS® 80% 1,25 1,25 1,25

Rhenofit® DDA 1,5 1,5 1,5


Summary II: Improved MTT curing

Summary Improved MTT curing

Baypren ® A VP grades have improved cure rates for MTT

Curing curve is close to an ideal curing curve

Polymer variations are possible to further adapt the vulcanization rate of MTT curing


b) linear, non-uniform configuration

c) linear, reactive endgroups

Cl

Cl

n

Cl

Cl

Cl

Cl

X

Cl Cl Cl Cl

X

n

R S S R

d) precrosslinked

R R

R

R RR

R RR

R R

R

R

e) sulphur modified

comonomer

a) linear, uniform configuration

variations in MW and MW-distribution

Ve

Cl Cl Cl Cl

n

determines Mooney viscosity

XD grades from alternative finishing

Low crystallization tendency

XD types

determines gel content

S types


B216 – B216A VP Comparison

Baypren® 216 100

Baypren® 216A VP 100

REGAL® SRF / N772 30 30

EDENOR® C 18 98-100 0,5 0,5

Scorchguard® O 5,3 5,3

ZINKWEISS ROTSIEGEL 5 5

RHENOGRAN® ETU-80 0,5 0,5


B216 – B216A VP Scorch (120°C) – MDR 160°C


B216 – B216A VP Mechanical properties

Mooney scorch,

comparable to standard

MDR, lower final torque

maximum with ETU,

slightly improved marching

modulus

Stress strain curve

comparable


B216 – B216A VP Compression set - Hardness

Compression set and

hardness are on a similar

level for the evaluated

formulation


Summary III: XD grades General summary

Summary XD grades

XD grades obtained by new finishing offer a very similar material performance in terms

of vulcanization and mechanical properties

Summary Improved MTT curing

Baypren ® A VP grades have improved cure rates for MTT

Polymer variations are possible to further adapt the vulcanization rate of MTT curing

Summary low Mooney grades

Baypren ® A VP low Mooney grades have comparable mechanical properties to

standard grades despite lower Mooney viscosity

Baypren ® A VP low Mooney grades can support to optimize processing


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Documents

T. Neuner; R. Josten; N. Sary, H. Stange - SGF[Kirk-Othmer Encyclopedia of Chemical Technology] Neutralization Coagulation Freeze roll Washing Drying Roping Chopping Coagulation Dewatering