Modern Rubber Additives To Avoid Hazardous Substances

Modern rubber additives to avoid hazardous substances
Harald Kleinknecht, Rhein Chemie Rheinau GmbH

Automotive Days Poland,
October 27-28, 2011
Modern rubber additives to avoid hazardous

substances Agenda
Introduction
Regulations
Critical products decomposition products
Possibilities to avoid hazardous products
Example 1: save handling and efficient production by Rhenogran
Advantage of polymerbound chemicals
Example 2: replacement of secondary amines, nitrosamine generating accelerators
Carbamat and Thiurams in EPDM compound
Example 3: replacement of Guanidines
DPG in silica tread compounds
DOTG in AEM compounds
Summary
Goal: safer production and safer rubber products
Regulations systems
Substances
Listing
Health and safety regulation
Working conditions
Transportation
Products
Consumer
Environment
3
Rhenogran classification, labeling
Hazardous
material
Dangerous
good
ADR 2009
REACh
Producer / importer
Knowledge about material
specific data
classification acc. GHS
* Global Harmonizing System

4
EU-GHS*
Risk =
classification acc. GHS x
exposition
Risk Management
User
Knowledge about
application
exposition
Regulation systems examples

Listing e.g.
all ingredients are on the following inventories or are exempted from listing:
REACh, TSCA, AICS, DSL, ENCS (JP), KECI (KR), PICCS (PH), INV (CN),
NZIOC, CH INV
Health and safety regulations H&S
by governments, organizations, companies
Regulations e.g.: (EC) No 1907/2006 MSDS
Classifications e.g.: GHS, EC:-directives 19999/45/EC Symbols,
R-Phrases, S-Phrases
MAK (max working space concentration) by DFG
GHS Global Harmonizing System (UN, world-Transport)
GADSL Global Automotive Declarable Substance List
Automotive industry
Regulation of companies
Many big companies have often their own H&S regulations in addition
5
Product Portfolio
Carbamates (1) CuDMC, ZBEC, ZDMC(2), ZDBC, ZDEC, ZPMDC, ZEPC, TEDC
Guanidines (4) DPG, DOTG, OTBG
Mercaptobenzothiazoles MBT MBTS
Sulfenamides (1) CBS, DCBS, MBS, TBBS, DIBS
Thiurams (1) DPTT, TBzTD, TETD, TIBTD, TMTD, TMTM
Thioureas ETU (2), DPTU (3), TBTU (1)(2)
Sulfurdonors CLD, DTDM (1), OTOS (1)(3), SDT, TBZTD
Curing agents ETU, MTT, MPBM (HVA-2)
Heavy metals (2) CdO, PbO, PB3O4 and others
(1) = Nitrosamine generating (3) = In toxic or canc. discussion

(2) = Toxic / cancerogen
6
(4) = Toxic cancer decomp. products
Product Portfolio Replacement (1/2)

Carbamates (1)
Dithophosphates
ZDBP, ZBOP, ZDT, ZAT, ZADT, XLA
Thiureas (1)(2)(3)
Zincamindithiophosphates
ZAT, ZADT, XLA, Geniplex (ZnNCO)
Guanidines (3)(4)
Dithiophosphates
ADT, SDT ZAT, ZADT,
XLA, HPCA

7
Product Portfolio Replacement (2/2)

Thiurams (1)
Dithiophosphates
SDT, ZBOP, ZDT, ZAT, ZADT, XLA
Can be used in all sulfur cured polymers
Sulfurdonors (1,3)
Dithiophosphate (SDT)
Caprolactamdisulfid (CLD)
Can be used in all sulfur cured polymers
Curing agents
ETU lead-free systems based on:

MTT, BCA > CR, Butyl
Triazine
> ECO, CR
Heavy metals (2)
Mg-talcid, MgO, HPCA > ECO, CR, CPE

8
Example 1: secure Handling with Rhenogran
Better dispersion
Easier processability
Good compatibility
Best storage stability
Automatic weighing
Clean working place
Easier disposal of paper bags /
reduced loss of remaining material
Safety features, e.g. no dusting
Reduction of risk during handling and

transport
Typ
Stoff
Label R-Stze
Labeling of polymerbound products

(50% -80% ingredient)
Xi, N
Xi, N
C, N
43-51/53
36/38-51/53
34-51/53
C, N
22-35-50/53
ZAT
C, N
21/22-34-51/53
ZBOP
ZDDT
ZDT
ZDEC
Xi, N
Xi, N
N
Xn, N
ZBEC
ZDBC
ZDMC
Xi, N
T+, N
ZEPC
HMDC
ZMBT
Xi
Xi
Xi
36-51/53
36-51/53
51/53
22-36/37/38-4350/53
53
36/37/38-43-50/53
22-26-37-41-4348/22-50/53
36-53
36-37-38
43
SDT
TP
ZABOP (dry
liquid)
ZADT (dry
Dithiophosphate liquid)
Carbamate
10
Xi, R43
Xi, R43
Xi, R43
Xi, R43
Example 2: Dithiophosphate
Thiuram and Carbamat accelerator replacement
Zn-dithiophosphates
Rhenogran TP-50
Rhenocure TP/S
Vocol ZBPD pdr
Specialities
Rhenogran CUT-50
Copper salt
Rhenogran ZAT-70
Rhenogran XLA-60
Rhenogran ZADT-50
Amine Activated DTP
Rhenogran ZBOP-50
Rhenocure ZBOP/S
Rhenogran ZDT-50
Rhenocure ZDT/S
Rhenogran SDT-50
Rhenocure SDT/S
Sulfur donor
Accelerating Effect
11
Dithioates additives for rubber compounds

Accelerator replacement
Dithiophosphates/
Sulphenamides
Modulus values
Dithiophosphates / Thiazoles
Dithiophosphates
Type of sulphenamide or
influence of Guanidines
Cure time
12
Dithiophosphates additives for rubber

compounds EPDM compound nitrosaminfree
Recipe
13
EPDM-Batch
100
100
100
100
100
100
100
100
100
100
Rhenogran S-80
Rhenogran ZDBC-80
Rhenogran TMTD-80
Rhenogran TDEC-70
Rhenogran MBT-80
Rhenogran ZBEC-70
Rhenoslab OBSH-75
g
g
g
g
g
g
g
0,18
0,25
0,13
0,08
0,41
0,22
0,07
0,2
0,2
0,2
0,2
0,2
0,2
0,2
0,2
0,2
0,42
0,22
0,07
0,42
0,22
0,07
0,07
0,07
0,07
0,07
Rhenogran SDT-50
Rhenogran AP 7
Rhenogran CBS-80
Rhenogran ZAT-70
Rhenogran ZABOP-50
Rhneogran ZBOP-50
Rhenogran Geniplex 70
Rhenogran CLD-80
g
g
g
g
g
g
g
g
0,3
0,3
0,3
0,4
0,3
0,4
0,5
0,4
0,3
0,3
0,3
0,2
0,2
0,3
0,2
0,07
0,07
0,07
0,3
0,5
0,3
0,5
0,3
0,3
0,5
0,3
0,2
0,2
0,4
0,3
0,3
0,3
0,2
0,2
0,3
0,2
0,2
0,3
0,2
0,2

compounds EPDM compound nitrosaminfree
Rheometer curves 195C / 3 min.
GEL 30161
Gttfert 195C
0,70
Batch 1
Batch 2
0,60
Batch 3
torque [Nm]
0,50
Batch 4
Batch 5
0,40
Batch 6
0,30
Batch 7
Batch 8
0,20
Batch 9
Batch 10
0,10
Batch 11
0,00
Batch 12
2
time [min]
14

compounds Summary
Form short sulfur crosslinks (mainly S1 and S2) suitable for
increasing under-hood temperatures
high dynamic loads
Give low compression sets and heat resistant vulcanizates
R O
Accelerator speed is widely adjustable
P
R O
Easy dispersible liquid accelerators

allow high dosages
show no blooming
Combinations with carbamates, thiurams, thiazoles, guanidines,

sulfenamides, retarders and others are possible
Synergetic effects with sulfenamides and thiazoles
Premixed combination can be prepared
Rhenogran
Dithiophosphates
Replacement of critical accelerator types, e.g.

carbamates, thiurams, thiazoles, guanidines, thioureas, OTOS and
others are possible
Do not form toxic N-nitrosamines
15

Replacement of Guanidines
Product portfolio replacement of Guanidines

(1/4)
Guanidines
Best replacement product has to be selected mainly depending on:
Polymer: e.g. AEM, ACM, CR, EPDM, NR, SBR, HNBR, NBR
Function as: Co-Accelerator, filler activator
Application: Tire (Silica tread), Technical Rubber Goods (TRG)
17

(2/4)
Di-o-tolyl guanidine (DOTG)
Di-phenyl guanidine (DPG)
Production of rubber articles for automobile

industry (tires, seals, hoses etc.)
18
Aromatic Amines:
Aniline and O-Toluidine

(3/4)
Aniline release, headspace GC/MS
Aniline
Analysis of aniline by headspace GC/MS (80C / 25 min)

Aniline already in significant amounts after 1st mixing step
Amount increasing, highest after vulcanization
Carbon Black compounds reveal higher amount of aniline release
Adsorption of aniline on silica surface?
19

(4/4)
DPG (3) > Tire (Silica tread)
curing and filler activator
aniline (3)
NR, SBR, BR
Dithiophosphates
SDT, ZDT, ZAT, ZADT, XLA: ADT
DPG (3) > TRG

Profiles, molded articles
curing activator
EPDM, AEM, ACM, CR, EPDM, NR, SBR, NBR

Zink(amin)dithiophosphates Geniplex(ZnNCO)
ZAT, ZADT, XLA, HPCA
DOTG (4) > TRG

Hoses, molded articles
curing activator with HMDC
Orthotoluidine (T+,4)
AEM, ACM, CR, HNBRX a.o.

Zink(amin)dithiophosphates
XLA, HPCA (Aminecomplex), ZDT, SDT

20

Example of DPG replacements in SBR-BR
Example of DPG replacements in SBR-BR (1/3)

Recipes
Ingredient
Control
No DPG
DTP 1.0
DBU/S
Arginin 1.0
Arginin 2.0
Lysin
VSL 5025-2
96.0
CB 24
30.0
Ultrasil GR 7000
80.0
Vivatec 500
10.0
TMQ
2.0
6PPD
2.0
Antilux 654
1.0
Stearic acid
2.0
ZnO WS
3.0
Si 69
6.4
Rhenogran S-80
1.5
Rhenogran CBS-80
2.0
Rhenogran DPG-80
2.5
Rhenogran SDT-50
Rhenogran XLA-60
L-Arginin
L-Lysin Hydrochloride
22
1.0
0.7
1.0
2.0
2.0

Mooney Scorch at 135 C
100
Mooney Viscosity [MU]
90
80
70
60
50
Control
XLA
DBU/S
Lysin
40
No DPG
Arginin 1.0
DTP 1.0
Arginin 2.0
30
0
23
10
20
30
Time [min]
40
50

Influence on modulus of different activators
14
Modulus 100
Modulus 300
12
Modulus [MPa]
10
8
6
4
2
0
Control
No
DPG
DTP
1.0
XLA Arginin Arginin

DBU/S
1.0
2.0
Lysin
Dithiophosphates seem to perform comparable to DPG as accelerator
24

Example 3: Rhenogran for AEM, ACM compounds
DOTG replacement
Reactions products at the vulcanization with

DOTG
After vulcanization
26
After post cure
AEM recipes
[phr]
27
AEM
CB
Stearic acid
Aflux 18
Procesing aid
Rhenogran ZDDT-50
Antioxidant
Plasticizer
100
80
2.0
0.5
1.0
100
80
2.0
0.5
1.0
100
80
2.0
0.5
1.0
100
80
2.0
0.5
2.0
8.0
2.0
8.0
2.0
8.0
2.0
2.0
8.0
Rhenogran HMDC-70/AEM
Rhenogran DOTG-70
Alternative
Rhenogran XLA-60
2.3
5.0
2.3
2.3
2.3
4.0
4.0
2.0
AEM compound
MDR 180C
28
Summary
For many hazardous substances exit, valid, useful alternatives
Rhenogran special polymerbound for efficient safer curing products
Dithiophosphate base for nitrosaminfree curing systems
Rhenogran-Triazine, Rhenogran HPCA base for ETU-lead-free curing systems
(Amin) Dithiophates, Rhenogran XLA, Rhenogran HPCA based Guanidinefree
curing systems
The goal
is possible
29
Safer production safer rubber products

for humans and environment
Thank you
Further questions?
30
31
Safe harbour statement
This information and our technical advice - whether verbal, in writing or by way of trials are
given in good faith but without warranty, and this also applies where proprietary rights of third
parties are involved. Our advice does not release you from the obligation to check its validity and
to test our products as to their suitability or the intended processes and uses. The application,
use and processing of our products and the products manufactured by you on the basis of our
technical advice are beyond our control and, therefore, entirely your own responsibility. Our
products are sold in accordance with the current version of our General Conditions of Sale and
Delivery.
32

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Modern rubber additives to avoid hazardous substances

Harald Kleinknecht, Rhein Chemie Rheinau GmbH