Rubber Chemicals & Specialties

From
FINORCHEM LIMITED
 FINORCHEM UNIT-I PRODUCTS

PRODUCTS
> 20 KT
SULPHUR
DONOR
ANTIOXIDANTS
• ACMECURE DTDM
& ANTIDEGRADANTS

ACCELERATORS

AUXILIARIES STAINING
OTHERS
• ACMENOX BL
• ACMECURE DPG • ACMETOL 44 ANTISTICK • ACMENOX BLS65
• ACMECURE TMTM • ACMETOL T/50 AGENT • ACMENOX BLB
SULPHENAMIDE • ACMETOL 60 ANTIDEGRADANT
• ACMECURE TPS • ACMEANTISTICK 300 STAINING
• ACMETOL 212/222
• ACMECURE DCBS • ACMETOL T • ACMENOX 100
DRY BONDING PEPTISER
AGENT
• PEPTIZOL 11
• CYREX 964I • PEPTIZOL 7
 FINORCHEM UNIT-II PRODUCTS

PRODUCTS
> 30 KT

ANTIOXIDANT AUXILIARIES

NON STAINING
STAINING TYPE ANTIOZONANT PEPTISER RETARDER
TYPE ACCELERATOR
 MERNOX 6C  MERTIZER DBD  MERETARD PVI
 MERNOX TQ  MERNOX SP
 MERNOX 445 (6-PPD)
 MERNOX CPL
 MERNOX MBI
SUPHENAMIDES THIAZOLES THIURAMS AND
 MERNOX MB2 Others
DITHIOCARBAMATES
 MERNOX ZMB2
 MERCURE MBS  MERCURE MBT
 MERCURE CBS  MERCURE MBTS  MERCURE TBzTD
 MERCURE TBBS  MERCURE F  MERCURE DPG  MERCURE TMT
 MERCURE DCBS  MERCURE ZMBT  MERCURE ZDC
 MERCURE TBSI  MERCIDE Na-MBT  MERCURE ZDBC
 VULCANIZATION

MODULUS VS CURE TIME

MODULUS

A B C D E
CURE TIME

A) INCUBATION B) SCORCH C) VULCANIZATION D) PLATEAU E) REVERSION

TIME TIME TIME

A) INCUBATION TIME : PHYSICAL PROCESS OF WARMING UP OF THE STOCK.

 MODULUS VS CURE TIME

B) INDUCTION TIME : NO CROSS LINKING THOUGH AT CURE-TEMPERATURE.

CHEMICAL PROCESS
PROCESSING SAFETY
BIN STORAGE LIFE
MOULD FLOW TIME
TOO SHORT : SCORCHING, IMPROPER FUSION, FLOW CRACKS, BAD KNITTING
TOO LONG : LONGER CURE TIME, SAGGING IN OPEN CURES.

C) VULCANIZATION TIME : SHOULD BE SHORT FOR BETTER PRODUCTIVITY

(MAJOR COMPONENT OF CYCLE TIME)
D) PLATEAU : PROPERTIES REMAIN CONSTANT AT MAXIMUM VALUE.
LONG PLATEAU NECESSRY IN INDUSTRIAL PRACTICE
ESPECIALLY FOR THICK ARTICLES.
E) REVERSION: ONLY IN NR, IR, IIR, DETERIORATION IN PHYSICALS.
IN SR MARCHING MODULUS
 ACCLERATORS & CURE CURVES

100

90

80
ZDEC
Modulus

70
CBS
60
MBT
50 MBTS

40 DPG

30

20

10

0 Time
 SULFENAMIDE ACCELERATORS
CBS
MBT

MODULUS
CURE TIME
SULFENAMIDE ACCELERATORS
LONGER PROCESSING SAFETY
FASTER CURE RATE,
HIGHER DEGREE OF CROSSLINKAGES.
VERY WELL SUITED FOR TYRE & SIMILAR TYPE COMPOUNDS.

(cont’d)
 ZINC OXIDE – FATTY ACID ACTIVATION

A B C D
Natural rubber 1 100.0 100.0 100.0 100.0
Antioxidant 2 0.8 0.8 0.8 0.8
Carbon black 3 40.0 40.0 40.0 40.0
Zinc oxide - 3.0 3.0 3.0
Fatty acid 4 - - 1.5 3.0
Sulphenamide 5 0.5 0.5 0.5 0.5
Sulphur 2.5 2.5 2.5 2.5
 ZINC OXIDE – FATTY ACID ACTIVATION

A B C D
Mooney – Viscosity
ML 100 (1+4) 102 102 78 70

ODR at 160°C

t2 (min.) 2.4 2.8 2.7 2.7

t90 (min.) 8.6 5.4 6.8 7.2

Cure at 160°C

(min) 25 12 13 13

M 300 (MPa) 4.4 9.5 11.9 14.2

TS (MPa) 16.8 24.6 27.4 27.3

EB (%) 610 520 490 450

Hardness Shore A 46 55 59 62
SULPHENAMIDE PROCESS OXIDATIVE COUPLING

S S R1
RNH
2
C SH + C S N
N R2 NH N R (H)
2

MBT Amine Sulfenamide

DCBS, TBBS, CBS, MBS

SULFENAMIDE ACCELERATORS ARE CHEMICAL CONDENSATION PRODUCTS OF

MBT AND AN AMINE.

 SULFENAMIDE ACCELERATORS

VULCANIZATION REACTION DOES NOT PROCEED TILL ALL THE SULFENAMIDE ACCELERATOR
QUANTITY HAS BEEN CONVERTED BACK INTO MBT + AMINE

BETTER PROCESSING SAFETY WITH FRESH /QUALITY & HIGHER DOSAGE.

HEMCE QUALITY OF SULPHENAMIDE IS IMPORTANT I.E. METHANOL INSOLUBLES & FREE AMINE

ONCE DECOMPOSITION IS COMPLETE,

THE RATE OF CURE IS THAT OF THE COMBINATION MBT+ AMINE

HENCE FAST RATE OF VULCANIZATION.

 DIFFERENT ACCLERATORS VS PROPERTIES

NR TIRE THREAD COMPOUND ACCELERATOR DOSAGE 0.5 PHR, SULFUR 2.5 PHR

ACCELERATOR SC/T OPT.C/T TS M300

THIAZOLE CLASS
MBT 35 32.5 23 10.9
MBTS 50.5 32.5 22 10.8
ZMBT 48 35.5 22 10
F(MBTS + BASIC ACCELERATOR) 38 24 24.5 11.6

SULFENAMIDE CLASS
CBS 56 21 26 12.7
TBBS 64 23 26 13.4
MBS 70 25 26 11.9
DCBS >120 36 24.5 11.4

SC/T : SCORCH TIME – MINUTES AT 110°C.

OPT.C/T : OPTIMUM CURE TIME – MINUTES AT 143°C.
TS : TENSILE STRENGTH – MPA.
M300 : 300 % MODULUS – MPA.
 ACCLERATORS & CURE CHARACTERSTICS
Relative
Special acc. Thiazoles Guanidine
Scorch Time
Sulfenamides Thiuram Dithiocarbamates

(in CR & CIIR)

DCBS
Long MBS
ETU TBBS
CBS

MBT MBTS

ZMBT DPG

TMTD
ZDEC/
/TMTM
ZDBC
AHB
Short

Fast Slow
Relative Cure Time
DEGRADATION OF SUPHENAMIDE, HYDROLYSIS OF S-N-BOND

S S S
H2O
C S NHR C S S C +
N N N

Sulfenamide MBTS
S
C SOx H + RNH2
N

MBT Sulfonic Acid Free Amine

• ADDITIONAL ONLY AT LOW RUBBER BATCH TEMPERATURE

• STORAGE UNDER COOL DRY CONDITIONS AWAY FROM DIRECT SUNLIGHT,
• AWAY FROM HYDROLYTIC INFLUENCES e.g. ACID FUMES.
• WET SKIDDING OF MASTERBATCH OR REMILLED MASTERBATCH TO BE AVOIDED.
• RAPID DEGRADATION OF SULFENAMIDES IN DRY BLENDS WITH SULFUR
SOLUBILITY OF ACCELERATORS IN EPDM

Solubility of accelerators in EPDM (pbw on 100 pbw rubber)

Upper limit of solubility International Abbreviation

0.3 TDEC, BiDMC, CuDMC

0.7 DTDM,TETD
TMTD
TMTM
1.5
ZDEC
ZDMC
2 ZDBC
2.5 TPS, CBS,TBBS ,MBS
MBT, MBTS
3
S
high solubility >3 ZBEC
ACCELERATORS IN EPDM QUANTITY GUIDELINES

General curative system Standard system 1

1.5 Sulphur 1.5 Sulphur
0.5-1.5 MBT 0.5 MBT
0.5-1.5 TMTD/TMTM 1.5 TMTM
O-2.5 ZDEC/ZDBC
O-4 TP/S (Zinc dialkyl dithiophosphate)

System with higher Standard system 2

processing safety 1.5 Sulphur
1.5 Sulphur 1.5 MBT
0.8 CBS 0.8 TMTD
0.8 TMTM 0.8 ZBEC

Very fast curing system

System with low
1.5 sulphur
compression set
1.5 MBT
0.6 TMTD
0.8 MBTS 2 ZDBC
0.8 TBzTD 1.5 TBzTD
1.5 ZDEC/ZDBC 2 DTDM

Test formulation EPDM 100, C-Black N 550- 120, Paraffinic oil- 75, ZnO-5, stearic acid- 1
 ACCELERATORS IN EPDM QUANTITY GUIDELINES

System with good ageing resistance System with high elongation &
2 Ni-DBC good ageing resistance
2.5 Sulphur 0.5 Sulphur
2 ZDBC 3.0 MBT
2 ZDEC 1.5 ZDBC
0.6 DTDM 0.8 TMTD
0.8 DTDM

Nitrosamine-free system
1.35 Sulphur
3.8 CBS
0.75 MBT

Nitrosamine-free system
2.0 Sulphur
1.0 ZBEC
1.5 MBT
2.5 TP/S
1.0 DTDC/TBzTD

Test formulation EPDM 100, C-Black N 550- 120, Paraffinic oil- 75, ZnO-5, Stearic acid- 1
 SULFUR DONORS

 These organic compounds contain sulfur in a thermally labile (changed) form. Under
normal curing conditions, free sulfur is released which, in contrast to normal sulfur, mainly
forms mono- and di-sulfidic bridges.

 Because of their higher bond energies, these di-sulfidic bridges are much more resistant to
reversion and are responsible for the excellent heat-aging resistance of the vulcanizates.

 Replacing sulfur with sulfur donors results in less free sulfur in the rubber compound
formulation, and this leads to advantages, such as:

1. Improved physical properties

2. Lower compression set
3. Excellent reversion resistance
4. Vulcanizates with improved aging resistance
5. No sulfur blooming
6. No contact staining with heavy metals.
7. Higher processing safety(scorch)

Ex. DTDM, DTDC, TMTD, TBzTD.

 Acmecure DTDM

Function : Sulphur donor (vulcanizing agent)

Chemical Name : Dithio dimorpholine
Active Sulfur, % : 13.6
% Active sulfur of some sulfur donors are as follows:

Ingredients % Active Sulfur

DTDC 28.8
MBSS 28.4
DPTT 16.6
TMTD 13.3
TBzTD 5.8

20
 SULFUR DONORS

% Tensile strength retention

EV
TBzTD
(Sulfur Donor)

Modulus
Semi EV
Normal
Sulfur
EV
Semi EV
Normal
Sulfur

Cure time at 160°C Ageing period at 100°C days

SULFUR DONORS
CHEMICALS WHICH DURING CURE RELEASE SULFUR TO GIVE ONLY MONO or Di
SULFIDIC CROSSLINKS

Ex. TMTD, TBzTD, DTDM , DTDC.

 Typical properties & uses
Typical properties:
Predominantly forms monosulfide linkages, which is a characteristic of EV systems.
This system network resists degradation due to heat.
Mercure DTDM may be used when a high amount of sulfur is not tolerated in the
compounding recipe, for example, high temperature vulcanization of rubber.
Unlike TMTD, does not accelerate the vulcanisation process.

Uses:
 Tyre & tread – Tyre base tread, high performance tread, wet traction tread.
 Heat resistant hose (EPDM)
 White UV resistant sheeting (EPDM)
 Electrical insulation (EPDM)
 Automotive bumpers (EPDM)

Cont’d
Application & uses (cont’d)

Uses:
Sour gasoline resistant fuel hose (NBR)
Power steering hose (NBR)
Air intake hose (NBR)
Automotive air conditioning hose (NBR)
Hydraulic service hose (NBR)
Firehose cover (NBR)

Oilwell cable jacket (NBR)

Typical properties & uses

Typical properties:
Compression set properties using DTDM are better when compared to conventional
vulcanization system
Uses:
Automotive window gaskets (EPDM)
Microwave cured profiles (EPDM)
Low temperature insulation gaskets (NBR)
Pipe gasket (SBR, EPDM)
Filter gaskets (NBR)
Typical dosage : 0.5 to 2 phr
Acmecure/Mercure DCBS

Chemical name: Dicyclohexyl benzothiazole sulphenamide

Delayed action sulphenamide accelerator, highest scorch safety.

Typical Properties:
Delayed action sulfenamide accelerator for NR, NR/SBR NR/BR blends and the slowest among all sulfenamides.
Has excellent processing characteristics and good storage stability.
Vulcanizates cured with DCBS show excellent resistance to flex cracking, good resilience and high tensile
strength.

Uses:
 Tyre belt skim compound
 Hot Tread, Cushion Gum
 Steel cord, hose wire compounds

 Conveyor belting

25
 ACMECURE TPS

Composition: 67 % zinc dialkyl dithiophosphate bound to 33 % silica

Appearance: Off white, crumbling, free-flowing powder

Function: Nitrosamine free, non-blooming (high solubility) secondary accelerator for the rapid vulcanization of
compounds based on EPDM and other diene rubbers.

Uses

It is a specialty nitrosamine free non blooming (high solubility) accelerator for EPDM compounds, used along
with accelerators of the thiazole and thiuram class.

Vulcanizates cured with Acmecure TP/S have high degree of crosslinking. Due to its high solubility in rubbers of
varying polarity, it does not show any signs of blooming.

EPDM compounds containing Acmecure TP/S are easy to process and exhibit good flow properties, even in
intricate moulds.
 ACMECURE TPS

Use: In the efficient vulcanization of NR and other rubbers, such as IR, SBR, NBR vulcanizates produced with
Acmecure TP/S provide an outstanding heat aging resistance.

In NR, when used along with sulfenamide accelerators, it improves reversion resistance. Care must be taken to
select the level of Acmecure TP/S to obtain the best compromise between scorch and reversion resistance.

Generally used along with other Nitrosamine free accelerators for maximum benefit.

Dosage: Usually 2-3 phr in combination with thiazoles, sulfenamides.

Typical applications: Large size Tires, Soild Tires. Moulded and extruded technical rubber articles of all kinds,
e.g. profiles, hoses, and thick moulded components like engine mounting, fenders and thick re-treads.
 INSOLUBLE SULPHUR

• ADDITION OF EXCESS/HIGHER DOSAGE OF NORMAL SUPHUR CAN CAUSED BLOOMING

• IN ORDER TO PREVENT BLOOMING A PART OF ORDINARY SULPHUR IS REPLACED BY

INSOLUBLE SULPHUR.

• IMPROVE BIN STORAGE STABILITY – ONLY COMPOUNDS PROCESSED AT LOW

TEMPERATURES.

• HIGH TEMPERATURE PROCESSING SAFETY–SAME WITH SOLUBLE OR INSOLUBLE SULFUR.

• RAPID CONVERSION OF INSOLUBLE SULFUR TO SOLUBLE SULFUR IN PRESENSE OF

ALKALINE MATERILAS SUCH AS SULFENAMIDE ACCELERATOR, DPG & HEHA

• TO AVOID DUST EXPLOSION IT IS OIL COATED UPTO 20 %.

• POLYMER BOUND CAN BE USED.

 RETARDER IN NR / BR TREAD TYPE COMPOUND

Scorch Time
I II III IV PVI (ta) at 130°C
PVI 0.0 0.25 0.50 0.75 p.b.w
50
4000 Sheer force [min]
[Cn] 40
3000
30

2000 I II III IV
20

1000
10

0 0
0 5 10 15 20 25 30(min) 0 0.25 0.50 0.75
Curemetering at 150°C PVI dosage (p.b.w.)

Recipe: NR 80, BR 20, N330 55, MIN. OIL 3, ZnO 5, ST. ACID 3 6 PPD 2.5, TMQ 1.5,
MC WAX 1, V. TBBS 1.2, S 2.0.
 SAFE ALTERNATIVES

Nitrosamine issue & safe alternative.

Accelerator Present Accelerators Accelerator having Safe
family being used Nitrosamine issue Accelerators
Sulphenamide MBS, CBS, TBBS, TBSI MBS CBS, TBBS, TBSI
Sulphenamide DCBS DCBS TBSI
Sulphur donor DTDM, DTDC, TMTD,TBzTD DTDM, TMTD TBzTD, DTDC

Secondary TMTD,TMTM, DPG, TPS TMTD,TMTM DPG, TBzTD,TPS

Thiocarbamate ZDEC, ZDBC, ZBEC, ZDMC ZDEC, ZDBC, ZDMC.. ZBEC

In Latex ZDEC, ZDBC, ZDMC… ZDEC, ZDBC, ZDMC… ZBEC

IMPORTANT CHARACTERISTICS OF ANTIOXIDANTS

IMPORTANT CHARACTERISTICS OF ANTIOXIDANTS:

A. STAINING/NONSTAINING/MIGRATORY STAINING/DISCOLORING
B. PROTECTIVE PROPERTIES
(I) ACTIVE GROUP CONTENT
E.G. –NH –, – OH –, OR – SH AND THEIR ACTIVITY; AND
(II) ABILITY TO GIVE PROTECTION TO THE VULCANIZATE
UNDER THE SERVICE CONDITIONS.
C. EFFECT ON CURING CHARACTERISTICS.
D. SOLUBILITY IN RUBBER.
E. DISPERSIBILITY IN RUBBER.
F. VOLATILITY.
G. MIGRATION CHARACTERISTICS.
H. LEACHING IN SERVICE FLUIDS (WATER OR OIL).
I. NONTOXICITY.
J. ECONOMICS.
 ANTIOXIDANTS SOME PRECAUSTIONS

ANTIOXIDANT ADDITION PREFERABLY AT FINAL STAGE OF MIXING @ 105-110 C

• ANTIOXIDANT PARTIAL LOSS DURING MIXING IN MASTER BATCH
• ANOTHER ADVANTAGE OF ADDITION OF A/O IN THE FINAL STAGE IS
THE REDUCED VISCOSITY OF COMPOUND HENCE BETTER
PROCESSABILITY OF COMPOUNDS IN CASE OF NR OR BLEND OF NR.
• ANTIOXIDANT WHOSE MELTING POINT ARE WELL BELOW THIS
TEMPERATURE IT WILL MELT & EASILY DISPERSED IN THE MASS
• WITH HIGHER MELTING POINT ESSENTIAL TO USE ONLY IN POWDER
FORM TO ENSURE SATISFACTORY DISPERSION.
• TMQ HARD BEADS ADVISABLE TO ADD IN THE BEGINING OF MB
LATEX: MOSTLY NON STAINING BUT TMQ IN COIR FOAM IS ACCEPTABLE
• POWDER A/O TO BE ADDED IN DSPERSION FORM
• LIQUID A/O TO BE ADDED IN EMULSION FORM.
PEROXIDE CURING: PPD CLASS NOT TO BE USED, IT WILL REACT WITH FREE
RADICAL & GET CONSUMED, TMQ IS BEST
 ACMENOX BL
A CONDENSATION PRODUCT OF ACETONE & DIPHENYLAMINE

GIVES GOOD PROTECTION AGAINST OXIDATIVE HEAT AGEING & ANTI FLEX CRACKING.

OTHER ADAVANTAGES :

BEING LIQUID ANTIOXIDANT REDUCE MOONEY VISCOSITY OF COMPOUND, IMPROVE TACK.

MIXING: LESS HEAT BUILT UP DURING PROCESSING, IMPROVE SCORCH SAFETY.

EXTRUSION & CALDERING: REDUCED DIE SWELL, BETTER CONTROL ON DIMENTIONS & GOOD
SURFACE FINISH. AVOID POROSITY IN EXTRUDATES. AVOID SCORCHING.

FRICTIONING: BETTER COMPOUND ANCHORING /PENETRATION INTO FABRIC/CORD OR

WETTING OF STEEL CORD OR WIRE. LEADING TO BETTER ADHESION IN RUBBER COMPOSITE
 ACMENOX BL

ADVANTAGE OVER TMQ

NO AMINE EFFECT SIMILAR TO TMQ *
NO CONVERSION OF INSOLUBLE SULPHUR TO SOLUBLE SULPHUR ON STORAGE IN GREEN
COMPOUND.
HENCE AVOID ANY POSSIBILITY OF SULPHUR BLOOMING THUS NOT IMPAIRING TACK
WHICH MAINTAINED THE TACK OVER LONG STORAGE, BETTER ADHESION.
APPLICATIONS :
 BONDING COMPOUNDS FOR RUBBER COMPOSITE (TIRES, BELTING, HOSES) WITH
FABRIC/CORD, STEEL CORD/WIRE.
 HOT RETREAD (SHELF LIFE MINIUM 6 MONTHS) COMPOUNDS FOR OTR & TRACTOR TIRES.
 CUSHION GUM COMPOUND (SHELF LIFE 6 MONTHS).
 DYNAMIC FLEXING TEST
UNAGED

KILOCYCLES TO FAILURE
688
700

600

500

405
400

300

200
133
100

0
Blank BLE TMQ

# Passenger Car Tire Carcass compound ‘’

‘’
FLEX TO FATIGUE FAILURE (100% EXTENSION)

KILOCYCLES TO FAILURE

300

270
257

240

210

180

150 Unaged
139 AGED 70 Hours @ 100 c

120

90
79

60

30
30
20
13

0
Blank BLE TMQ

# Passenger Car Tire Carcass compound

 ACMENOX BL

IMPORTANT CHARACTERISTICS :
UNMATCHED CUT – GROWTH RESISTANCE

EXCELLENT FLEX – CRACK RESISTANCE

GOOD HEAT AGEING RESISTANCE

BEING LIQUID HELP IN PROCESSING

COMPATIBLE WITH ALL POLYMERS

COST EFFECTIVE

Hence can be used as partial replacement for 6 PPD in many

Non Tire products

 ACMENOX BL/BLS/BLB

ACMENOX BLB AND BLS-75 ARE NON LIQUID VERSIONS OF ACMENOX-BL. BOTH ARE
FREE FLOWING SOFT GRANULES HAVING ACTIVE INGREDIENT AS UNDER

A. ACMENOX-BLB - 50 ± 2% ACTIVE INGREDIENT WITH

BALANCE CARBON BLACK CARRIER

B. ACMENOX – BLS-65/75 – 65/75± 2% ACTIVE INGREDIENT WITH BALANCE

TYRE GRADE SILICA AS CARRIER

THE DOSE COULD BE ADJUSTED ON THE BASIS OF ACTIVE

INGREDIENT. (ACMENOX-BL)
 ACMENOX 100

Chemical Name: Mixture of diaryl- p- phenylene diamines – DTPD

Function: Good & long-lasting antioxidant & antiozonant effect
Typical Property:

Migrates very slowly to surface. Limited solubility in GP Rubber. Suggested dosage is 0.7 pbw max

Advantages:
Used as secondary antiozonant along with 6PPD.
It starts migrating slowly after 6 PPD starts getting consumed, offering extended/long term protection.
Uses:
Agricultural semi pneumatic tyres
Motor/Engine mounts
Special auto parts of NBR/EPDM warranting extreme conditions and long life

39
Non Staining Antioxidanats

Mernox SP: Styrenated Phenol (SPH)

Meronx CPL: Butylated reaction product of p-cresol and dicyclopentadiene

Mernox 445 : 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl) phenyl] aniline

Mernox MBI: 2-mercaptobenzimidazole (MBI)

Mernox MB2: 4 and 5-methyl-2-mercaptobenzimidazole (MMBI)

Mernox ZMB2: Zinc salt of 4-and 5-methyl-2-mercaptobenzimidazole (ZMMBI)

 MERNOX MBI/MB2/ZMB2

Mernox MB--2-mercaptobenzimidazole (MBI)

Mernox MB 2: 4- and 5-methyl-2-mercaptobenzimidazole (MMBI)

Mernox ZMB 2: Zinc salt of 4- and 5-methyl-2-mercaptobenzimidazole (ZMMBI)

Typical Properties:

Works in only in synergy with other amine & phenolic antioxidants like Mernox TQ, 6C, BL to provide excellent aging resistance.

Best protection is provided in thiuram and dithiocarbamate curing systems, containing little or no sulphur.

Mernox MB 2 also protects against rubber poisons, in combination with Mernox 6C (6PPD).

Uses:

High performance conveyor belting of NBR

Cable sheath using NBR/PVC

Filter and low temperature gaskets

Hydraulic hose, LPG hose and air intake hose of NBR

EPDM roofing membranes

41
# • ZMB2 provides best protective effect against ageing in hot oils, especially in combination with OCD
 SYNERGY OF ANTIOXIDANTS

100 –

80 –

Tensile strength
TMTD
60 – 1.5 TMQ + 1.5 MB2
TMTD
3 MB2
40 – TMTD
3 TMQ

20 – TMTD
Normal Sulfur No A/o.
1 TMQ
0–
4 8 12 16 20 24
DAYS IN HOT AIR AT 100°

NR TREAD TYPE COMPOUND

 MERNOX MBI/MB2/ZMB2

Typical Property:

Inhibits flex cracking

Used in articles exposed to repeated flex cycles and expected to last long

Highly suitable for polychloroprene compounds (6 PPD not recommended as too scorchy)

Uses:

Bridge bearing pads

Fire resistant conveyor belting

Rubber Springs

Use in dock fenders, expected to last 20 – 25 years (to be explored)

 Why is bonding needed ?

A good bonding is required to ensure a proper performance of the rubber – reinforcement structures.
These structures can considered to be composites of
– a relatively low strength/high elongation elastomeric matrix
– and a high strength/low elongation reinforcing material
Curing only gives adhesion due to a mechanical interaction

Reinforcing elastomeric
material matrix

Required : Adhesion due to physical/chemical interaction

Reinforcing Elastomeric
Adhesive
system
material matrix
 BONDING SYSTEMS

IMPREGNATION (DIPPING) DRY – BONDING

RFL
(RESORCINOL –
FORMALDEHYDE LATEX)
RFS COBALT
(RESORCINOL, SALTS
FORMALDEHYDE
DONOR, SILICA)

RUBBER RUBBER
TO TO
TEXTILE STEEL – CORD
BONDING BONDING
 BONDING SYSTEMS
DRY BONDING SYSTEMS
RESORCINOL FORMALDEHYDE SILICA (RFS) SYSTEM
SUITABLE FOR BONDING OF
RUBBER COMPOUND BASED ON FABRIC
NR RAYON
SBR TO NYLON
BR
CR POLYESTER WITH SPECIAL
SPIN FINISH.
NBR GLASS WITH SPECIAL
SPIN FINISH.
STEEL CORD

RESORCINAOL FORMALDEHYDE SILICA

COMPONENT COMPONENT

BOND FABRIC – RF RESIN – SILICA – RUBBER

ALL THREE COMPONENTS NECESSARY i.e RESORCINOL, FORMALDEHYDE, SILICA
Influence of sulphenamide-accelerators on cord adhesion

25 Rayon Nylon Polyester

CBS
DCBS
20 TBBS

CBS

Pull-out-strength (kgf/20 mm)

MBS
DCBS
DCBS TBBS
15 CBS
TBBS
MBS
MBS

10

0
Influence of accelerators on steel cord adhesion in the RFS process

AS THE SCORCH SAFETY OF THE COMPOUND INCREASES, THE ADHESION IMPROVES. ACCLERATOR
DCBS GIVES THE BEST ADHESION TO BOTH BRASS COATED AND ZINC PLATED STEEL CORD.

60
Steel cord, brass plated
7 × 3 ×0,15 DCBS
Pull-out strength (kgf/20mm) 50

TBBS MBS Steel cord, zinc plated

40 CBS 7 × 3 ×0,15
MBTS

30 DCBS

20
CBS TBBS MBS
10
MBTS

0
Allnex & Finorchem (Acmechem)

Allnex: A leading global supplier of environmentally

friendly coating resins & additives.

Cyrez resin: HMMM i.e. Hexamethoxy methyl

melamine, a methylene donor, being used by Tire &
Rubber Industry.

Relatively nontoxic & present little hazard of

dermatitis. Non corrosive steel & Polyester cord &
metal moulds.

Allnex granted an exclusive licence of Cyrez 964I to

Finorchem (Acmechem for Manufacturing in India,
Marketing, Selling & Distributing allnex Cyrez 964I

With the right to use brand name CYREZ 964I in the

territory of India & Sri Lanka
 Processing Aids - Function

Process aids were designed to overcome the common day to day processing
problems, enhance production rates, reduce energy costs and material rejection.

Processing aids generally perform the following functions:

 Peptizing/mastication i.e. reduction in viscosity mainly of NR

 Homogenization of polymer blends, decreasing mixing time and load

 Improving filler dispersion with greater uniformity in Viscosity

 Improving compound flow, smoother extrusion and uniform filling of mould

cavities

 Some processing aids perform more than a single function, therefore called as
multifunctional processing aid

50
Processing Aids from Acmechem - Classification

Processing Aids may be broadly classified in to following categories :

Processing Aids
Dispersing Agents & Peptizers
Flow Promoters
Acmetol 44, 50, 212, 222

Homogenizer Internal Release

Acmetol T Agents Acmetol 212, 222

Physical Peptizers Chemical Peptizers

Acmetol 50, 60 Peptizol
Peptizers
Mastication study

80

70

60

50

40

30

20
4 8 12
Blank P 7 (0.1) P 11(0.1)
 Carbon black master batching

Two step CB master Integrated CB master

Premastication with 0.1 phr Directed CB master batch with

Peptizol unmasticated rubber Peptizol dosage
0.25 phr
Ageing and Reweighing of
rubber

Carbonblack
masterbatch

Final Final
COMPARISON 3A BANBURY TRIALS
Energy requirements KW/Hrs
21.4 13.9
Labour required Man Minutes
49 25.5
Overheads
100 64
 ADVANTAGES of Integrated CB master

1 Lower energy requirements.

2 Less housekeeping problems due to elimination of handling of sticky premasticated

rubber and reweighing of premasticated rubber.

3 Less floorspace requirement due to elimination of floorspace for storage of masticated

rubber.

4 30% increase in the mixing capacity of the mixer and hence lower labour costs and
overheads.

5 Carbonblack is added to the high viscosity rubber and hence better dispersion of
carbonblack and zinc oxide resulting in better wear and tear properties of the finished
product.
 Acmetol 44

Funtion: Dispersing aid, flow promoter and cure activator

Composition: Mixture of Zinc salt of fatty acid and alkali soap
Advantages:
Acmetol 44 is a processing aid suited for NR and synthetic rubber like SBR and EPDM
(except for halogenated elastomers)
Improves dispersion of mineral fillers and Carbon black, providing uniformity of viscosity from
batch-to-batch
Suited for applications in extruded compounds, but also offers advantages on transfer
molding and injection molding
Also acts as a cure activator, therefore, dosage of stearic acid may be reduced in compound
recipe.
Dosage – 1 to 3 phr

56
 Acmetol 50

Function : Physical peptizer, lubricant and flow promoter

Composition : Zinc salt of unsaturated fatty acid
Advantages:
Physical peptizer for natural rubber
Improves reversion resistance and produces vulcanizates with greater resilience and tear
strength
Being highly soluble in rubber compound, Acmetol 50 can be used without blooming or
negatively impacting rubber to metal or rubber-to-rubber adhesion
Due to the polymer chain lubricating effect, compounds containing Acmetol 50 exhibit lower
viscosities under shear as well as enhanced flow rates, which improves mill roll release and
provides smoother extrusion and calendaring.
Also suitable for solution SBR
Typical Dosage : 3 to 5 phr
57
 Acmetol 60

Function : Physical Peptizer

Composition : Mixture of Zinc soaps of high molecular weight and rubber compatible
carbonic soap

Advantages:

Acmetol 60 is a rubber soluble zinc soap effecting faster physical peptization of natural rubber.

Peptization action starts in the lower temperature range of compounding, which leads to
shorter mixing cycles

Suitable for mastication in a separate stage, as well as for single stage mixing.

Shore hardness of the vulcanizates is not influenced

Being highly soluble in rubber, Acmetol 60 does not bloom from the vulcanizates. Reduction
of high dosages of stearic acid or paraffin wax is possible

Dosage : 3 to 5 phr 58
 Acmetol T
Function: Homogenizer and general processing aid
Composition: Blend of Zinc salts of fatty acids
Advantages:
Acmetol T helps in mastication and homogenizing where a blend of polymers like NR/ PBR,
NR/SBR etc is used in formulation.
Acmetol T also helps in very good dispersion of the filler in loaded compounds
Process of mastication of polymer can be avoided by using Acmetol, which helps in time and
energy savings.
Improves extrusion speed and reduces die swell
Dosage:
2.0 phr in Natural rubber
2.5 to 3.0 phr in carbon loaded compound

2.0 to 3.0 phr in microcelluar sheets and Inner soles 59

 Acmetol 212
Function : Emulsion plasticizer, dispersing and lubricant
Composition : Distearyl phthalate Pentaeryhritol Ester I &II
Advantages :
Acmetol 212 is a processing additive for rubber polymers and normally used to improve the general compound
processing without significant influence on physical properties
Shortens the mixing time by faster filler incorporation
Prevents sticking of elastomers and compounds to rotors and rolls.
Addition of Acmetol 212 can reduce the risk of scorching, particularly in highly loaded compounds
Due to the good plasticizing properties of Acmetol 212, molds can be filled faster with lower pressures during
injection and transfer molding.
Effect on the vulcanization behavior is neutral; this applies also to peroxide cure systems
Typical Dosage : 1 to 2% of the total batch weight or about 2 phr

60
 Acmetol 222

Function : Emulsion plasticizer, dispersing aid and lubricant

Composition : Distearyl phthalate Pentaerythritol Ester I &II
Advantages :
Suited for Nitrile Rubber based compounds.
Acmetol 222 is a dispersing aid, which also provides plasticizing and lubricating effect. Shortens
the mixing time by faster filler incorporation.
Prevents sticking of elastomers and compounds to rotors and rolls.
Addition of Acmetol 222 can reduce the risk of scorching, particularly in highly loaded compounds
Due to the good plasticizing properties of Acmetol 222, molds can be filled faster with lower
pressures during injection and transfer molding.
Dosage: 0.5 to 2% of the total batch weight or about 2 phr

61
Processing Aids Typical Applications
 Process Aids – Typical Applications
Product Peptizol 7 Peptizol 11 Acmetol 44 Acmetol 50 Acmetol 60 Acmetol T Acmetol 212 Acmetol 222
Homogenizer and
Filler dispersion General process aid, extrusion
Environmentally safe
improvement and reduces viscosity, aid.Blend of NR Flow modifier, Flow modifier,
Characteristic Reduces mooney peptizer. More Physical
batch uniformity. Also improves filler with SBR, PBR dispersing aid, dispersing aid,
s viscosity of NR suited for mixing on peptizer
activates cure to dispersion, resilence etc.Useful in filler lubricant lubricant
Intermix.
some extent. and tear strength loaded
compounds.
Dosage 0.1 to 0.2 phr 0.1 to 0.2 phr 1 to 3 phr 3 to 5 phr 3 to 5 phr 2 to 3 phr 2 phr 2 phr
Suitable for NBR,
All types of
HNBR, XNBR
Suitable for NR and synthetic rubber.
Typical Mainly used for etc.Extrusion,
NR blends with SBR, Extrusion, injection
applications NR injection molding
PBR etc. molding and
NR, SBR, EPDM and transfer
transfer molding.
Tread Tread Extruded compounds Tread molding.
Tyre Tyre Tread Tread Auto tubes Profiles Profiles
Conveyor belting Conveyor belting Tyre Tyres Footwear Auto components Rollers
Hose Hose Conveyor belting Molded goods Sheets
V belts V belts Hose EPDM membranes Auto components
Matting Rubber mats V belts Sheets Molded goods
NR Sheeting for Butyl tubes
NR Sheeting exports Rubber mats
Footwear Sheeting
Molded goods
Rubber to metal
bonded components
Note: Not suitable for
CR
Need for Antistick agent/Anti-tack

Rubber compound sheets after completion of mixing process has relatively high
temperature of 70 to 100 deg C.
It has to be cooled to ambient temperature, before stacking on pallets. Otherwise, the
compound may scorch.
The sheets therefore are cooled by passing through water or under fan.
However, the un-vulcanized sheets tend to be tacky and (if stacked as it is) would stick to
one another, which would be troublesome for further process.
Therefore, to overcome this problem, the following methods are adopted in the industry:
a) Applying talc on the rubber sheets
b) Using a semi embossed polyethylene film between 2 sheets
c) Use an anti-tack

(cont’d)
Need for Antistick agent/Anti-tack (cont’d)

However, there are some problems when the methods a) & b) are followed:

a) Creates a dusty environment in the entire shop-floor, harming the health of workmen
and machines

b) Inventory of plastic sheets have to be maintained, stored after use and plastic sheets
disposed off after getting worn out.

The use of anti-tack/ anti-stick is therefore the easiest and economical method for handling
of un-vulcanized rubber sheet
 Anti-stick agents in general

The following products are usually being used in the industry as anti-tack/ anti-stick.
Soap solution
Sulfonated oils with mineral fillers
Surfactants with mineral fillers
Calcium stearate, Zinc stearate and Magnesium stearate dispersions with surfactants
Water soluble polymers with surfactants
Anti-stick agents are diluted with water and used as dispersions/ solution in dip tank or
batch off.
Dip tank and batch off units

Dip tank process: When the production volume is not too large eg: about 2 MT, the anti-
tack may be diluted in MS tanks of 2 – 3 KL capacity, the sheets then dipped in to the
solution to cool and dried on hanger under fan.

Batch off: This is a kind of semi continuous operation, where the sheet/strips are
continuously fed through conveyors, pass through the tank containing anti-tack and
subsequently dried by air draught and stacked. Used when mixing volumes are high –
Intermix operation.
Acmeantistic-300

Function: Compound anti-sticking release agent in powder form for batch-off operations
Composition: Consists of inorganic fillers, active substances and tensides (surfactant made from
biomass), containing approx. 95% of active ingredients
How to use?
It is recommended to dilute Acmeantistick 30 in the proportion of 1 + 30 (1 part powder + 30 parts
water). This means a solid content of about 3% in the dilution.
It is recommended to use hot water, about 60 deg C and stir for about 20 to 30 minutes to obtain
a good dispersion.
During dipping, a fine coat of filler gets deposited on the sheet surface, which after drying,
prevents sticking of sheet surfaces.
Acmeantistic-300
Typical Properties:
Used in a dipping process to prevent the adhesion of uncured rubber and milled sheets
Shows excellent dispersion stability in water and excellent wetting of the rubber sheets.
Low sedimentation, which prevents formation of slurry at the bottom of dipping tank
Offers good release effect and inorganic fillers provide sufficient friction to prevent the
sheets from slipping during storage and to allow for smooth, continuous feeding of
extruders.
The film formed on the rubber surface is non dusty and equipment fouling is minimized
Typical Dosage : 3 ± 0.1% concentration in water
Note: Anti-stick agents are generally used by medium to large scale rubber
manufacturers.
The small scale manufacturers do not have the infrastructure and production volumes to
use a batch off unit/ dip tank.
69
Acmeantistic-300
Thank you very much for patience hearing.