modern rubber additives to avoid hazardous substances

8/10/2019 Modern Rubber Additives to Avoid Hazardous Substances

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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)






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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)






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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)



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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.)



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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


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)







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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



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Mooney Scorch at 135 C


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



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Dithiophosphates seem to perform comparable to DPG as accelera

Influence on modulus of different activators


0

2

4

6

8

10

12

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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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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.

modern rubber additives to avoid hazardous substances

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