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Harald Kleinknecht, Rhein Chemie Rheinau GmbH
Automotive Days Poland,
October 27-28, 2011
Modern rubber additives to avoid hazardous su
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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 accelerato 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
Modern rubber additives to avoid hazardoussubstancesAgenda
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Regulations systems
Substances
Listing
Health and safety regulation
Working conditions
Transportation
Products
Consumer
Environment
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Rhenogran classification, labeling
Hazardous
material
Dangerou
good
REACh EU-GHS*
ADR 20
Risk Management
Risk =
classification acc. GHS xexposition
Producer / importer
Knowledge about material
specific data
classification acc. GHS
* Global Harmonizing System
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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
Regulation systems examples
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Carbamates (1) CuDMC, ZBEC, ZDMC(2), ZDBC, ZDEC, ZPMDC, ZEPC, TED
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
Product Portfolio
(3) = In toxic or canc. discussion
(4) = Toxic cancer decomp. products
(1) = Nitrosamine generating
(2) = Toxic / cancerogen
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Carbamates (1) Dithophosphates
ZDBP, ZBOP, ZDT, ZAT, ZADT, XLA
Thiureas (1)(2)(3) ZincamindithiophosphatesZAT, ZADT, XLA, Geniplex (ZnNCO)
Guanidines (3)(4) Dithiophosphates
ADT, SDT ZAT, ZADT,
XLA, HPCA
Product Portfolio Replacement (1/2)
(3) = In toxic or canc. discussion
(4) = Toxic cancer decomp. products
(1) = Nitrosamine generating
(2) = Toxic / cancerogen
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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
Product Portfolio Replacement (2/2)
(3) = In toxic or canc. discussion
(4) = Toxic cancer decomp. products
(1) = Nitrosamine generating
(2) = Toxic / cancerogen
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Reduction of risk during handling andtransport
SDT Xi, N 43-51/53 -
TP Xi, N 36/38-51/53 -
ZABOP (dryliquid)
C, N 34-51/53 -
ZADT (dry
liquid)
C, N 22-35-50/53 -
ZAT C, N 21/22-34-51/53 -
ZBOP Xi, N 36-51/53 -ZDDT Xi, N 36-51/53 -
ZDT N 51/53 -
ZDEC Xn, N 22-36/37/38-43-
50/53
Xi, R43
ZBEC - 53 -
ZDBC Xi, N 36/37/38-43-50/53 Xi, R43
ZDMC T+, N 22-26-37-41-43-
48/22-50/53
Xi, R43
ZEPC Xi 36-53 -
HMDC Xi 36-37-38 -
ZMBT Xi 43 Xi, R43
Dithiophosphate
Carbamate
Labeling of polymerbound products
(50%-80% ingredient)
Typ Stoff Label R-Stze
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Example 2: DithiophosphateThiuram and Carbamat accelerator replacement
Accelerating Effect
Zn-dithiophosphates
Rhenogran TP-50
Rhenocure TP/S
Vocol ZBPD pdr
Rhenogran ZBOP-50
Rhenocure ZBOP/S
Rhenogran ZDT-50
Rhenocure ZDT/S
Specialities
Rhenogran
Copper s
Rhenogran
Rhenogran
Rhenogran
Amine Ac
RhenogranRhenocure
Sulfur don
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Dithioates additives for rubber compounds Accelerator replacement
DithiophosphatesDithiophosphates/
Sulphenamides
Dithiophosphates / Thiazoles
Type of sulphenamide or
influence of Guanidines
Cure time
Modulusvalues
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Dithiophosphates additives for rubbercompounds EPDM compound nitrosaminfree
Recipe
EPDM-Batch g 100 100 100 100 100 100 100 100 1
Rhenogran S-80 g 0,18 0,2 0,2 0,2 0,2 0,2 0,2 0,2 0
Rhenogran ZDBC-80 g 0,25Rhenogran TMTD-80 g 0,13
Rhenogran TDEC-70 g 0,08
Rhenogran MBT-80 g 0,41 0,42 0,42
Rhenogran ZBEC-70 g 0,22 0,22 0,22
Rhenoslab OBSH-75 g 0,07 0,07 0,07 0,07 0,07 0,07 0,07 0,07 0
Rhenogran SDT-50 g 0,3 0,3 0,3 0,3 0,3 0,3 0
Rhenogran AP 7 g 0,5 0,5 0,5 0,4 0,4 0
Rhenogran CBS-80 g 0,3 0,3 0,2 0,2 0,3
Rhenogran ZAT-70 g 0,3
Rhenogran ZABOP-50 g 0,3 0,3 0,3 0,3 0
Rhneogran ZBOP-50 g 0,3
Rhenogran Geniplex 70 g 0,2 0,2 0,2 0,2 0,2 0,2 0,2
Rhenogran CLD-80 g 0,3
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Dithiophosphates additives for rubbercompounds EPDM compound nitrosaminfree
Rheometer curves 195C / 3 min.
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0 1 1 2 2 3 3 4
torque[Nm
]
time [min]
Gttfert 195C
GEL 30161
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Dithiophosphates additives for rubbercompounds Summary
Rhenogran
Dithiophosphates
P
S
S
O
O
R
R
Form short sulfur crosslinks (mainly S1 and S2) suitable
increasing under-hood temperatures
high dynamic loads
Give low compression sets and heat resistant vulcaniza
Easy dispersible liquid accelerators
allow high dosages
show no blooming
Accelerator speed is widely adjustable
Combinations with carbamates, thiurams, thiazoles, gua
sulfenamides, retarders and others are possible
Synergetic effects with sulfenamides and thiazoles
Premixed combination can be prepared
Replacement of critical accelerator types, e.g.
carbamates, thiurams, thiazoles, guanidines, thiourea
others are possible
Do not form toxic N-nitrosamines
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Modern rubber additives to avoid hazardous s
Replacement of Guanidines
P d t tf li l t f G idi
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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)
Product portfolio replacement of Guanidines(1/4)
P d t tf li l t f G idi
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Product portfolio replacement of Guanidines(2/4)
Di-o-tolyl guanidine (DOTG)
Di-phenyl gua
Aromatic Amines
Aniline and O-Tolui
Production of rubber articles for automobile
industry (tires, seals, hoses etc.)
P d t tf li l t f G idi
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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?
Aniline release, headspace GC/MS
Aniline
Product portfolio replacement of Guanidines(3/4)
Prod ct portfolio replacement of G anidines
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DPG (3) > Tire (Silica tread) NR, SBR, BR
curing and filler activator Dithiophosphates
aniline (3) SDT, ZDT, ZAT, ZADT, XLA: ADT
DPG (3) > TRG EPDM, AEM, ACM, CR, EPDM, NR, SBR
Profiles, molded articles Zink(amin)dithiophosphates Geniplex(ZnN
curing activator ZAT, ZADT, XLA, HPCA
DOTG (4) > TRG AEM, ACM, CR, HNBRX a.o.
Hoses, molded articles Zink(amin)dithiophosphates
curing activator with HMDC XLA, HPCA (Aminecomplex), ZDT, SDT
Orthotoluidine (T+,4)
(3) = In toxic or canc. discussion
(4) = Toxic cancer decomp. products
(1) = Nitrosamine generating
(2) = Toxic / cancerogen
Product portfolio replacement of Guanidines(4/4)
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Modern rubber additives to avoid hazardous s
Example of DPG replacements in SBR
Example of DPG replacements in SBR BR (1/3)
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Example of DPG replacements in SBR-BR (1/3)
Recipes
Ingredient Control No DPG DTP 1.0 DBU/S Arginin 1.0 Arginin
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 1.0
Rhenogran XLA-60 0.7
L-Arginin 1.0
L-Lysin Hydrochloride
Example of DPG replacements in SBR BR (2/3)
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Mooney Scorch at 135 C
Example of DPG replacements in SBR-BR (2/3)
30
40
50
60
70
80
90
100
0 10 20 30 40 50
Time [min]
MooneyViscosity[MU
]
Control No DPG DTP 1.0
DBU/S Arginin 1.0 Arginin 2.0
Lysin
XLA
Example of DPG replacements in SBR BR (3/3)
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Dithiophosphates seem to perform comparable to DPG as accelera
Influence on modulus of different activators
Example of DPG replacements in SBR-BR (3/3)
0
2
4
6
8
10
12
14
Control No
DPG
DTP
1.0
DBU/S Arginin
1.0
Arginin
2.0
Lysin
Mo
dulus[MPa]
Modulus 100 Modulus 300
XLA
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Modern rubber additives to avoid hazardous s
Example 3: Rhenogran for AEM, ACM com
DOTG replacement
Reactions products at the vulcanization with
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Reactions products at the vulcanization withDOTG
After vulcanization After post cure
AEM recipes
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AEM recipes
AEM 100 100 100 100
CB 80 80 80 80
Stearic acid 2.0 2.0 2.0 2.0
Aflux 18 0.5 0.5 0.5 0.5
Procesing aid 1.0 1.0 1.0
Rhenogran ZDDT-50 2.0
Antioxidant 2.0 2.0 2.0 2.0Plasticizer 8.0 8.0 8.0 8.0
Rhenogran HMDC-70/AEM 2.3 2.3 2.3 2.3
Rhenogran DOTG-70 5.0Alternative 2.0
Rhenogran XLA-60 4.0 4.0
[phr]
AEM compound
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AEM compound
MDR 180C
Summary
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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 sy
(Amin) Dithiophates, Rhenogran XLA, Rhenogran HPCA based Guanidi
curing systems
The goal
is possible
Safer production safer rubber products
for humans and environment
Thank you
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Thank youFurther questions?
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Safe harbour statement
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This information and our technical advice - whether verbal, in writing or by way of tr
given in good faith but without warranty, and this also applies where proprietary rig
parties are involved. Our advice does not release you from the obligation to check
to test our products as to their suitability or the intended processes and uses. The a
use and processing of our products and the products manufactured by you on the b
technical advice are beyond our control and, therefore, entirely your own responsib
products are sold in accordance with the current version of our General Conditions
Delivery.