Rubber Curing
Systems
R.N. Datta
1. A commissioned expert review, discussing a key topic of current interest, and referring to the References and
Abstracts section. Reference numbers in brackets refer to item numbers from the References and Abstracts
section. Where it has been necessary for completeness to cite sources outside the scope of the Rapra Abstracts
database, these are listed at the end of the review, and cited in the text as a.1, a.2, etc.
2. A comprehensive References and Abstracts section, resulting from a search of the Rapra Abstracts database.
The format of the abstracts is outlined in the sample record below.
3. An index to the References and Abstracts section, derived from the indexing terms which are added to the
abstracts records on the database to aid retrieval.
Item 1
Source of
Macromolecules
original article
33, No.6, 21st March 2000, p.2171-83
Title EFFECT OF THERMAL HISTORY ON THE RHEOLOGICAL
BEHAVIOR OF THERMOPLASTIC POLYURETHANES
Authors and
Pil Joong Yoon; Chang Dae Han affiliation
Akron,University
The effect of thermal history on the rheological behaviour of ester- and
ether-based commercial thermoplastic PUs (Estane 5701, 5707 and 5714
from B.F.Goodrich) was investigated. It was found that the injection
moulding temp. used for specimen preparation had a marked effect on the
variations of dynamic storage and loss moduli of specimens with time
observed during isothermal annealing. Analysis of FTIR spectra indicated
that variations in hydrogen bonding with time during isothermal annealing Abstract
very much resembled variations of dynamic storage modulus with time
during isothermal annealing. Isochronal dynamic temp. sweep experiments
indicated that the thermoplastic PUs exhibited a hysteresis effect in the
heating and cooling processes. It was concluded that the microphase
separation transition or order-disorder transition in thermoplastic PUs could
not be determined from the isochronal dynamic temp. sweep experiment.
The plots of log dynamic storage modulus versus log loss modulus varied
with temp. over the entire range of temps. (110-190C) investigated. 57 refs. Companies or
GOODRICH B.F. organisations
Location USA mentioned
Accession no.771897
Please contact the Document Delivery Department for availability, current prices and delivery methods.
Report 87 Rubber to Metal Bonding, B.G. Crowther, Rapra Report 114 Developments in Polyacetylene - Nanopolyacetylene,
Technology Ltd. V.M. Kobryanskii, Russian Academy of Sciences.
Report 88 Plasticisers - Selection, Applications and Implications, Report 115 Metallocene-Catalysed Polymerisation, W. Kaminsky,
A.S. Wilson. University of Hamburg.
Report 116 Compounding in Co-rotating Twin-Screw Extruders,
Report 89 Polymer Membranes - Materials, Structures and
Y. Wang, Tunghai University.
Separation Performance, T. deV. Naylor, The Smart
Chemical Company. Report 117 Rapid Prototyping, Tooling and Manufacturing,
R.J.M. Hague and P.E. Reeves, Edward Mackenzie
Report 90 Rubber Mixing, P.R. Wood. Consulting.
Report 91 Recent Developments in Epoxy Resins, I. Hamerton, Report 118 Liquid Crystal Polymers - Synthesis, Properties and
University of Surrey. Applications, D. Coates, CRL Ltd.
Report 92 Continuous Vulcanisation of Elastomer Profiles, Report 119 Rubbers in Contact with Food, M.J. Forrest and
A. Hill, Meteor Gummiwerke. J.A. Sidwell, Rapra Technology Ltd.
Report 93 Advances in Thermoforming, J.L. Throne, Sherwood Report 120 Electronics Applications of Polymers II, M.T. Goosey,
Technologies Inc. Shipley Ronal.
Volume 11
Report 121 Polyamides as Engineering Thermoplastic Materials,
I.B. Page, BIP Ltd.
Volume 12
Report 133 Advances in Automation for Plastics Injection
Moulding, J. Mallon, Yushin Inc.
Report 134 Infrared and Raman Spectroscopy of Polymers,
J.L. Koenig, Case Western Reserve University.
Report 135 Polymers in Sport and Leisure, R.P. Brown.
Report 136 Radiation Curing, R.S. Davidson, DavRad Services.
Report 137 Silicone Elastomers, P. Jerschow, Wacker-Chemie GmbH.
Report 138 Health and Safety in the Rubber Industry, N. Chaiear,
Khon Kaen University.
Report 139 Rubber Analysis - Polymers, Compounds and
Products, M.J. Forrest, Rapra Technology Ltd.
Report 140 Tyre Compounding for Improved Performance,
M.S. Evans, Kumho European Technical Centre.
Report 141 Particulate Fillers for Polymers, Professor R.N.
Rothon, Rothon Consultants and Manchester
Metropolitan University.
Report 142 Blowing Agents for Polyurethane Foams, S.N. Singh,
Huntsman Polyurethanes.
Report 143 Adhesion and Bonding to Polyolefins, D.M. Brewis
and I. Mathieson, Institute of Surface Science &
Technology, Loughborough University.
Rubber Curing
Systems
R.N. Datta
(Flexsys BV)
ISBN 1-85957-326-6
Rubber Curing Systems
Contents
1. Introduction .............................................................................................................................................. 3
1.1 Conventional Vulcanisation, Semi-Efficient Vulcanisation and Efficient Vulcanisation .............. 3
1.2 Measuring Cure ............................................................................................................................... 3
1.3 Test Equipment and Conditions ...................................................................................................... 5
2. Curing Systems ........................................................................................................................................ 5
2.1 Sulfur Curing Systems .................................................................................................................... 5
2.1.1 Accelerators ........................................................................................................................ 5
2.1.2 Sulfur Donors ................................................................................................................... 12
2.2 Cures for Speciality Elastomers ........................................................................................................ 16
2.2.1 Cure Systems for EPDM .................................................................................................. 16
2.2.2 Cure Systems for Nitrile Rubber ...................................................................................... 19
2.2.3 Cure Systems for Polychloroprene ................................................................................... 19
2.2.4 Cure Systems for Butyl and Halobutyl Rubber ............................................................... 21
2.3 Peroxide Cure Systems ................................................................................................................. 26
2.3.1 Peroxide Vulcanisation of EPDM .................................................................................... 29
2.4 Sulfur Free Curing Systems .......................................................................................................... 30
2.4.1 Phenolic Curatives, Benzoquinone Derivatives and Bismaleimides ............................... 30
2.4.2 Vulcanisation by Triazine Accelerators ............................................................................ 30
2.4.3 Urethane Crosslinkers ...................................................................................................... 30
2.4.4 Other Crosslinking Agents ............................................................................................... 31
2.5 New Developments ....................................................................................................................... 31
1
Rubber Curing Systems
References ...................................................................................................................................................... 45
The views and opinions expressed by authors in Rapra Review Reports do not necessarily reflect those of
Rapra Technology Limited or the editor. The series is published on the basis that no responsibility or
liability of any nature shall attach to Rapra Technology Limited arising out of or in connection with any
utilisation in any form of any material contained therein.
2
Rubber Curing Systems
3
Rubber Curing Systems
Figure 1
A typical cure curve
The curve exhibits a number of features which are used at which the torque rises to a prescribed level
to compare cure: above minimum. Suitably chosen, this provides
a measure of the scorch time at the curing
• Maximum torque, MH temperature.
• ts2, T2 or T5: There is a delay or induction time ts2 or T2: The time to reach a 2 unit increase in
before the torque or resistance value begins to rise. torque above minimum. This is another way to
Because the onset of this rise is difficult to express scorch safety. ts2 is defined as the time to
determine precisely, it is normal to note the point achieve 2% cure above minimum.
4
Rubber Curing Systems
T5: The scorch time at lower temperature is of elastic constant (C1) and finally into the concentration
importance too. This can be obtained by using a of chemical crosslinks. The proportions of mono-, di-,
Mooney Viscometer at lower temperature. A and polysulfidic crosslinks in the vulcanisates were
Mooney Viscometer is also used to measure the determined using thiol amine chemical probes.
viscosity of the compounds (important for dictating Following the cleavage of the poly- and disulfidic
injection-moulding behaviour). The viscometer is crosslinks, the samples were treated with methyl iodide
also used to assess the tendency to scorch, and to distinguish carbon-carbon based crosslinks from
sometimes the rate of cure of a compound. A useful monosulfidic crosslinks.
estimate of scorch behaviour is represented by T5,
the time taken from the beginning of the warm-up The brass coated steelcord used in adhesion tests was
period to that at which the Mooney value rises five of a 3+9x 0.22+1 construction with a Cu content of
units above the minimum value. 63%. The rubber to metal adhesion characteristics were
determined according to ASTM 2229-85. The wire
• T90: The most useful information obtained from adhesion data quoted are averages of 10 individual tests.
the rheometer curve is T90, which is defined as Wire adhesion samples were aged under the following
the time to achieve 90% cure. Mathematically, T90 conditions:
is the time for the torque to increase to:
• Heat aged - 3 days at 105 °C in the presence of air
90/100(MH − ML)+ ML
• Steam aged - 2 days at 121 °C
• Cure rate: A rise in the value of torque with time, • Salt aged - 7 days at 25 °C in a 10% solution of NaCl.
the slope of the curve, gives the measure of cure
rate. Sometimes cure rates of various cure systems
are compared with T90−ts2 data.
2 Curing Systems
5
Rubber Curing Systems
Aniline, however, is too toxic for use in rubber Accelerated sulfur vulcanisation is the most widely
products. Its less toxic reaction product with carbon used method. This method is useful to vulcanise NR,
disulfide, thiocarbanilide, was introduced as an SBR, BR, IIR, NBR, chloroprene rubber (CR), XIIR
accelerator in 1907. Further developments led to and EPDM rubber. The reactive moiety present in all
guanidine accelerators (a.3). Reaction products formed these rubbers is:
between carbon disulfide and aliphatic amines
(dithiocarbamates) were first used as accelerators in 1919
(a.4). These were and still are the most active accelerators
in respect to both crosslinking rates and extent of
crosslink formation. However, most dithiocarbamate
accelerators give little or no scorch resistance and
therefore cannot be used in all applications.
Figure 2
Crosslinking activities of different accelerators in NR at 140 °C. The approximate year of commercial
introduction is given in parentheses (405)
6
Rubber Curing Systems
Functionally, accelerators can also be classified into primary at about 1 phr and a secondary (or booster)
two broad categories: at 0.1 to 0.5 phr. These combinations cause faster
vulcanisation than each product separately and a
• Primary accelerators: Primary accelerators are considerable activation of cure which is positive
mercapto based accelerators, generally efficient for the general property spectrum of the
and confer good processing safety to the rubber vulcanisates. Examples are guanidines, thiurams,
compounds, exhibiting a broad vulcanisation dithiocarbamates, dithiophosphates, etc. Secondary
plateau with relatively low crosslink density. accelerators are usually scorchy, and very fast cure.
Examples are sulfenamides and thiazoles. Primary
accelerators provide considerable scorch delay, In order to rationalise the extensive range of accelerator
medium fast cure, and good modulus development. materials it is useful to classify them in terms of their
generic chemical structure listed next, some examples
• Secondary accelerators: Some rubber compounds are shown in Figure 3. The structures of commonly
use only one accelerator but most contain two, a used accelerators are given in Table 3.
Figure 3
Chemical structure of accelerators
7
Rubber Curing Systems
2-mercaptobenzothiazole MBT SH
N
2,2´-dithiobenzothiazole MBTS S
S 2
Benzothiazolesulfenamide
N-cyclohexylbenzothiazole-2-sulfenamide CBS S NH
N
N-butylbenzothiazole-2-sulfenamide TBBS S NH
2-morpholinothiobenzothiazole MBS S N O
N-dicyclohexylbenzothiazole-2-sulfenamide DCBS S N
Thiuram
S S
8
Rubber Curing Systems
S
tetrabenzylthiuram disulfide TBzTD CH2 N
S
2
2
Dithiocarbamate
S
S
zinc dibenzyldithiocarbamate ZBEC CH2 N
S Zn
2
2
Guanidines
H H
N N
diphenyl guanidine DPG
NH
H H
N N
di-o-tolylguanidine DOTG
NH
9
Rubber Curing Systems
Table 4 provides comparisons of the different classes Table 4 Comparison of different classes of
of accelerators based on their rates of vulcanisation. accelerators (a.11)
The secondary accelerators are seldom used alone, but
Class Vulcanisation rate
generally are found in combination with primary
accelerators to gain faster cures. Aldehyde-amine Slow
Guanidines Medium
Figure 4 compares five different classes of accelerators Thiazoles Semi-fast
in NR compounds. Thiurams and dithiocarbamates are Sulfenamides Fast-delayed action
fast but relatively scorchy. Thiazoles (e.g., MBTS) and
Sulfenimides Fast-delayed action
guanidines (e.g., DPG) are scorchy, slow accelerators
and seldom used alone. On the other hand sulfenamides Dithiophosphates Fast
(e.g., TBBS) exhibit excellent scorch safety and Thiurams Very fast
moderate cure rate with a good torque development. Dithiocarbamates Very fast
Figure 5
Comparison of primary accelerators/sulfur (0.5/2.5 phr) in NR at 144 °C (a.11)
10
Rubber Curing Systems
Figure 6
Comparison of primary accelerators/sulfur (1.2/1.5 phr) in SBR (a.11)
A comparison of cure between different primary A large number of secondary accelerators can be used
accelerators in NR and SBR is shown in Figures 5 with primary accelerators, thereby providing a great
and 6 respectively. The thiazole based accelerators deal of flexibility in processing and curing properties.
show different cure patterns in different rubbers. For Tables 5 and 6 (a.11) examine some of the more
example, TBBS shows better scorch than CBS and commonly used secondary accelerators and their effect
MBS in NR, whereas MBS shows improved scorch with sulfenamide accelerator, TBBS. Seven different
compared with TBBS and CBS in SBR. secondary accelerators are evaluated with TBBS in both
11
Rubber Curing Systems
NR and SBR compounds with MBTS/DPG as the A sulfur donor system in NR (DTDM 1.5; CBS 1.5;
control. The secondary accelerators also change the TMTD 0.5) yields a stable network structure with a
network structures. The polysulfidic crosslinks are contribution of 80% mono- and disulfidic crosslinks
converted to monosulfidic exhibiting heat stability. at the optimum cure at 143 °C or 183 °C curing (411).
12
Rubber Curing Systems
4,4´-dithiodimorpholine
O N S S N O 13.6 125
(DTDM)
N
2-morpholino-dithio-benzothiazole
S S N O 28.4 129
(MBSS)
S
O O
caprolactam disulfide
28.8 131
(CLD) N S S N
S S
Dipentamethylenethiuram tetrasulfide
N S4 N 16.6 120
(DPTT)
N-oxydiethylene thiocarbamyl-N´-
oxydiethylenesulfenamide N S N O 12.9 136
(OTOS)
O
S
TBzTD* CH2 N 5.8 124
S
2
2
13
Rubber Curing Systems
dynamic properties (119, a.12), as well as the dynamic properties. Datta and co-workers (4)
nitrosamine issue. The solution to this has been to investigated the effects of using a small amount of
introduce nitrosamine safe ultra accelerators such TBzTD in NR formulations cured at 150 °C for 90
as TBzTD (396, a.13). minutes. Table 8 lists the formulations used, Table 9
illustrates the processing and cure characteristics of
Unlike TMTD, TBzTD is unique since use of a small the different rubbers, Table 10 shows the vulcanisate
amount of TBzTD (0.1-0.2 phr) with a sulfenamide properties, Table 11 indicates the crosslink types
system does not influence the processing found in network studies and Table 12 gives the
characteristics, but does improve cure rate and viscoelastic properties of the different formulations.
Table 8 Formulations
Ingredients/stocks 1 2 3 4 5
NR SMR CV 100 100 100 100 100
N-330 50 50 50 50 50
Zinc oxide 5 5 5 5 5
Stearic acid 2 2 2 2 2
Santoflex 6PPD 2 2 2 2 2
Santocure CBS 0.6 0.6 0.6 0.6 0.6
Perkacit TBzTD - 0.1 0.2 - -
Perkacit TMTD - - - 0.1 0.2
Sulfur 2.3 2.3 2.3 2.3 2.3
14
Rubber Curing Systems
15
Rubber Curing Systems
2.2 Cures for Speciality Elastomers In all cases, nitrosamine free or safe alternatives are
looked for. For System 1, the following alternative was
The curing systems used to vulcanise speciality suggested:
elastomers such as EPDM, CR, IIR and NBR are
different than those used to cure NR, SBR, BR and its
blends. The former elastomers are less unsaturated and
therefore need a high ratio of accelerator to sulfur. System 1 NA free alternative
S 1.5 S 1.3
MBT 0.5 MBT 0.75
2.2.1 Cure Systems for EPDM TMTD 1.5 CBS 3.8
16
Rubber Curing Systems
System 2, the ‘Triple 8’ system can be replaced by an Recently an EPDM formulation has been developed
NA-safe alternative as shown next. The comparative based on DTDM, TMTD, ZDBC and DPTT called the
properties are listed in Table 15. ‘2828’ system, it comprises:
17
Rubber Curing Systems
18
Rubber Curing Systems
2.2.2 Cure Systems for Nitrile Rubber 2.2.3 Cure Systems for Polychloroprene
Cure systems for nitrile rubber are somewhat Chlorobutadiene or chloroprene rubbers (CR), also
analogous to those of NR, SBR or BR except that called neoprene rubbers, are usually vulcanised by
magnesium carbonate (MC) treated sulfur is usually the action of metal oxides. The crosslinking agent is
used to aid sulphur dispersion into the polymer usually zinc oxide in combination with magnesium
(a.12). Common accelerator systems include oxide (a.16). CR can be vulcanised in the presence of
thiazole, thiuram, thiazole/thiuram, or sulfenamide/ zinc oxide alone, but magnesium oxide is necessary
thiuram types. Examples of these systems are shown to confer scorch resistance. The reaction may involve
in Table 18. the allylic chlorine atom, which is the result of the
small amount of 1,2 polymerisation (a.17).
As operating requirements for nitrile rubber become
more stringent, improved ageing and set properties Cl
become important. In order to address those
Cl
requirements, formulations with sulfur donor systems
(as a partial or total replacement of rhombic sulfur)
CH2
have been proposed. These are summarised in
Tables 19 and 20. The advantages of these systems
n 0.015n
are improved set and ageing resistance while adequate
processing safety and fast cures are maintained.
19
Rubber Curing Systems
Table 19 High sulfur versus low sulfur cure systems for nitrile rubber
Curatives/stocks 1 2
MC treated sulfur 1.5 0.3
MBT 1.5 0
TBBS 0 1.0
TMTD 0 1.0
Mooney scorch at 135 °C
T5 (minutes) 8.1 8.1
Rheometer at 160 °C
T90 (minutes) 15.2 10.2
Physical properties (Cure: 160 °C/T90)
Hardness (Shore A) 71 69
Modulus at 100% elongation (MPa) 3.6 3.1
Tensile strength (MPa) 16.2 15.1
Elongation at break (%) 475 485
Heat ageing at 100 °C/70 h)
Hardness (Shore A) 78 74
Tensile strength retention (%) 68 89
Compression set
100 °C/22 h (%) 50 24
20
Rubber Curing Systems
Most accelerators used in the sulfur vulcanisation of Table 21 Vulcanisation systems for CR (phr)
other high diene rubbers are not applicable to the metal
oxide vulcanisation of CR. An exception is the use of Curatives/Stock 1 2 3
a so-called mixed curing system for CR, in which metal Zinc oxide 5 5 5
oxide and accelerated sulfur vulcanisation are
combined. Along with the metal oxides, TMTD, DOTG Magnesium oxide 4 0 4
and sulfur are used. This is a good method to obtain Calcium stearate 0 5.5 0
high resilience and dimensional stability. Stearic acid 0 0 1
The accelerator that has been widely used with metal TMTM 0 0 1
oxide cures is ethylene thiourea (ETU) or 2- DOTG 0 0 1
mercaptoimidazoline. Further extensive use of ETU in
ETU 0.5 0.5 0
vulcanisation of CR is restricted because it is a
suspected carcinogen. The related compound, Sulfur 0 0 1
thiocarbanilide, used formerly as an accelerator for
sulfur vulcanisation, has been revived for CR
vulcanisation; other substitutes for ETU have been
proposed (401, 406). 2.2.4 Cure Systems for Butyl and Halobutyl Rubber
The following mechanism for ETU acceleration has Isobutylene-based elastomers include butyl rubber, the
been proposed (a.18), Figure 7. copolymer of isobutylene and isoprene, halogenated
butyl rubber, star-branched versions of these polymers
Recipes for metal oxide vulcanisation of CR are given and the terpolymer isobutylene-para-methylene
in Table 21. In one case, calcium stearate was used styrene-bromo-para-methyl styrene (BIMS). A number
instead of magnesium oxide to obtain better ageing of reviews on isobutylene-based elastomers are
characteristics (a.19). available (395, a.20, a.21).
Cl S S
N -O N
Cl H H
ZnCl+ CH2
- ethylene CH2
urea
CH2
S + ZnCl2
S-
Cl
H2C
Figure 7
CR crosslinking
21
Rubber Curing Systems
Butyl rubber is used in tyre tube applications among One investigation suggested (19) adding 0.75 phr of
others. A typical formulation (mix 01) is shown in antireversion chemical, 1,3-bis(citraconimidomethyl)
Table 22. The performance needs for inner tubes are: benzene (Perkalink 900) for improving heat resistance
(mix 02). It is known that Perkalink 900 provides heat
• Low air permeability resistance to sulfur cured diene elastomers. The effect of
Perkalink 900 on IIR is shown in Figure 8. It is clear that
• Improved heat resistance
Perkalink 900 has a positive effect on the torque retention,
• Low tension set which can be translated into better heat resistance.
Figure 8
Cure characteristics of the mixes 01 (Control) and 02 (+ Perkalink 900) at 170 °C
22
Rubber Curing Systems
The cure data are shown in Table 23. The data presented Table 24 presents some data concerning physical
clearly show that Perkalink 900 does not influence the properties of the vulcanisates cured at 170°C for T90
processing characteristics. Although a longer T90 and 30 minutes. A careful comparison of the data clearly
seems to be negative, raising the temperature by 5 or shows the decline in the properties of the control,
10 °C will neutralise this effect with the additional whereas a higher retention of vulcanisate properties is
advantage of higher cure rate and stabilisation of tan observed for the vulcanisate containing Perkalink 900.
delta characteristics.
Table 25 presents the relevant data concerning air
permeability. It is evident that Perkalink 900 does not
have any negative influence on air permeability.
Table 23 Cure characteristics of mixes 01
and 02 at 170 °C Sulfur crosslinks have limited stability at elevated
Properties/stocks 01 02 temperatures and can rearrange to form new
crosslinks. This results in poor permanent set and
MH-ML (Nm) 0.78 0.95
creep for vulcanisates when exposed for long periods
Scorch safety, ts2 (minutes) 2.6 2.3 of time at high temperatures. Resin cure systems
provide C-C crosslinks and heat stability. Alkyl
Optimum cure time, T90 (minutes) 9.5 11.9
phenol formaldehyde derivatives are usually
Tan δ (30'-T90) 0.112 0.056 employed for tyre bladder applications. A typical
vulcanisation system is shown in Table 26 (mix 03).
ML (1+4) @ 100 °C (MU) 55 53
Perkalink 900 has been added at 0.5 phr (mix 04)
Table 24 Properties of butyl rubber mixes 01 and 02 before and after ageing
(cure 170 °C/T90 and 30 minutes, in the parentheses)
Properties 01 01 (aged) 02 02 (aged)
Hardness (Shore A) 47 (45) 50 (48) 48 (48) 50 (50)
Modulus (MPa) at
50% elongation 0.94 (0.87) 0.82(0.72) 0.94 (0.90) 0.90(0.88)
100% elongation 1.62 (1.5) 1.27 (1.01) 1.60 (1.58) 1.63 (1.60)
300% elongation 4.9 (4.6) 4.2 (3.2) 5.2 (5.2) 4.8 (4.7)
Tensile strength (MPa) 11.2 (10.0) 8.8 (6.2) 11.6 (11.0) 11.1 (9.5)
Elongation at break (%) 630 (615) 590 (530) 640 (625) 620 (510)
Tension set (%) 7.1 12.5 5.7 6.2
23
Rubber Curing Systems
Table 28 Physical properties of the butyl rubber formulations (cure: 190 °C/T90+2')
Properties/stocks 03 04 05
At room temperature
Hardness (Shore A) 65 65 65
Modulus at 100% elongation (MPa) 1.7 1.6 1.7
Modulus at 300% elongation (MPa) 5.2 5.0 5.5
Tensile strength (MPa) 13.0 13.2 13.5
Elongation at break (%) 670 680 660
300% Tension set (%) 12.5 10.0 9.1
At 190 °C
Modulus at 100% elongation (MPa) 1.7 1.6 1.8
Modulus at 300% elongation (MPa) 5.3 4.8 5.8
Tensile strength (MPa) 6.1 7.0 7.7
Elongation at break (%) 350 370 380
Aged 2 d/177 °C; Pulled at 190 °C
Modulus at 100% elongation (MPa) 3.1 3.2 3.4
Tensile strength (MPa) 4.2 5.0 6.2
Elongation at break (%) 210 220 230
200% Tension set (%) 28 20 18
and 0.75 phr (mix 05). The comparative properties rapid rate of cure with reduced curative levels, cure
of these formulated rubbers are summarised in compatibility with other polymers and good cure
Tables 27 and 28. adhesion to themselves and other elastomers (394,
415, a.24-a.26). This combination of properties
makes them potentially superior base elastomers for
2.2.4.2 Halobutyl Rubber the manufacture of a variety of mechanical goods
ranging from heavy duty shock absorbers to smaller
Halobutyl rubber (XIIR) vulcanisates are generally sound and vibration damping mountings, hoses,
acoustic loss materials having essentially the same belting and many other tyre and non-tyre
physical and dynamic mechanical properties as applications. One of the primary applications for
regular butyl rubber. They have the advantage of XIIR is in the inner liners for tyres.
24
Rubber Curing Systems
The type and level of a suitable chemical crosslinking benzene (Perkalink 900) is being explored in this
system for compounding must be selected very carefully application to bring the desired properties. The model
to achieve the desired combination of properties and formulations are shown in Table 29. The cure data and
service life. Several crosslinking systems are available, physicomechanical properties of these vulcanisates are
one of them is crosslinking via bis-maleimides (HVA- tabulated in Table 30. The data clearly show that
2) (400). Unfortunately crosslinking with HVA-2 does Perkalink 900 acts as an efficient crosslinker in XIIR.
not generate sufficient advantage with respect to heat This can be explained via the reaction mechanism as
generation and set characteristics. The use of shown in Figure 9.
antireversion agent, 1,3 bis(citraconimidomethyl)
ΔT in 25' 60 30 18 20
*nm = not measured
25
Rubber Curing Systems
Figure 9
Reaction of Perkalink 900 with XIIR in the presence of zinc oxide
It can be concluded from this study that Perkalink 900 A further limitation with regard to the suitability of
can be used as a crosslinker in XIIR and could provide peroxides concerns the efficiency of crosslinking.
additional advantages such as better high temperature Higher efficiencies are observed for those peroxides
compression set and lower heat built up in the Goodrich that form one of the radicals shown in Figure 12 during
Flexometer test over HVA-2. homolytic decomposition (a.28).
26
Rubber Curing Systems
Figure 10
Organic peroxides for crosslinking elastomers
Figure 11
Peroxides containing more than one peroxy group
Figure 12
Radicals formed during the homolytic cleavage of peroxides that are most effective in producing crosslinks
27
Rubber Curing Systems
• inferior tensile, tear and flex properties, Polymers that cannot be effectively crosslinked with
peroxides are:
• inferior abrasion resistance,
28
Rubber Curing Systems
29
Rubber Curing Systems
EPDM rubber preferred for a great number of specific 2.4 Sulfur Free Curing Systems
applications. For many years peroxide-cured EPDM
based compounds have been applied, e.g., for window Some special vulcanising agents can cure diene rubbers
seals, automotive hoses, steam hoses, conveyer belts, such as NR, SBR and BR. These are now discussed.
roof sheeting, tank lining, roll coverings, mouldings,
and last but not least, for electrical insulation and
jacketing compounds. Two formulation types (403) are 2.4.1 Phenolic Curatives, Benzoquinone
illustrated in Tables 33 and 34. Derivatives and Bismaleimides
30
Rubber Curing Systems
OH
N NO
[O]
+ H2O
N NO
OH
Benzoquinonedioxime Dinitrosobenzene
NO
Ene reaction
+
Rubber HO N
NO
Figure 13
Vulcanisation by benzoquinonedioxime
31
Rubber Curing Systems
O O
N N
O
O
BCI-MX
S SO3-+Na
Na+-O3S S .2 H2O
HTS
Figure 14
Structures of HTS and BCI-MX
bis(citraconimidomethyl) benzene (BCI-MX, Perkalink wet, ice or snow but with minimum noise generation.
900) (26, 157, 181, 210, 260, 263, 284, 289, 309, 392, Trying to balance the three main apparently conflicting
a.42-a.44), an antireversion agent. The structures of HTS needs of wear, wet grip and rolling resistance, together
and BCI-MX are shown in Figure 14. with many other performance requirements leads to a
wide range of tread formulations covering several natural
and synthetic rubbers combined with different ratios of
alternative filler types. Compounds need good flexibility,
3 Some Practical Examples with thermal resistance and abrasion resistance. The cure
system should be CV/SEV. Accelerators used are
Varying Cure Systems sulfenamide class (TBBS, CBS, MBS).
Good compounding means formulas are developed that A typical formulation for a radial tyre truck tread is
are environmentally safe, factory processable, provide shown in Table 35. For improving heat resistance, the
a satisfactory service life, and are cost competitive to use of Perkalink 900 is recommended (289). The
other compounds used in the same applications. Costs recommended loading for this cure system is 0.5 phr.
are always a major concern and constantly increasing
environmental safety regulations most not be
overlooked. In this section, the focus is on cure systems
and formulations of practical interest. This provides a Table 35 Radial truck tread formulation
guideline for compounding in various applications.
Ingredients phr
NR 100
The tread is probably the most critical component of the Aromatic oil 8
tyre determining the final performance. It is also the 6PPD 2
thickest component of the tyre and it contributes most
TMQ 1.5
of the energy losses that in turn will cause a rise in the
tyre’s running temperature and an increase in fuel TBBS 1.5
consumption for the vehicle. Tread is also responsible PVI 0.1
for the safety component of the tyre and its surface is
designed to provide good grip in all conditions of dry, Sulfur 1.5
32
Rubber Curing Systems
A typical formulation for a bias tyre truck tread is shown order to maximise these benefits the silane coupling
in Table 36. agent bis-(3-triethoxysilylpropyl) tetrasulfide
(TESPT) is often employed, functioning by
A typical formulation for a passenger tyre tread is chemically bonding the filler particles to the
shown in Table 37. To raise the curing temperature, elastomer network. In addition, this coupling agent
the use of antireversion chemical, Perkalink 900 has may act as a delayed action sulfur donor, providing
been recommended (119). some degree of reversion resistance via the formation
of sulfidic crosslinks of low sulfur rank. A passenger
Silica as a reinforcing filler is being used more tread containing silica needs a cure system based on
extensively in the tyre industry to provide improved sulfenamide/sulfur (SEV/CV system) and guanidine
tear resistance and decreased rolling resistance. In activators (DPG).
33
Rubber Curing Systems
Table 39 Model OTR tyre tread formulation 3.1.2 Tread Base or Sub Tread
Ingredients phr
A natural rubber rich undertread layer can enhance the
NR SMR 10 100 adhesion between belt or cap-ply and tread whilst a
Carbon black N-220 40 thicker subtread compound may be included to offer
Silica, Perkasil KS 408 20 some additional benefits of low hysteresis for car tyres
and low heat generation for truck tyres within the bulk
Zinc oxide 5 of a thick section. The cure system needs better flexibility
Stearic acid 2 and low heat generation. Typically the cure system will
Aromatic oil 3 be based on CV/SEV. A general composition for a tyre
tread base is depicted in Table 41.
Resin cumarone 3
Coupling agent, TESPT 3.0
TMQ 1.5 Table 41 Tyre tread base formulation
6PPD 2.5
Ingredients ph r
Wax Sunolite 240 1.0
NR 100
CBS 1.4
N-550 45
DPG 1
Zinc oxide 5
Sulfur 1.4
Stearic acid 2
Aromatic oil 10
Aircraft tread requires a high modulus, better abrasion
6PPD 2.5
resistance and low heat generation. The above
requirements could be satisfied by using a CV/SEV Microcrystalline wax 2
cure system with DCBS as accelerator and insoluble CBS 0.9
sulfur (IS) as crosslinker. For achieving high modulus,
HMT and a resorcinol system is used. In order to reduce PVI 0.1
the heat generation, the use of Perkalink 900 has been Sulfur 1.5
suggested. A typical formulation for an aircraft tyre
tread recipe is shown in Table 40. Perkalink 900 0.5
34
Rubber Curing Systems
Addition of Duralink HTS (hexamethylene-1,6- The cure system of choice for a carcass compound is
bis(thiosulfate), disodium salt dihydrate) improves based on a scorch resistant cure package. Care must
adhesion characteristics under ageing environments also be taken that the necessary high loadings of sulfur
(157). Formulations without H/R bonding systems are or other additives do not bloom to the surface of the
also available (157). calendered sheet since good tack levels must be
maintained throughout the building stage. For this
reason, thermally stable, insoluble sulfur and bloom
3.1.4 Sidewall resistant adhesion additives are required. Because of
the importance of adhesion to brass plated steel cord,
The sidewall rubber provides protection for the body the cure system suitable for this application is based
plies and in the case of heavy-duty truck tyres may be on a slow accelerator such as DCBS with a high
of significant gauge in areas where abrasion or damage amount of insoluble sulfur (generally 4-5 phr). A
from kerb strikes is a likely occurrence. Sidewall typical formulation for a truck radial carcass
compounds cover the thinnest part of the tyre where compound is shown in Table 44.
most flexing occurs as the tyre deflects. They therefore
need to have a high degree of flex resistance and good A passenger tyre carcass formulation is shown in
dynamic properties, as well as excellent age resistance. Table 45. In this application, adhesion to fibres is a
Sidewall compounds contain additional ingredients to consideration. The cure system suitable for this
prevent oxidative or ozone attack since this part of the application is based on TBBS/MBTS/IS.
tyre will be particularly exposed to the sun and the
elements. The cure system should be CV or between
CV/SEV. A typical formulation is shown in Table 43. 3.1.6 Bead
35
Rubber Curing Systems
3.1.7 Apex
Table 45 Passenger tyre carcass formulation The apex or filler insert components provide the gradual
Ingredients ph r shape and stiffness reduction from the rigid bead coil
to the flexible mid-sidewall of the tyre. These
NR 60
components need to be very hard to provide good
BR 20 vehicle handling and to reduce the risk of flexural
SBR 27.5 fatigue at component endings. High loadings of filler
or reinforcing resins make such components difficult
N-660 40 to process and notoriously dry, lacking in tack.
Zinc oxide 3 Tackifying additives and process aids may therefore
be required to help in the tyre manufacturing process.
Stearic acid 2.0 The cure system is shown in the formulation tabulated
Processing oil 13 in Table 47. TBzTD is used to obtain cure activation.
TMQ 0.5
Octylated diphenylamine 1 3.1.8 Cap-Ply
Resin 1.0
Cap-plies are more commonly used on high
MBTS 0.1
performance car tyres. Having a circumferential cord
TBBS 0.7 direction they provide an additional contractive force.
They are also found more often now in normal
IS OT 20 2.8
performance tyres where they can act as a barrier layer
PVI 0.1 between the tread and the casing to restrict migration
of chemicals from the tread into the belt. Cap-ply
requires high modulus and good adhesion behaviour.
The cure system used to achieve the target properties
require high modulus and good adhesion to steel wires. is based on a combination of CBS and DCBS with a
High modulus is achieved by using resorcinol/HMMM high amount of insoluble sulfur. A resorcinol/HMMM
or phenol formaldehyde resins. The cure system is based system is used to obtain the required high modulus. A
on sulfenamide with a high amount of insoluble sulfur. A typical formulation of a cap-ply (passenger) compound
typical cure package is shown in Table 46. is shown in Table 48.
36
Rubber Curing Systems
Table 47 Tyre apex formulation the liner was a separate tube of natural or butyl or
more particularly, halobutyl rubber compound as an
Ingredients phr integral part of the tyre structure. Adhesion levels of
NR 100 butyl compounds can be critically low requiring an
insulating or barrier layer of a natural rubber
N-351 55
compound to act as an interface between the liner and
Zinc oxide 10 the casing. Zinc oxide with MBTS and a small amount
Stearic acid 2 of sulfur is used to crosslink halobutyl rubber. A
typical formulation of an inner liner is documented
SP 6700 Resin 2
in Table 49.
Phenol formaldehyde resin 10
Bonding agent 2
6PPD 2 Table 49 Inner liner formulation
TMQ 1 Ingredients phr
TBBS 0.6 Chlorobutyl 1065 100
TBzTD 0.2 N-660 60
PVI 0.2 Naphthenic oil 8
IS OT 20 5.0
Stearic acid 2
Phenolic resin tackifier 4
Homogenisers 7
Table 48 Passenger tyre cap-ply formulation
Magnesium oxide 0.15
Ingredients phr
Zinc oxide 3
NR 80
Sulfur 0.5
BR 20
MBTS 1.5
Mineral oil 7
N-326 55
Silica 7.5
3.2 Industrial Rubber Products
Mixture of N,N´-diaryl-p- 1
phenylenediamines (DTPD)
This section provides information on the property
TMQ 1 requirements and the best cure systems in compounds
Resorcinol 1.25 typical of some industrial rubber products (IRP).
Examples of industrial rubber products and typical
HMMM 1.5 polymers used are shown in Table 50. In a recent study
CBS 0.4 the effect of an antireversion agent (Perkalink 900) was
also reported (a.45).
DCBS 1.0
ZnO 8
Zinc stearate 1.0
Table 50 Examples of industrial rubber
IS OT 20 4.5 product applications
Application Polymer
Conveyor belt cover NR
3.1.9 Inner Liner
Engine mount NR
The inner liner forms the vital internal membrane Tank pad NR/SBR/BR blend
which hold the inflation medium at an elevated
Oil seal NBR
pressure within the structure of the tyre. In early days
37
Rubber Curing Systems
3.2.1 Conveyor Belt Cover - NR Cure characteristics for these two formulations are
shown in Figure 15. The antireversion agent has no
The key performance properties of conveyor belts, effect on scorch resistance and time to optimum cure.
particularly belt cover compounds, are flex resistance, The beneficial effect becomes apparent when reversion
abrasion resistance and low heat build up. In order to occurs, as observed in the control compound: the
achieve better flex resistance, a conventional cure compound containing the antireversion agent maintains
package is recommended. However, such a system a torque level close to the maximum.
suffers from the adverse effects of heat generation. In
a recent study, the addition of Perkalink 900 was The antireversion effect is also evident in the stability
recommended, the effect is shown in a typical, NR of vulcanisate properties following overcure or air
based belt cover formulation in Table 51. ageing at 100 °C. Tensile, flex/cut growth
characteristics and abrasion resistance are superior for
the compound containing the antireversion agent.
Table 51 Conveyor belt cover formulations Figure 16 shows the improvement in tensile strength
of aged compounds containing Perkalink 900.
Ingredients Control + Perkalink 900 Figure 17 illustrates the superior flex/cut growth
NR 100 100 properties of compound containing Perkalink 900.
Figure 18 shows an improvement in abrasion resistance
N330 45 45
of formulations containing Perkalink 900.
Aromatic oil 4 4
ZnO 5 5 A major benefit imparted by the antireversion agent
Stearic acid 2 2 concerns heat build up under dynamic conditions as
encountered during the service of conveyor belts. Both
6PPD 1 1 at optimum cure and overcure the antireversion agent is
CBS 0.5 0.5 extremely effective in reducing heat build up as
Sulfur 2.5 2.5
determined by the Goodrich Flexometer test (Figure 19).
The control compound, containing no antireversion
Perkalink 900 - 1 agent, exhibits a significantly higher heat build up. This
Figure 15
Cure characteristics of conveyor belt cover formulations at 150 °C
38
Rubber Curing Systems
Figure 16
Tensile strength of conveyor belt cover formulations
Figure 17
De Mattia flex/cut growth of conveyor belt cover formulation (cure 30'/150 °C)
Figure 18
Abrasion loss (DIN) of conveyor belt cover formulations
39
Rubber Curing Systems
Figure 19
Goodrich Flexometer heat build up at 100 °C after 30 minutes – tests on conveyor belt cover compounds
(Load 108 N, Stroke 4.45 mm, Frequency 30 Hz)
suggests that rolling energy losses can be reduced Table 52 Engine mount formulations
through the use of Perkalink 900, an important
consideration in today’s energy conscious environment. Ingredients Control Perkalink 900
NR 100 100
N-660 42 42
3.2.2 Engine Mount - NR
Zinc oxide 5 5
The essential performance properties for an engine Stearic acid 2 2
mount are low heat build up and low dynamic
compression set. In order to achieve the desired Oil 9 9
properties, a cure system comprising of sulfenamide MC wax 2 2
(moderate loading, 1.2-1.7 phr) with sulfur (2-2.5
phr) is recommended. A small amount of ultra 6PPD 2 2
accelerator might be necessary to generate a TMQ 2 2
crosslink network capable of improving dynamic
compression set as well as heat build up. In spite of Resin 2 2
this modified cure system (CBS/TMTD/S), the Santocure CBS 2.5 2.5
properties are still not optimum, particularly with
regard to heat build up. The addition of an Perkacit TMTD 0.2 0.2
antireversion agent might provide advantage and Sulfur 2.25 2.25
with this in mind the effect of Perkalink 900 has been
Perkalink 900 - 0.75
studied. The formulations are shown in Table 52.
These have been determined for a typical engine
mount compound based on natural rubber, with and
without Perkalink 900.
overcure (at 150 °C and 170 °C) and ageing at 100 °C
The engine mount formulation contains a cure indicate a trend of improved strength (Figure 20).
package tending to an SEV system; this will provide
a greater degree of reversion resistance compared to The important vulcanisate properties demanded by
a CV cure system. this application, low heat build up and low dynamic
set, have been determined in the Goodrich Flexometer
The cure data show that Perkalink 900 does not affect test. The compound containing the antireversion agent
scorch time or time to optimum cure, this is exhibits a marked decrease in heat build up and
illustrated in Table 53. Tensile data following dynamic permanent set (Figures 21 and 22).
40
Rubber Curing Systems
Table 53 Cure characteristics at 150 °C, (170 °C) and Mooney scorch
Control Perkalink 900
ML (Nm) 0.17 (0.16) 0.16 (0.15)
MH-ML torque (Nm) 1.49 (1.35) 1.43 (1.34)
ts2 (minutes) 4.1 (1.1) 4.1 (1.1)
T90 (minutes) 8.7 (2.5) 8.4 (2.4)
Mooney scorch, T5, 121 °C 25.6 25.4
Figure 20
Tensile strength tests on engine mount compounds
Figure 21
Goodrich Flexometer heat build up at 100 °C after 30 minutes – tests on engine mount compounds
(Load 108 N, Stroke 4.45 mm, Frequency 30 Hz)
41
Rubber Curing Systems
Figure 22
Goodrich Flexometer Dynamic Permanent Set at 100 °C after 30 minutes – tests on engine mount compounds
(Load 108 N, Stroke 4.45 mm, Frequency 30 Hz)
Even at the increased cure temperature of 170 °C the agent have been evaluated, are listed in Table 54. Cure
compound containing the antireversion agent is little characteristics are given in Table 55.
changed with regard to heat build up and dynamic set
compared to the lower cure temperature. The control
compound on the other hand exhibits both increased Table 54 Tank pad formulations
heat build up and dynamic set at the higher cure Ingredients 1 2 3
temperature. This suggests that increasing the cure
temperature as a means of increasing productivity NR 60 60 60
would have no detrimental effect on compound SBR 1500 20 20 20
performance in this application. BR Buna CB10 20 20 20
N-220 70 70 70
Zinc oxide 4 4 4
3.2.3 Tank Pad – NR/SBR/BR Blend
Stearic acid 2 2 2
The required properties for a tank pad are heat stability, Oil 40 40 40
low heat generation, improved flex and good Santoflex 6PPD 1 1 1
compression set. This can be achieved by selecting a
MC wax 3 3 3
cure package between SEV and towards an EV cure. A
combination of a sulfenamide with a thiazole is suitable. Santocure TBBS 1 1 1
Generally the sulfenamide level should be low and the Perkacit MBTS 2 2 2
thiazole accelerator should be high. This is to allow a Santogard PVI 0.15 0.15 0.15
reaction between the sulfenamide and the thiazole
Sulfur 2 2 2
accelerator so that the intermediate can function as an
efficient accelerator. The sulfur loading is generally Perkalink 900 - 0.5 0.75
high to address the improved flex requirements.
Because of high sulfur loadings, the system suffers from
the adverse effects of heat and reversion resistance. Table 55 Cure characteristics of tank pad
formulations at 155 °C
Perkalink 900 is active in compounds based on blends
1 2 3
of NR with the synthetic elastomers SBR and BR. An
evaluation in a tank pad formulation has provided ML (Nm) 0.18 0.18 0.18
evidence of reduced heat build up on overcure; overcure MH-ML torque (Nm) 1.37 1.33 1.31
is a common problem in the manufacture of these ts2 (minutes) 3.4 3.6 3. 7
relatively bulky components. The control and test
formulations, in which two levels of the antireversion T90 (minutes) 7.2 7.3 7. 3
42
Rubber Curing Systems
Although little advantage is observed with regard to greater thermal stability in terms of blow-out resistance
vulcanisate physical properties (Table 56), a benefit is (Figure 24). This observation is of important practical
apparent in terms of reduced heat build up as shown in significance since it is not uncommon for tank pads to
Figure 23. In addition, the antireversion agent provides blow-out during service.
Figure 23
Goodrich Flexometer heat build up at 100 °C after 60 minutes – tests on tank pad formulations
(Load 108 N, Stroke 4.45 mm, Frequency 30 Hz)
Figure 24
Goodrich Flexometer blow-out at 100 °C – tests on tank pad formulations
(Load 216 N, Stroke 4.45 mm, Frequency 30 Hz, test time 60')
43
Rubber Curing Systems
4 Concluding Remarks
Table 57 NBR based oil seal formulations
Cure systems play an important role in achieving
Ingredients Control +Perkalink 900 the performance requirements of rubber articles.
NBR 100 100 Furthermore, these performance requirements are
N-550 60 60 becoming more and more demanding due to the
severity of service conditions, health and safety
ZnO 5 5
concerns and quality expectations.
Stearic acid 1 1
DOP 15 15 Today, more and more know how is available to
design a cure system capable of meeting these
TMQ 2 2
demanding requirements. New developments in
MBTS 1 1 materials allow compounders to reformulate a cure
TMTD 0.1 0.1 system capable of providing improved performance.
Sulfur 1.5 1.5 Antireversion chemicals constitute a class of such
materials, and can improve service performance.
Perkalink 900 - 0.75 Health and safety issues, for example the concerns
about the possible carcinogenicity of N-
nitrosamines, have also lead to the introduction of
new rubber additives.
Table 58 Cure characteristics at 170 °C of
NBR oil seal formulations
Cure systems, however, paint only part of the picture
Control + Perkalink 900 with regard to the manufacture of rubber articles;
MH-ML torque (Nm) 1.36 1.39 polymers and fillers are equally important in meeting
ts2 (minutes) 0.9 0.9 performance requirements. In addition, compound
mixing and processing play a critical role in
T90 (minutes) 1. 9 2.1 achieving the final vulcanisate properties.
Table 59 Physical properties of NBR oil seal formulations - cure 5'/170 °C (and 120'/170 °C)
Properties Control + Perkalink 900
Modulus at 300% elongation (MPa) 12.9 (13.6) 13.3 (14.0)
Tensile strength (MPa) 19.0 (18.2) 20.4 (21.1)
Elongation at break (%) 530 (470) 560 (470)
Tear strength (kN/m) 62 (55) 65 (60)
44
Rubber Curing Systems
Figure 25
Goodrich Flexometer Dynamic Permanent Set at 100 °C after 120 minutes – tests on NBR oil seal formulations
(Load 108 N, Stroke 4.45 mm, Frequency 30 Hz)
Figure 26
Swelling in ASTM oil #3, 168 hours at 150 °C (cure 5'/170 °C) – tests on NBR oil seal formulations
a.2 L. Bateman, C.G. Moore, M. Porter and B. a.6 L.B. Sebrell and C.W. Bedford, inventors;
Saville in The Chemistry and Physics of Rubber Goodyear Tire & Rubber Company, assignee;
like Substances, Ed., L. Bateman, John Wiley US Patent 1,544,687, 1925.
and Sons, NY, 1963, Chapter 19.
a.7 G. Bruni and E. Romani, Indian Rubber
a.3 M.L. Weiss, inventor; Dovan Chemical Corp., Journal, 1921, 62, 63.
assignee; US Patent 1,411,231, 1922.
a.8 E. Zaucker, M. Bögemann and L. Orthner,
a.4 S.B. Molony, inventor; Michigan Chemical inventors; I.G. Farben Industrie AG, assignee;
Company, assignee; US Patent 1,343,224, 1920. US Patent 1,942,790, 1934.
45
Rubber Curing Systems
a.9 M.W. Harman, inventor; Monsanto Chemical a.27 I.I. Ostromysklenki, Russian Physical-
Company, assignee; US Patent 2,100,692, Chemical Society Journal, 1915, 47, 1467.
1937.
a.28 R.C. Keller, Rubber Chemistry and
a.10 A.Y. Coran and J.E. Kerwood, inventors; Technology, 1988, 61, 238.
Monsanto Company, assignee; US Patent
a.29 L. Gonzales, A. Rodriguez and A. Macros,
3,546,185, 1970.
Recent Res. Dev. Polym. Sci., 1998, 2, 485.
a.11 B.H. To, Rubber Technology, Ed., J.S. Dick,
a.30 J. Johansson, Peroxide dispersions and their
Hanser, Munich, 2001, Chapter 15.
applications, Presented at the Southern Rubber
a.12 R.M. Russell, T.D. Skinner and A.A. Group, Inc., Winter Technical Session, March
Watson, Rubber Chemistry and Technology, 2000.
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a.31 A.J. Wildschut, Rubber Chemistry and
a.13 D. Seeberger, Flexsys Technical Bulletin, Technology, 1946, 19, 86.
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a.14 M. Morton, Rubber Technology, Third Technology, 1946, 19, 900.
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a.15 B.H. To, Rubber Technology, Ed. J.S. Dick, a.34 A.B. Sullivan, J. Org. Chem., 1966, 31, 2811.
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a.35 C.S.L. Baker, D. Barnard and M. Porter,
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Stevenson, G. Alliger and I.J. Sjothun, 141.
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a.37 Th. Kempermann, Rubber Chemistry and
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a.19 R.O. Becker, Rubber Chemistry and a.38 Th. Kempermann, Bayer AG, Internal report,
Technology, 1964, 37, 76. AN 594.
a.20 E.N. Kresge and H.C. Wang in Kirk Othmer a.39 W. Hofamann, Vulkanisation und
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a.40 P.G. Moniotte, inventor; Monsanto Europe SA,
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a.41 J.M. Delseth, D.E. Mauer and P.G. Moniotte,
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46
Rubber Curing Systems
47
Rubber Curing Systems
48
References and Abstracts
indicates that the curing mechanisms of Zn(MAA)2 in OPTIMISATION OF CROSSLINKING AND GAS
two curing systems are different. 8 refs. LIBERATION IN CELLULAR RUBBER
CHINA Vinje K
Accession no.829001 SINTEF Materials Technology
(Rapra Technology Ltd.)
Item 25
International Journal of Polymeric Materials Item 27
49, No.2, 2001, p.191-204 Polymer Testing
COMPARISON EFFECTS OF PALM OIL FATTY 20, No.6, 2001, p.607-14
ACID AND STEARIC ACID ON DYNAMIC COMPARISON OF
PROPERTIES, CURING CHARACTERISTICS CETYLTRIMETHYLAMMONIUM MALEATE
AND MECHANICAL PROPERTIES OF CARBON AND SULPHENAMIDE AS AN ACCELERATOR
BLACK FILLED EPOXIDIZED NATURAL IN CARBON BLACK FILLED NATURAL
RUBBER COMPOUNDS RUBBER COMPOUNDS
Ismail H; Kamal S K; Mark S E Ismail H; Ahmad Z; Ishak Z A M
Universiti Sains Malaysia Universiti Sains Malaysia
The effects of palm oil fatty acid and stearic acid on The effects of using cetyltrimethylammonium
dynamic properties, curing characteristics and mechanical maleate(CTMAM) and N-cyclohexyl-2-benzothiazole-2-
properties of carbon black-filled epoxidised NR sulphenamide(CBS) as accelerators in carbon black-filled
compounds were studied. It was found that the scorch NR compounds were studied. The results obtained showed
time and cure time increased with increasing that cure time and scorch time were faster for CTMAM
than for CBS. CTMAM could function in its own right as identify the structure of the crosslinks. As a complex
an accelerator for sulphur vulcanisation, without the variety of hybrid bridges must be expected, the simple
presence of zinc oxide and stearic acid as activators. The model olefin 2,3-dimethyl-2-butene, which did not further
use of CTMAM in the absence of zinc oxide and stearic increase the complexity of the vulcanisation products, was
acid gave good tensile and tear strengths, tensile modulus, selected. 20 refs.
rebound resilience and hardness. 9 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
MALAYSIA USA; WESTERN EUROPE
Item 28 Item 30
159th ACS RUBBER DIVISION MEETING - SPRING 159th ACS RUBBER DIVISION MEETING - SPRING
2001. Held Rhode Island. 24th-27th April 2001. 2001. Held Rhode Island. 24th-27th April 2001.
Akron,Oh., 2001, Paper No.37, pp.26. 012 Akron,Oh., 2001, Paper No.34, pp.12. 012
HIGH MOLECULAR WEIGHT TETRA ALKYL COMPARISON OF RUBBER CURING SYSTEMS:
THIURAM DISULFIDE(TATD) IN TIRE PEROXIDE-COAGENT VERSUS SULFUR-
COMPOUNDS TO INCREASE CURE RATE ACCELERATOR IN POLYISOPRENE
WITHOUT SACRIFICING SCORCH SAFETY McElwee C B; Lohr J E
AND DYNAMIC PROPERTIES Sartomer Co.Inc.
Hong S W; Hannon M J; Kounavis J; Greene P K (ACS,Rubber Div.)
Uniroyal Chemical Co. A new generation of peroxide-initiated solid functional
(ACS,Rubber Div.) coagents was introduced for curing of synthetic
The use of TATD in various tyre compounds was polyisoprene elastomers. The resulting physical properties
evaluated with the aim of increasing cure rate and were shown to be similar to those of classical sulphur-
maintaining properties. Comparison was made with the accelerator cure systems. In addition, the flexural
use of tetrabenzylthiuram disulphide(TBzTD). TATD properties obtained by using the new system were found
provided equivalent scorch time to TBzTD in NR greatly to surpass those of the sulphur system, while still
compounds, lower modulus and higher elongation. maintaining the superior ageing characteristics. The
Tetramethylthiuram disulphide gave the fastest cure, but combination of properties obtained provided the
worst scorch safety, lowest elongation and higher opportunity of use in a wide range of applications
modulus. TBzTD provided equivalent scorch time to the previously unavailable to peroxide-coagent curing of
control, but reduced elongation and increased modulus. elastomers.
TATD had similar properties to the control with faster USA
cure. Abrasion resistance with TBzTD and TATD was Accession no.824950
much better than the control compound without a
secondary accelerator. 4 refs.
Item 31
USA
159th ACS RUBBER DIVISION MEETING - SPRING
Accession no.824952 2001. Held Rhode Island. 24th-27th April 2001.
Akron,Oh., 2001, Paper No.33, pp.27. 012
Item 29 MODIFYING THE PERFORMANCE OF
159th ACS RUBBER DIVISION MEETING - SULFENAMIDE ACCELERATORS WITH
SPRING 2001. Held Rhode Island. 24th-27th April THIURAMS
2001. Chasar D W
Akron,Oh., 2001, Paper No.35, pp.38. 012 Goodrich B.F.,Co.
CARBASULFANES AS CROSSLINKER FOR (ACS,Rubber Div.)
DIENE RUBBER - A MODEL COMPOUND Cure-Rite IBM and Cure-Rite IBT from B.F.Goodrich, a
STUDY thiuram monosulphide and disulphide, respectively, based
Hahn J; Palloch P; Walter E; Thelen N upon diisobutylamine, are new low nitrosamine-
Cologne,University producing accelerators. These additives, together with
(ACS,Rubber Div.) other commercial thiuram compounds, were compared
The potential of polycarbasulphanes (Sx(CH2)y)p as as co-accelerators for benzothiazole sulphenamides in
crosslinking agents was investigated by studying the SBR/polybutadiene and NR compounds. The effects that
structures of the crosslinks generated by these polymers these thiurams had on the scorch safety and cure rates
in dependence on the parameters x (x = 2-4) and y (y = 1- during curing and on the reversion resistance of the
3, 6). Model compound vulcanisation in combination with vulcanisates were demonstrated. Cure-Rite IBM excelled
reversed-phase high performance liquid chromatography, in improving the scorch safety of the benzothiazole while
NMR spectroscopy and mass spectrometry were used to improving the cure rates. Cure-Rite IBT appeared to be a
suitable replacement for the more expensive benzyl dynamic properties reported. Conclusions were drawn
thiurams. Both new materials improved reversion about the existence and level of effects of the control
resistance and blow-out properties in NR. Differences in factors on the various properties. 1 ref.
the types of sulphur crosslinks developed by the various USA
thiurams during vulcanisation are discussed. 6 refs. Accession no.824939
USA
Accession no.824949 Item 34
International Polymer Science and Technology
Item 32 28, No.5, 2001, p.T/29-30
159th ACS RUBBER DIVISION MEETING - SPRING EVALUATION OF THE EFFICIENCY OF A
2001. Held Rhode Island. 24th-27th April 2001. BINARY SYSTEM OF ACCELERATORS
Akron,Oh., 2001, Paper No.30, pp.18. 012 CONSISTING OF PHOSPHONIUM SALT AND
COAGENT SELECTION FOR WIRE AND METAL DIPHENYLDITHIOPHOSPHATE
CABLE APPLICATIONS Ovcharov V I; Okhtina O V
Costin R
An evaluation is reported into the effect of using a binary
Sartomer Co.Inc.
system of accelerators consisting of a cation-active
(ACS,Rubber Div.)
phosphonium salt and an anion-active metal
The effect of Type I and Type II coagents on the properties dithiophosphate. The studies were carried out using model
of peroxide-cured EPDM, EPM and chlorinated PE(CPE) unsaturated elastomer compositions based on butadiene-
compounds was studied. The coagents contributed to the methylstyrene rubber. Also investigated was the efficiency
crosslink network by forming more C-C bonds relative of this system on the action of the thiazole accelerator
to the peroxide control. In addition, compounds cured with dibenzothiazolyl disulphide. A synergistic effect was
peroxides and coagents were superior to sulphur-cured noted in relation to the process of sulphur vulcanisation,
compounds in many properties, including heat aged the degree of crosslinking, and the elastic strength
performance, fluid resistance and electrical properties. properties. The proposed system of secondary accelerators
Commercially-available coagents were compared in wire was shown to provide a higher degree and rate of
and cable formulations based on the above polymers. In
vulcanisation of elastomer compositions in combination
the EPDM and EPM formulations, the liquid high 1,2-
with scorch resistance, than the systems of the individual
vinyl polybutadiene(PBD) coagents often exceeded the
accelerators. 7 refs. (Article translated from Kauchuk i
performance of the trimethylolpropane trimethacrylate.
Rezina, No.5, 2000, p.41)
The PBD-modified compounds particularly excelled in
RUSSIA
heat aged, water resistance and electrical properties. All
the coagents improved performance of the CPE Accession no.824314
compound. The liquid maleinised PBD coagent was found
to be particularly effective in CPE, resulting in the best Item 35
physical properties and good electrical properties. 7 refs. Journal of Applied Polymer Science
USA 81, No.4, 25th July 2001, p.800-8
Accession no.824946 NR-EPDM COVULCANIZATION: A NOVEL
APPROACH
Arup Kumar Ghosh; Subhas Chandra Debnath;
Item 33
Nityananda Naskar; Dipak Kumar Basu
159th ACS RUBBER DIVISION MEETING - SPRING
Indian Association for the Cultivation of Science
2001. Held Rhode Island. 24th-27th April 2001.
Akron,Oh., 2001, Paper No.21, pp.22. 012 An elastomer blend consisting of highly unsaturated
EFFECTS OF NBR POLYMER VARIATIONS ON natural rubber (NR) and ethylene propylene diene rubber
COMPOUND PROPERTIES (EPDM) of low unsaturation was co-vulcanised using
Del Vecchio R J; Ferro E B bis(diisopropyl)thiophosphoryl disulphide (DIPDIS) as
Technical Consulting Services; Corry Rubber Corp. a novel coupling agent/accelerator. The blend vulcanisates
(ACS,Rubber Div.) obtained showed improved physical properties, which was
Using a designed experiment, variations in Mooney further improved by two-stage vulcanisation combined
viscosity, acrylonitrile content, polymerisation method with judicious selection of the NR to EPDM ratio, which
and cure system (sulphur or low sulphur) were gave a coherent and homogeneous blend. The cure-rate
investigated in relation to their effects on processing mismatch problem was solved by formation of rubber-
characteristics and standard physical properties, including bound intermediates and a multifunctional rubber
heat ageing, oil resistance, compression set and stress additive, i.e. DIPDIS, which restricted the curative
relaxation. The use of a specialised polymeric additive migration from lower to highly unsaturated rubber. The
(polyoctenylene) was also examined and testing of blend morphology as revealed by scanning electron
Xuzhou,School of Chemical Technology of zinc oxide in the final stage of mixing together with IS
causes reduction of IS reversion. During processing, IS
The effect of type and level of polyol on the properties of
reverts faster in compounds of high viscosity. These
silica-filled NR compound was investigated. The test
results should help rubber technologists to better utilise
results showed that the vulcanisation of silica-filled NR
advantages of IS based mainly on its non-blooming
compound was accelerated by polyols, the diglycol being
behaviour and to reduce to the lowest level IS reversion
the most active, giving the fastest vulcanisation and good
during processing. 12 refs.
physical properties, followed by triethanolamine, glycol,
EASTERN EUROPE; POLAND
polyglycol and glyceryl alcohol. There was an optimum
level for each polyol. 1 ref. Accession no.811180
CHINA
Accession no.813827 Item 51
Patent Number: US 6140427 A1 20001031
Item 49 VULCANIZATION ACCELERATORS SUITABLE
China Rubber Industry FOR THE INTRODUCTION OF POLAR
48, No.3, 2001, p.133-7 SUBSTITUENTS
Chinese Scholl T; Weidenhaupt H-J; Kelbch S; Engels H-W
EFFECTIVE FACTORS ON HEAT AGING Bayer AG
PROPERTIES OF IIR VULCANIZATE Vulcanization accelerators of given formula are
Guo Jian-hua; Luo Quan-kun particularly suitable for the production of vulcanised
South China,University of Technology rubbers modified with lateral polar groups.
The effect of different curing systems and other additives EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
on the heat ageing properties of butyl rubber vulcanisate USA; WESTERN EUROPE
was investigated. The test results showed that the physical Accession no.809220
property retention of butyl rubber cured with resin after
160C heat ageing for 24 h was superior to that of those Item 52
cured with sulphur or sulphur donor. The optimum heat Journal of Applied Polymer Science
ageing properties of butyl rubber vulcanisate were 79, No.6, 7th Feb.2001, p.1074-83
obtained when about 5 to 10 phr of resin, 5 to 9 phr of NEW MECHANISM FOR REACTION OF
tin(II) chloride and 5 phr of zinc oxide were used and the AMINES WITH ZINC DITHIOCARBAMATES
heat ageing properties were further improved by adding Dirksen A; Nieuwenhuizen P J; Hoongenraad M;
ISAF/GPF and ricinus oil. 9 refs. Haasnoot J G; Reedijk J
CHINA Leiden,University
Accession no.813824
Based on work with model compounds, a new
mechanism is proposed for the reactions between
Item 50
bis(dithiocarbamato)zinc(II) (ZDAC) and amines. These
Elastomery
reactions are an integral part of the reactions involved
4, No.6, 2000, p.24-36
in the curing of unsaturated rubbers, especially
Polish
polybutadiene, and are shown to be catalysed by
TECHNICAL ASPECTS OF USING INSOLUBLE
elemental sulphur. In this proposed mechanism, the
SULPHUR
formation of an amine- dithiocarbamic intermediate is
Pysklo L; Glijer T
suggested, from which two known products of the
Instytut Przemyslu Gumowego Stomil Piastow
reaction of ZDAC with primary amines, 1,1,3-
Physicochemical properties of insoluble sulphur (IS) trisubstituted and 1,3-disubstituted thioureas can be
grades applied by the Polish rubber industry are tested. formed. With secondary amines a mixture of zinc
Effects of some ingredients of rubber compounds, dithiocarbamates is found and thiourea products are not
viscosity of compounds and processing temperature on formed. 13 refs
IS reversion are also evaluated. It is found that Polsinex EUROPEAN COMMUNITY; EUROPEAN UNION;
33 has the best properties of all Polish IS grades. It has NETHERLANDS; WESTERN EUROPE
better reversion resistance and dispersibility than Flexsys’ Accession no.808782
Crystex OT33. To assure maximum IS stability during
processing, it is necessary to eliminate from rubber
Item 53
compounds ingredients of strong basic character. In the
China Synthetic Rubber Industry
case of using the antioxidant TMQ and sulphenamide
24, No.2, 2001, p.82-6
accelerators, only products containing minimum quantity
Chinese
of free amines should be applied. The sequence of addition
VULCANISATION CHARACTER OF TRANS-1,4-
of ingredients is also important. It is observed that addition
POLYISOPRENE AND MECHANICAL
Purified natural rubber (PNR) is of interest because of its powder metal salts as reinforcing agent. High hardness
potentially lower toxicological effects than whole natural and strength are imparted and high elongation is retained.
rubber (WNR) due particularly to the reduction in protein Optimum levels are indicated for a balance of properties.
content. Improved dynamic mechanical properties have 2 refs.
also been reported. Comparison of both gum and filled CHINA
compounds, vulcanised using conventional cure systems Accession no.794764
(CV) and efficient vulcanisation systems (EV) prepared
from PNR and WNR indicate that generally properties of
the PNR are poorer than WNR. The exception is in the Item 65
flex cracking resistance and the heat build up in the filled China Synthetic Rubber Industry
samples where PNR shows an improvement. Using the 23, No.6, 2000, p.357-61
EV cure system on filled PNR gives properties almost Chinese
comparable to WNR. A study of the distribution of the APPLICATION OF CROSSLINKING COAGENTS
types of sulphur crosslink in both pNR and WNR MPBM AND TMPTA IN HNBR
vulcanisates indicates a more uniform distribution of Xiang T; Jun Y; Dizhen W; Dongshan L
monosulphidic (S), disulphidic (S2) and polysulphidic South China,University of Technology
(Sx) crosslinks in the PNR samples (38.7/25/36.4 in PNR The effect is studied of the use of bis-functional
compared to 64.1/29.7/6.6 in WNR respectively). This is crosslinking coagent, N,N’-m-benzyl bismaleimide
believed to be the reason for the better dynamic properties (MPBM) and tri-functional crosslinking coagent
of PNR vulcanisates. 7 refs trimethylpropane triacylate (TMPTA) on the properties
THAILAND of hydrogenated nitrile rubber, (HNBR). The results
Accession no.796699 showed that MPBM and TMPTA could decrease the Tg
of HNBR more than a half and one-third respectively,
Item 63 and increase the crosslinking density. FTIR analysis
Journal of Applied Polymer Science confirmed that MPBM and TMPTA both joined the
78, No.10, 5th Dec.2000 p.1769-75 crosslinking reaction. Small amounts of MPBM
XANTHATE ACCELERATORS FOR LOW improved the heat resistance of HNBR, and TMPTA was
TEMPERATURE CURING OF NATURAL shown to improve ozone resistance and maintain heat
RUBBER resistance. 5 refs.
Palaty S; Joseph R CHINA
Cochin,University of Science & Technology Accession no.794758
Laboratory preparation of zinc salts of ethyl, isopropyl,
and butyl xanthates was carried out. These were purified Item 66
by reprecipitation and characterised by IR, NMR, and 158th. ACS Rubber Division Meeting - Fall 2000.
thermogravimetric analysis techniques and melting points Conference preprints.
determined. The rubber compounds with different Cincinnati, Oh., 17th.-19th. Oct. 2000, paper 98
xanthate accelerators were cured at temperatures from 30 NEW CABOT CARBON BLACK FOR
to 150 degrees Celsius. Moulding of the sheets was IMPROVED PERFORMANCE IN PEROXIDE
performed and properties such as tensile strength, tear CURED INJECTION MOLDED COMPOUNDS
strength, crosslink density, elongation at break, and Bussolari S; Laube S
modulus at 300 percent elongation were calculated. The Cabot Corp.
results revealed that all three xanthate accelerators are (ACS,Rubber Div.)
effective for room temperature curing. 12 refs.
Details are given of Spheron 4000, a furnace black
INDIA
developed by Cabot for use in peroxide cured injection
Accession no.794915 moulded compounds. The product solves the problems
normally associated with injection moulding peroxide
Item 64 cured systems, namely those relating to flow, and for
China Synthetic Rubber Industry which processing aides are often used, which can lead to
23, No.6, 2000, p.375 an increase in mould fouling and consequently downtime.
MECHANICAL PROPERTIES AND CROSSLINK Lowering the viscosity of the compound through the use
DENSITY OF ZINC DIMETHACRYLATE of a filler is an alternative to using processing aids. Cabot
REINFORCED EPDM has developed Spheron 4000 furnace black with a surface
Zonglin P; Yong Z; Yinxi Z area of about 32, which is demonstrated to improve flow
Shanghai,Jiao Tong University properties and reduce mould fouling.
The mechanical properties and crosslink density is studied USA
of peroxide cured EPDM containing zinc dimethacrylate Accession no.794196
automotive hose and belt specifications have changed, applications would lead to sulphur bloom on the surface
requiring longer product life in terms of wear and heat of uncured components due to its relatively low solubility
ageing. Sulphur cure systems suffer from embrittlement in elastomers; around 1 phr at room temperature in natural
due to poor heat age resistance. Efforts have been made rubber based compounds. Insoluble sulphur, however, is
to develop improved cure systems. Peroxide-coagent cure sometimes difficult to disperse in rubber compounds.
systems do provide the improvement needed in heat During mixing agglomeration can occur leading to poorly
ageing while maintaining the desirable sulphur cure dispersed material. Cool processing temperatures will aid
properties of good dynamic properties, tensile strength in obtaining good dispersion. A high mixing temperature
and wear. In addition, by selecting the right coagent, on the other hand reduces the viscosity of the compound
excellent adhesive properties can be achieved between and results in lower effective shear forces, unfavourable
rubber and reinforcement without the use of external towards good dispersion. Additives such as oil and silica
bonding agents. A review of these coagents appropriate can improve dispersion significantly and even further
for peroxide cured hoses and belts is presented. 6 refs. improvements can be achieved through the use of pre-
EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; dispersed masterbatches. However, the preparation of pre-
WESTERN EUROPE dispersed masterbatches and silica containing grades
Accession no.769255 involves additional costs. A new grade of insoluble
sulphur has been developed making use of a special
Item 108 additive package that leads to enhanced dispersion and
Rubberchem ’99. Conference proceedings. reduced incorporation time. This new product provides
Antwerp, Belgium, 22nd-23rd Nov.1999, paper 12 superior flow characteristics allowing ease of handling.
BETTER VULCANISATE PROPERTIES USING The special additive package also provides increased
N-NITROSAMINE FREE CURING SYSTEMS thermal stability of the insoluble sulphur, ensuring
Schuch A enhanced bloom resistance following mixing and
Rhein Chemie Rheinau GmbH processing.
(Rapra Technology Ltd.) EUROPEAN COMMUNITY; EUROPEAN UNION;
NETHERLANDS; USA; WESTERN EUROPE
It has been shown that almost 60% of common curing
Accession no.769252
agents are critical with regard to their toxicological
potential and should be substituted by harmless
accelerators. Generally dithioates can replace many Item 110
critical curing agents. In some applications like OTOS in Journal of Applied Polymer Science
NR, the first steps toward this substitution are promising. 75, No.6, 7th Feb.2000, p.735-9
The results on ageing show a good consistency of IMPROVEMENT OF FILLER-RUBBER
elasticity but there is still room for improvements in terms INTERACTION BY THE COUPLING ACTION
of consistency of tensile data. The substitution of MBS OF VEGETABLE OIL IN CARBON BLACK
by dithioates in SBR results in improved dynamic REINFORCED RUBBER
behaviour and higher heat stability of the network at Kundu P P
similar other physical properties. Even the substitution Sant Longowal,Institute of Engineering & Technology
of TMTM by dithioates in coloured blends gives colour Small amounts of vegetable oil added to a natural rubber/
stability, faster curing speed and handling advantages. 6 polybutadiene blend compound during mixing has a very
refs. significant effect on both vulcanisation and physical
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; properties. Some of the effects may be from a lower
WESTERN EUROPE
crosslink density, or plasticisation. 14 refs.
Accession no.769254 INDIA
Accession no.769014
Item 109
Rubberchem ’99. Conference proceedings.
Antwerp, Belgium, 22nd-23rd Nov.1999, paper 10 Item 111
IMPROVED FORM OF INSOLUBLE SULPHUR China Rubber Industry
Ingham F A A; To B H 47, No.2, 2000, p.90-3
Flexsys BV; Flexsys America LP Chinese
(Rapra Technology Ltd.) APPLICATION OF CURING AGENT DL-268 TO
NR/SBR COMPOUND
Insoluble sulphur is a high molecular weight polymeric
Pang J
form of sulphur and is insoluble in rubber. This feature
Double Happiness Tyre Industries Corp.Ltd.
provides the rubber compounder with the freedom to
formulate compounds containing high levels of sulphur Addition of curing agent DL-268 to a natural rubber
but with no detrimental effect on green compound tack. styrene butadiene rubber blend was investigated.
The use of ordinary rubber makers sulphur (RMS) in such Reversion and thermooxidatively aged physical properties
were examined. Adhesion between the compound and tyre solvent, which resulted in recovery and even improvement
cord was found to be improved, but fatigue heat build-up of the original properties such as stress at constant
was decreased. deformation, TS, crosslink density and storage modulus.
CHINA The temps. of the two transitions observed in the
Accession no.768048 relaxation spectra, the Tg of the polymer and the ionic
transition corresponding to ionic aggregates, were
displaced to higher values when ionic structures were
Item 112 regenerated. 7 refs.
Polymers for Advanced Technologies
EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;
11, No.1, Jan.2000, p.1-8 WESTERN EUROPE
EVALUATION OF THE PROPERTIES OF SOME Accession no.766016
NITRILE-BUTADIENE RUBBER/
POLYCHLOROPRENE MIXES AND
VULCANIZATES Item 114
Abdel-Bary E M; von Soden W; Helaly F M Rubber Chemistry and Technology
Mansoura,University; Ulm,University; Egypt,National 72, No.2, May-June 1999, p.334-42
Research Centre STUDIES OF PEROXIDE CURING OF CIS-1,4-
POLYISOPRENE/DIALLYL PHTHALATE
Nitrile rubber was blended with polychloroprene(CR) in BLENDS BY SPECTROSCOPIC TECHNIQUES
a weight ratio of 1:1. The vulcanising systems in the blend Sung Joon Oh; Koenig J L
formulations were varied to obtain non-crosslinked CR Case Western Reserve University,Dept.of
embedded in vulcanised nitrile rubber and non- Macromolecular Science
crosslinked nitrile rubber embedded in vulcanised CR.
The effects of these two different phases on the rheological Differential scanning calorimetry (DSC), solid state
and mechanical characteristics were evaluated. The nuclear magnetic resonance (NMR), Fourier transform
dynamic compliance of the blends was also measured over infrared spectroscopy (FTIR) and equilibrium swelling
wide ranges of frequency and temp. It was found that the techniques were used to study the peroxide curing of cis-
mechanical and rheological properties of the vulcanised 1,4-polyisoprene with addition levels of coagent diallyl
blends depended on the type of vulcanising system, its phthalate from 0 to 20 percent by weight. It is postulated
concentration and the presence of reinforcing filler. The that, although reaction kinetics are controlled by rate of
mechanical properties of the blend containing N- peroxide decomposition, the coagent catalyses the curing
cyclohexyl-2-benzthiazyl sulphenamide/sulphur as reactions and undergoes both copolymerisation and
vulcanising system suitable for nitrile rubber were higher homopolymerisation during the reaction. Chemically
than those of the blend containing non-sulphur vulcanising bound coagent domains, which are phase separated are
system (zinc oxide/magnesium oxide and ethylene suggested to cause a decrease in segmental mobility with
thiourea) suitable for CR. The rubbers in the blend were increase in crosslink density. 20 refs
incompatible as two Tgs were observed. 14 refs. USA
EGYPT; EUROPEAN COMMUNITY; EUROPEAN UNION; Accession no.763828
GERMANY; WESTERN EUROPE
Accession no.766102
Item 115
Rubber Chemistry and Technology
Item 113 72, No.2, May-June 1999, p.318-33
Polymer International INSIGHTS INTO SULFUR VULCANISATION
49, No.1, Jan.2000, p.115-21 FROM QSPR QUANTITATIVE STRUCTURE-
VULCANIZATION OF CARBOXYLATED PROPERTY RELATIONSHIPS STUDIES
NITRILE RUBBER(XNBR) BY A MIXED ZINC Ignatz-Hoover F; Katritzky A R; Lobanov V S;
PEROXIDE-SULPHUR SYSTEM Karelson M
Ibarra L; Alzorriz M Flexsys America; Florida,University; Tartu,University
Instituto de Ciencia y Tecnologia de Polimeros
Studies on the vulcanisation of a black and oil filled styrene-
Vulcanisation of XNBR with a mixed system based on butadiene rubber compound accelerated by a number of
zinc peroxide and sulphur accelerators was shown to different sulphenamide and sulphenimide compounds were
produce materials with favourable mechanical properties made using a conventional curemeter operated to normal
because of the formation of ionic aggregates which gave ASTM standards. The vulcanisation reactions were also
the vulcanised compounds a certain rigidity. These studied using different modelling software, CODESSA
properties were drastically reduced by the effect of software for deriving quantitative structure-property
saturated ammonia vapour which plasticised the ionic relationships and MOPAC software for semiempirical
aggregates. This plasticisation, however, was reversible molecular orbital calculations which together yielded
and the aggregates could be regenerated by addition of a excellent correlation to onset of cure and maximum cure
Orlando, Fl., 21st-23rd Sept.1999, paper 26 Xingheng Yuan; Zongling Peng; Yong Zhang; Yinxi
EFFECT OF CURE SYSTEM ON NATURAL Zhang
RUBBER BONDING Shanghai,Jiao Tong University
Halladay J R; Krakowski F J
The mechanical properties and cross-linked network
Lord Corp.
structure of a peroxide-cured nitrile rubber containing
(ACS,Rubber Div.)
magnesium methacrylate are investigated and discussed.
It is perceived within the rubber industry that the choice of Some typical properties of the material are compared with
cure system may have an influence on the ease of bonding those of carbon black reinforced nitrile rubber. 8 refs.
of general-purpose elastomers. The effect on bonding of CHINA
varying sulphur level combined with accelerator level and Accession no.758187
type in a NR formulation is investigated using designed
experiments. Bond integrity is evaluated using ASTM D
429 Method B and buffer specimens (proposed Method F) Item 127
with various commercial solvent based and aqueous Rubber World
adhesives. The results contradict some conventional 221, No.3, Dec.1999, p.18/69
wisdom with respect to bonding. 13 refs. EFFECT OF CURE SYSTEM ON NR BONDING
Halladay J R; Krakowski F J
USA
Lord Corp.
Accession no.758324
Much literature has been published on bonding rubber to
metal and testing rubber to metal bonds. This article continues
Item 125
the bond investigations by concentrating on the influence of
156th ACS Rubber Division Meeting - Fall 1999.
sulphur and accelerator choices in natural rubber. To
Conference preprints.
determine the effect of sulphur, two levels were chosen. Four
Orlando, Fl., 21st-23rd Sept.1999, paper 21
different accelerators, and two solvent-based and two
ACTION OF N-
aqueous adhesive systems were chosen. The two test methods
(CYCLOHEXYLTHIO)PHTHALIMIDE AS A
used for comparison were ASTM D 429 Method B and the
PREVULCANISATION INHIBITOR OF 2-
proposed Method F buffer specimens. 13 refs.
BISBENZOTHIAZOLE-2,2'-DISULPHIDE
USA
ACCELERATED SULPHUR VULCANISATION
Gradwell M H S; Stephenson N R Accession no.758078
Port Elizabeth,University
(ACS,Rubber Div.) Item 128
Prevulcanisation inhibitors (PVI) provide an important Applied Spectroscopy
delay in the curing reactions that occur in accelerated 74, No.11, 9th Dec.1999, p.2756-63
sulphur vulcanisation. The reactions of N- STUDIES ON DYNAMIC AND STATIC
cyclohexylthiophthalimide (CTP) are investigated in the CROSSLINKING OF ETHYLENE VINYL
presence and absence of rubber. The CTP is shown to ACETATE AND ETHYLENE PROPYLENE
react very readily with 2-mercaptobenzothiazole (MBT) DIENE TERCOPOLYMER BLENDS
and this reaction has previously been credited with the Mishra S; Baweja B; Chandra R
delay observed. However, recent studies have shown that North Maharashtra,University; Delhi,College of
MBT is not formed until crosslinking has started. In a 2- Engineering
bisbenzothiazole-2,2'-disulphide (MBTS) accelerated Both mechanical (torque rheometer) and thermal (differential
sulphur cure, CTP is shown not to delay the onset of scanning calorimetry) tests were used to study the effect of
crosslinking, but once crosslinking begins, with the the blend ratio of ethylene vinyl acetate (EVA) and ethylene
concurrent formation of MBT, the CTP reacts with the propylene diene terpolymer (EPDM) on peroxide
MBT inhibiting further polysulphide formation, pendent vulcanisation. Static cure in the calorimeter was noted to be
group formation and thus crosslinking. Crosslinking much slower than dynamic cure using the torque rheometer.
continues after the CTP has been consumed. 25 refs. Increasing the EVA/EPDM ratio reduces optimum cure time
SOUTH AFRICA and energy consumption during cure, indicating increased
Accession no.758319 rate of cure. Increasing the EVA content was found to
decrease the activation energy. 19 refs.
INDIA
Item 126
Polymers & Polymer Composites Accession no.756017
7, No.6, 1999, p.431
PROPERTIES AND STRUCTURES OF Item 129
PEROXIDE-CURED NBR CONTAINING Innovations in Rubber. Conference proceedings.
MAGNESIUM METHACRYLATE Shawbury, 14th May 1999, paper 3
and polyisoprene alone, with the addition of zinc oxide, 72, No.1, March-April 1999, p.15-26
with the addition of sulphur and with the addition of both HOMOGENEOUS ZINC(II) CATALYSTS IN
sulphur and zinc oxide. With TBBS alone crosslinking ACCELERATED VULCANIZATION II.
occurred at a very high temperature. With TBBS and ZnO, (POLY)OLEFIN OXIDATION, DEHYDRATION,
crosslinking followed a similar method but at a slightly AND REACTION WITH ANTI-REVERSION
lower temperature and resulted in higher crosslink COAGENTS
densities With TBBS and sulphur, and with the addition Nieuwenhuizen P J; Haasnoot J G; Reeduk J
of ZnO crosslinking started at a much lower temperature. Leiden,University
Formation of MBT and MBTS during the reaction was
Reversion mechanisms in diene rubbers were studied.
noted in each case, but the reaction mechanisms proposed
Using model 1,5-polyolefins in the presence of dioxygen
indicate that the delayed action of TBBS is due to
benzothiazole terminated pendant groups rather than the at temperatures of 140 degree C and above, and via allylic
formation of the butylamine salt of MBT as postulated alcohols or hydroperoxides which dehydrate when
by others. catalyzed by ZDMC bis(dimethyldithiocarbamato)
SOUTH AFRICA
zinc(II) or ZMBT bis(mercaptobenzothiazolato)zinc(II),
a new route for the formation of dienes and trienes has
Accession no.753123
been indicated. A 1,2-dehydration route has been observed
exclusively in this process with no evidence of 1,4-
Item 134
dehydration. A complete reaction between squalene and
Rubber Chemistry and Technology
NBCI (N-benzylcitraconimide, a model compound for the
72, No.1, March-April 1999, p.27-42
HOMOGENEOUS ZINC(II) CATALYSTS IN anti-reversion agent BCIMB (1,3-bis(citraconimido-
ACCELERATED VULCANIZATION III. methyl)benzene) has been observed in the absence of
DEGRADATION MODES OF MONO- AND DI- vulcanisation chemicals at a temperature of 170 degrees
SULFIDIC CROSS-LINKS C which appears to follow the same mechanism. From
Nieuwenhuizen P J; van Veen J M; Haasnoot J G; the evidence of these two reactions it would appear that
Reeduk J oxidation of the rubber backbone followed by dehydration
Leiden,Institute of Chemistry; Leiden,University may account for the presence in vulcanised rubber of
dienes and trienes. This is in contrast to accepted belief
Reversion mechanisms in diene rubbers were examined
that the presence of dienes and trienes in a cured rubber
by studying the reaction products from degradation of
is attributed only to reactions involving the breaking of
mono and disulphidic crosslinks in model compounds.
crosslinks. 32 refs.
No evidence was found to support the theory that these
crosslinks degrade to form cyclic disulphides and zinc EUROPEAN COMMUNITY; EUROPEAN UNION;
NETHERLANDS; WESTERN EUROPE
sulphide. Studies were based on the model compound
vulcanisation of dimethylbutene which allows two Accession no.753120
isomeric crosslink attachments. Degradation of
monosulphidic crosslinks resulted in olefins and a 1,3- Item 136
dithiin which was postulated to result from dimerisation Journal of Polymer Engineering
via a Diels-Alder reaction of unstable unsaturated 19, No.1, 1999, p.13-26
thioaldehydes. Degradation of disulphidic crosslinks were EFFECT OF OLIGOAMIDE PHOSPHATE AND
shown to be catalysed by zinc diethyl dithiocarbamate ITS AMMONIUM DERIVATIVE IN
(ZDEC) (and presumably other zinc complexes) via a DIBENZOTHIAZOLYL DISULPHIDE-
previously unpostulated mechanism to result in a 1,2- ACCELERATED NATURAL RUBBER
dithia-3-cyclopentene. Attempts to reduce the degradation COMPOUNDS
reactions by introducing nitrogen containing ligands (to Vladkova T G
complex with the zinc dithiocarbamate), dienophiles (to Sofia,University of Chemical Technology & Metallurgy
scavenge dienes and trienes formed during vulcanisation
The modifying and accelerating effects of
reaction) or dipolarophiles (to react with 1,3 dipolar
species) did not prove successful. Typical vulcanisation oligoamidephosphate and its ammonium derivative on the
temperatures of 140 degrees C were used for this work properties of dibenzothiazolyldisulphide-accelerated
rather than higher temperatures commonly used sulphur-vulcanised natural rubber was investigated. Both
previously. 35 refs. materials enhanced the fatigue resistance of the rubber, the
EUROPEAN COMMUNITY; EUROPEAN UNION; number of cycles to failure being increased by at least one
NETHERLANDS; WESTERN EUROPE order of magnitude. The ammonium derivative also provided
Accession no.753121 an additional accelerated effect, being most effective when
added in the second preparation stage. 11 refs.
BULGARIA; EASTERN EUROPE
Item 135
Rubber Chemistry and Technology Accession no.752410
Chicago, Il., 13th-16th April 1999, Paper 63, pp.25 mechanical properties in these applications through the
DIFFERENCES AMONG THIURAM selection of curing systems and antioxidants is discussed.
ACCELERATORS THAT CAN AFFECT TIRE 26 refs.
DURABILITY USA
Chasar D W Accession no.749865
Goodrich B.F.,Co.
(ACS,Rubber Div.)
Item 144
Two thiuram accelerators developed by Goodrich, Cure- 155th ACS Rubber Division Meeting, Spring 1999.
rite IBM tetraisobutylthiuram monosulphide and Cure- Conference Preprints.
rite IBT tetraisobutylthiuram disulphide, were evaluated Chicago, Il., 13th-16th April 1999, Paper 16, pp.53
along with other commercial thiurams as co-accelerators STUDY OF EPDM/SBR BLENDS
for benzothiazole sulphenamides in the vulcanisation of Zhao J; Ghebremeskel G; Peasely J
NR and SBR/polybutadiene tyre compounds. The effects Ameripol Synpol Corp.
of these thiurams on scorch safety and cure rates during (ACS,Rubber Div.)
vulcanisation and on the reversion resistance of
vulcanisates were investigated, and differences in the The influence of mixing techniques, sulphur, peroxide
types of sulphur crosslinks developed by the various and coagent curing systems, carbon black levels and oil
thiurams were examined. 6 refs. content on the performance of EPDM/SBR blends was
investigated. The mechanical properties, heat ageing and
USA
ozone resistance of the blends were studied in comparison
Accession no.749876 with 100% EPDM compounds. 15 refs.
USA
Item 142 Accession no.749833
155th ACS Rubber Division Meeting, Spring 1999.
Conference Preprints.
Chicago, Il., 13th-16th April 1999, Paper 53, pp.16 Item 145
SELECTING ACRYLIC TYPE COAGENTS FOR Macromolecular Chemistry & Physics
HOSE AND BELT APPLICATIONS 200, No.8, Aug.1999, p.1965-74
Costin R; Nagel W PHOTOCROSSLINKING OF FUNCTIONALIZED
Sartomer Co.Inc. RUBBERS, VIII. THE THIOL-POLYBUTADIENE
(ACS,Rubber Div.) SYSTEM
Decker C; Nguyen Thi Viet T
Sartomer’s Saret zinc diacrylate and zinc dimethacrylate Haute-Alsace,Universite
coagents were evaluated in the peroxide vulcanisation of
EPDM automotive belt and hose compounds. Cure The light-induced crosslinking of styrene-b-butadiene-b-
characteristics and effects on mechanical properties, heat styrene block copolymer, using a trifunctional thiol and
and water resistance and adhesion of EPDM to metal and phosphine oxide photoinitiator, was studied using infrared
synthetic fibre reinforcements and to other rubbers were spectroscopy, and solubility and hardness measurements.
investigated. The results of this study and other Under intense illumination in air at ambient temperature,
experiments with Saret coagents in rubber formulations the curing proceeded extensively within less than 1 s. The
are discussed. 6 refs. relative reactivity of the thiyl radicals towards the
USA
polybutadiene vinyl and butene double bonds, and the
competition between homo- and copolymerisation for the
Accession no.749866
propagating alkyl radical, were determined. The
crosslinking process was little affected by an increase of
Item 143 the SBS vinyl content from 8 to 59%, as it mainly
155th ACS Rubber Division Meeting, Spring 1999. enhanced intramolecular reactions. It was concluded that
Conference Preprints. the thiol/ene polymerisation was much more effective in
Chicago, Il., 13th-16th April 1999, Paper 52, pp.36 crosslinking thermoplastic SBS elastomers than was the
CURE SYSTEMS AND ANTIDEGRADANT copolymerisation of the polybutadiene double bonds with
PACKAGES FOR HOSE AND BELT POLYMERS a diacrylate monomer. 16 refs.
Ohm R F; Callais P A; Palys L H EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;
Vanderbilt R.T.,Co.Inc.; Elf Atochem North America WESTERN EUROPE
Inc. Accession no.749667
(ACS,Rubber Div.)
Types of rubbers used in the manufacture of hoses and Item 146
belts for the automotive industry are reviewed, and the Industria della Gomma
improvement of heat resistance, flexural fatigue and other 43, No.4, May 1999, p.39-44
Item 155 properties of steel cord skim compounds, but also can be
Revue Generale des Caoutchoucs et Plastiques used effectively to replace the bonding system based on
No.773, Dec.1998, p.75-7 resorcinol and hexamethoxy-methylmelamine, it is found.
French 19 refs.
STRENGTHENING LEGISLATION ON EUROPEAN COMMUNITY; EUROPEAN UNION;
POLLUTION IN THE WORKPLACE NETHERLANDS; WESTERN EUROPE
Aubin C Accession no.735014
LRCCP
A survey is made of French and European Union Item 158
legislation relating to hazardous chemicals in the Kautchuk und Gummi Kunststoffe
workplace, and particular attention is paid to regulations 52, No.5, May 1999, p.316-9
concerning exposure to chemicals in the rubber industry. EFFECT OF THE VULCANISING SYSTEM ON
The carcinogenicity of nitrosamines formed during THE QUALITY OF NR LATEX CONDOMS
vulcanisation processes is examined, and methods used Maret J; Mathew M; Francis D J; Sahayadasan J
in their detection are discussed. 2 refs. Kottayam,Rubber Research Institute;
EU; EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; Cochin,University of Science & Technology; Hindustan
WESTERN EUROPE; WESTERN EUROPE-GENERAL Latex Ltd.
Accession no.736308 The quantity of sulphur and the type of accelerators used
in the vulcanisation of natural rubber condoms was found
Item 156 to affect the tensile properties, burst volume and burst
Rubber and Plastics News pressure of condoms. Different accelerator combinations
28, No.19, 19th April 1999, p.14-5 were studied, including S-5-ZMBT and NTP-ZMBT
VARIOUS VULKALENT E ROLES EXAMINED combinations, which were found to impart high
Moakes C A mechanical strength. The S-ZMBT system was found to
Bayer Corp. give maximum ageing resistance to condoms, compared
to other accelerator combinations. Mechanical strength
The primary function of Vulkalent E is as a scorch retarder of condoms was found to increase with an increase in the
in sulphur vulcanisation of unsaturated rubbers. This paper concentration of sulphur, but was accompanied by a
examines the accelerating affect of this chemical, decrease in ageing resistance. 7 refs.
particularly in mercapto accelerated sulphur vulcanisation INDIA
where it can replace other nitrosamine forming, secondary
Accession no.735013
accelerators. This accelerating effect is combined with
its delaying effect on the onset of cure. Examples are
shown of its utility in improving crosslink density and Item 159
hence compression set resistance as well as increasing Journal of Applied Polymer Science
modulus. Vulkalent E does not form carcinogenic 72, No.4, 25th April 1999, p.487-92
nitrosamine during vulcanisation. RUBBER SEED OIL: A MULTIPURPOSE
USA ADDITIVE IN NR AND SBR COMPOUNDS
Accession no.735636 Nandanan V; Joseph R; George K E
Cochin,University of Science & Technology
Rubber seed oil was used as a multipurpose plasticiser
Item 157
and fatty acid component of the activator in NR and SBR
Kautchuk und Gummi Kunststoffe
compounds. The oil, when substituted for conventional
52, No.5, May 1999, p.322/8
plasticiser, imparted good mechanical properties to the
STEEL CORD ADHESION. EFFECT OF 1,3-
vulcanisates, and improved ageing resistance, reduced
BIS(CITRACONIMIDOMETHYL)BENZENE
cure time, increased abrasion resistance and flex
AND HEXAMETHYLENE-1,6-
resistance, and reduced blooming. 17 refs.
BIS(THIOSULPHATE), DISODIUM SALT,
INDIA
DIHYDRATE
Datta R N; Ingham F A A Accession no.734903
Flexsys BV
Results of studies are examined regarding factors affecting Item 160
the adhesion of steel cord to rubber. The adhesion is International Rubber Exhibition and Conference 1999.
balanced with improved aged compound characteristics Conference proceedings.
and reduced compound heat build-up through the use of Manchester, 7th-10th June 1999, Materials paper 10.
1,3-bis(citraconimidomethyl)benzene, and hexa- HIGH TEMPERATURE CURING OF
methylene-1,6-bis(thiosulphate) disodium salt dihydrate. PASSENGER TYRES BY USING 1,3 BIS-
This combination of chemicals not only improves the (CITRACONIMIDOMETHYL) BENZENE
vulcanisation temps. was established. 3 refs. (Full The polyquaternary ammonium salt and sodium
translation of Kauch.i Rezina, No.5, 1991, p.39) diisobutyldithiophosphate were used together and
RUSSIA separately to accelerate the sulphur vulcanisation of
Accession no.733369 polyisoprene. Kinetic curves showed that vulcanisation
in the presence of the polyquaternary salt alone resulted
in a considerable induction period, a slow rate and a low
Item 165
degree of vulcanisation, so that the polyquaternary salt
Rubber Chemistry and Technology
alone can be considered to have low effectiveness as an
71, No.4, Sept-Oct. 1998, p.766-77
accelerator. The sodium diisobutyldithiophosphate was
NITROSAMINE FORMATION IN RUBBER. II.
an accelerator and its accelerating effect was enhanced
INFLUENCE OF CURE
by the presence of the polyquaternary salt. Use of both
Willoughby B G; Scott K W
Rapra Technology Ltd. substances accelerated the formation of sulphide
complexes and the crosslink formation. Thus it is
Details are given of nitrosamine formation in twenty-nine established that the binary system of sodium
different EPDM cures. Both ingredient and process- diisobutyldithiophosphate and polyquaternary ammonium
related effects were investigated. Two different levels of salt exhibit synergism in relation to different stages of
tetramethylthiuram disulphide and carbon black were sulphur vulcanisation, the degree of crosslinking and the
variables in this study, as was the type of carbon black elastic strength properties. The polyquaternary salt is a
used. Batch effects with respect to both polymer and co-accelerator. 8 refs.
carbon black were also studied as was the presence or UKRAINE
absence of mercaptobenzothiazole. 14 refs. Accession no.729161
EUROPEAN COMMUNITY; EUROPEAN UNION; UK;
WESTERN EUROPE
Accession no.730170 Item 168
International Polymer Science and Technology
25, No.7, 1998, p.67-70
Item 166 WAYS OF SOLVING THE PROBLEM OF
International Polymer Science and Technology NITROSOAMINES IN THE PRODUCTION OF
25, No.9, 1998, p.T/22-7 TYRES AND MECHANICAL RUBBER GOODS
INFLUENCE OF TEMPERATURE ON Novopol’tseva O M; Novakov I A; Krakshin M A
NETWORK FORMATION IN POLYISOPRENES Volgograd,State Technical University
Sokolova L V; Shershnev V A
Moscow,Lomonosov Institute The carcinogenicity of nitrosamines, compounds which
are formed during vulcanisation by the reaction of amines
NR and synthetic cis-1,4-polyisoprene were vulcanised by produced during the thermal decomposition of certain
quinol ether at temperatures of 87C and 143C for 1h under vulcanisation accelerators with nitrosing agents, is
20MPa. The degree of crosslinking was varied by the amount discussed. Methods of eliminating conditions where
of quinol ether. The vulcanisates were studied by swelling nitrosamines may be formed and enter the human body
in various solvents, uniaxial elongation and relaxation are considered. Particular attention is paid to the
experiments, and EB measurements. Variations in Mooney- elimination of the possibility of formation of nitrosamines
Rivlin parameters and swelling are discussed in terms of and/or the creation of conditions for reactions of
differences between NR and synthetic polyisoprene, degree nitrosamines with certain reactants with the formation of
of crosslinking, orientation, uneven distribution of crosslinks non-toxic compounds and to the replacement of
and ordering. It is shown that supermolecular formations vulcanisation accelerators and other rubber mix
have a considerable influence on the process of network ingredients that are capable of forming nitrosamines with
formation in polyisoprenes. 25 refs. amine-free compounds or with compounds containing
RUSSIA primary amines instead of secondary amines. 30 refs. (Full
Accession no.729162 translation of Kauch.i Rezina, No.2, 1998, p.5)
RUSSIA
Averko-Antonovich I Yu; Smirnov A A; Fomina L I to the Rapra produced International Polymer Science and
Kazan,State Technological University Technology.
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
The authors describe the use of Tiotex dispersion, a stable
WESTERN EUROPE
aqueous dispersion of polysulphide polymer, as a
vulcanising agent for use with latex compositions. The Accession no.710108
effect of this vulcanising agent on the crosslinking of
compositions based on butadiene-styrene, butadiene- Item 182
vinylidene chloride, butadiene-vinylidene chloride Nippon Gomu Kyokaishi
carboxylated and butadiene-acrylonitrile carboxylated 70, No.1, 1997, p.43-9
latices is described. Physico-mechanical properties of Japanese
films made from latices and of the vulcanisates are given. KINETIC STUDY OF THE PEROXIDE
5 refs. Articles from this journal can be requested for CROSSLINKING PROCESS OF RUBBERS
translation by subscribers to the Rapra produced USING AN OSCILLATING RHEOMETER
International Polymer Science and Technology. Sato T
RUSSIA Nippon Zeon Co.Ltd.
Accession no.713245 A formula is proposed for analysis of the kinetics of
peroxide crosslinking of rubber, showing the relation
Item 180 between the rate of crosslinking and the initial peroxide
IRC ’98. Conference Proceedings. concentration. Calculated values for the coefficients A
Paris, 12th-14th May 1998, p.259-60. 012 and B for SBR, BR, MBR and HNBR with varying
French peroxide concentrations showed that the crosslinking
STUDY OF THE INFLUENCE OF mechanism varies according to the type of rubber. 11 refs.
VULCANISATION ON N-NITROSAMINE Articles from this journal can be requested for translation
FORMATION MECHANISMS IN RUBBERS by subscribers to the Rapra produced International
Amelot V; Derouet D; Brosse J C; Aubin C; Gomez E Polymer Science and Technology.
Maine,Universite; LRCCP; IFOCA JAPAN
(AFICEP; Societe de Chimie Industrielle) Accession no.710060
The methodology used in a study of nitrosamine formation
in vulcanisation processes accelerated by Item 183
tetraethylthiuram disulphide is described. This involved Gummi Fasern Kunststoffe
the characterisation of nitrosable species and the 49, No.12, Dec.1996, p.984-95
mechanisms of their formation, and studies of the German
influence of vulcanisation reactions and curing systems REVERSION RESISTANCE OF NATURAL
on the formation of nitrosable species. The results of the RUBBER MIXES WITH THE USE OF
study are summarised. DITHIOPHOSPHATE CURING SYSTEMS
EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; Graf H-J; Johansson A H
WESTERN EUROPE Rhein Chemie Corp
Accession no.710619
Curing systems consisting of sulphur, MBTS and
dithiophosphate comparison systems which permit amines
Item 181 to be split off are studied with regard to thermal ageing
Gummi Fasern Kunststoffe properties, and show considerably less reversion. 9 refs.
49, No.11, Nov.1996, p.892-9 Articles from this journal can be requested for translation
German by subscribers to the Rapra produced International
CROSSLINK COMPENSATION: A NEW WAY TO Polymer Science and Technology.
COUNTERACT REVERSION EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
Datta R N; Talma A G; Wagenmakers J C; Seeberger D WESTERN EUROPE
Flexsys BV Accession no.710022
The basic chemistry of crosslinking and reversion is
discussed, and a new concept is proposed to counteract Item 184
reversion, based on the use of 1,3-bis(citraconimido- Technical Rubber Goods - Part of our Everyday Life.
methyl)benzene (BCI-MX, tradename Perkalink 900). Conference proceedings.
The effect of BCI-MX in natural rubber compounds with Puchov, 23rd-24th May 1996, p.279-87. 4
regard to suppression of reversion, hysteresis and dynamic REVERSION RESISTANCE TO NR WITH
properties is investigated. A theory on the mechanism of SPECIAL DITHIOPHOSPHATE CURE SYSTEMS
reversion prevention is proposed. 22 refs. Articles from Graf H-J; Fruh T
this journal can be requested for translation by subscribers Rhein Chemie Rheinau GmbH
addition of allylglycidyl ether or glycidyl methacrylate not much different compared to commercial stearic acid,
and polyfunctional alcohols or carboxylic acids. The effect especially at concentrations below 3 phr. Incorporation
of these on pure EPDM and NBR/EPDM blends was of both acids increases the scorch and cure times, t90,
examined, and data are given on the crosslinking effect and the MHR - ML (maximum torque - minimum torque)
and mechanical properties. 2 refs. Articles from this passes through a maximum value and decreases slightly
journal can be requested for translation by subscribers to with increasing amounts of acids. Tensile modulus and
the Rapra produced International Polymer Science and hardness for stearic acid increase up to 5 phr and then
Technology. decrease with increasing acid concentration. However,
JAPAN for palm oil fatty acid, these properties show an optimum
Accession no.704950 value at 3 phr and then start to decrease. The fracture
properties also pass through a maximum as the
Item 195 concentration of both acids increase. 15 refs.
Patent Number: US 5777012 A 19980707 MALAYSIA
POLYSULPHIDES OF N- Accession no.704284
METHYLPYRROLIDINONE
Wideman L G; Futamura S Item 198
Goodyear Tire & Rubber Co. Polymer Plastics Technology and Engineering
These are added to rubber to improve hysteresis, 37, No.4, Nov.1998, p.469-81
accelerate cure rate and improve filler dispersion. EPOXIDISED NATURAL RUBBER
USA COMPOUNDS: EFFECT OF VULCANISATION
SYSTEMS AND FILLERS
Accession no.704870
Ismail H; Ishiaku U S; Arinab A R; Ishak Z A M
Universiti Sains Malaysia
Item 196
Kauchuk i Rezina (USSR) The effects of various vulcanisation systems and fillers
No.2, 1995, p.35-37 in epoxidised NR (ENR) at 50% epoxidation (ENR 50
Russian compounds) are examined. ENR compounds cured with
INFLUENCE OF MESITYLENE DINITRILE the semi-EV (efficient vulcanisation) system show the
OXIDE ON THE PROCESSING PROPERTIES OF shortest cure and scorch times but the highest torque
ELASTOMER COMPOSITIONS values. White rice husk ash (WRHA) filled compounds
Boiko V V; Grinev I V have the shortest cure and scorch times followed by
carbon black and silica. The presence of a silane coupling
The effect of mesitylene dinitrile oxide (MDNO) as a low- agent, gamma-mercaptopropyl trimethoxysilane,
temperature vulcanising agent for unsaturated elastomers enhances the curing characteristics but the trend is similar.
is investigated. For the purpose of predicting the ENR compounds cured with the semi-EV system give
processing properties of elastomer compositions when
the best overall mechanical properties. A significant
mesitylene dinitrile oxide is introduced, the authors
enhancement of the mechanical properties is observed in
examined the change in Mooney viscosity of polyisoprene
the presence of a silane coupling agent, especially for
(SKI-3), butadiene-styrene (SKS-30ARKM-15),
WRHA- and silica-filled compounds. 17 refs.
butadiene-nitrile (SKN-18) and polybutadiene rubbers. 7
MALAYSIA
refs. Articles from this journal can be requested for
translation by subscribers to the Rapra produced Accession no.704283
International Polymer Science and Technology.
RUSSIA Item 199
Accession no.704334 Nippon Gomu Kyokaishi
68, No.6, 1995, p.430-31
Japanese
Item 197
NOCCELER-DZ DELAYED ACTION
Polymer Plastics Technology and Engineering
VULCANISATION ACCELERATOR (3)
37, No.4, Nov.1998, p.483-94
PALM OIL FATTY ACID AS AN ACTIVATOR IN Test results are given on the mechanical properties of
NATURAL RUBBER GUM COMPOUNDS rubber containing Nocceler-DZ and on the coupling effect
Ismail H; Ruhaizat T A of this accelerator in rubbers containing cobalt
Universiti Sains Malaysia naphthenate. Articles from this journal can be requested
The potential of palm oil fatty acid as an activator in for translation by subscribers to the Rapra produced
NR gum compounds is studied. The curing International Polymer Science and Technology.
characteristics and mechanical properties of NR gum JAPAN
compounds with palm oil fatty acid as an activator are Accession no.704161
this study, as was the type of carbon black used (N330 and Item 218
N550). The use of statistical experimental design showed Patent Number: US 5684202 A 19971104
that reliable data on nitrosamine formation in vulcanisates TERTIARY AMINES, A PROCESS FOR THEIR
could be obtained by paying strict attention to process PREPARATION AND THEIR USE AS
history. For the SBR, NR and NBR rubbers, a correlation HARDENING ACCELERATORS
was observed between the temp. reached on mixing and Meier H M; Fischer W; Clemens H
the level of nitrosamine generated on subsequent Bayer AG
vulcanisation. For these rubbers, the effect of this process
The present invention relates to novel tertiary amines
history outweighed that of any ingredient variable. While
derived from bisphenols, diepoxides and aromatic
allowing new insights to be gained on nitrosamine
secondary amines, to a process for their preparation and
formation in rubber, these results allow development of a
to their use as hardening accelerators for ethylenically
self-consistent mechanism for nitrosation processes where
unsaturated cold hardenable acrylic and polyester resins.
the reactions in diene rubbers mirrored those in air. 14 refs.
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE
WESTERN EUROPE
Accession no.678064
Accession no.692441
Item 219
Item 216
Patent Number: US 5684091 A 19971104
Revue Generale des Caoutchoucs et Plastiques
SULPHUR VULCANISABLE RUBBER
No.760, June/July 1997, p.83-6
COMPOUND
French
Maly N A; McGilvrey J R
FLAME RETARDANT PROPERTIES OF EPDM
Goodyear Tyre & Rubber Co.
COMPOUNDS
Krans J; Eichler H J This invention relates to the discovery that the
Martinswerk GmbH; DSM Elastomers Europe combination of tetrabenzylthiuram disulphide, cashew nut
oil modified novolak-type phenolic resin, a bismaleimide
Results are presented of a study of the influence of
compound and a sulphenamide compound provides for
different fillers, plasticiser oils and curing systems on the
excellent vulcanisation of rubbers and results in desirable
limiting oxygen index and smoke emission of EPDM
final rubber vulcanisate physical properties in the absence
compounds, and of flammability tests undertaken on roof
of generating undesirable nitrosamines and fumes during
coverings based on three different compounds. 5 refs.
processing and cure.
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
NETHERLANDS; WESTERN EUROPE USA
The effect of a new class of accelerators of the donor- Leiden,University; DSM Research; Port
acceptor type - phosphated alkylamides of fatty acids on Elizabeth,University
the kinetics of SBR and properties of the vulcanisates
Research methodologies for the investigation of the
were studied, and compared with mixes of the same
mechanism of vulcanisation are described and the
composition, but containing Altax (MBTS) as the
reactivity of thiuram and dithiocarbamate chemicals
accelerator. 7 refs. Translation of Kauchuk i Rezina, No.2,
1997, p.46 is discussed. The mechanism and chemistry of both
thiuram- and dithiocarbamate-accelerated sulphur
RUSSIA
vulcanisation are then considered. The integration of
Accession no.676672 the original mechanistic ideas from the 1960s and the
results obtained in the past three decades are shown to
Item 222 lead to a more balanced appraisal of events during
International Polymer Science and Technology vulcanisation. Proposals for future research are made.
24, No.11, 1997, p.T/53-4 262 refs.
COPOLYMERS OF GASEOUS SULPHUR AND EUROPEAN COMMUNITY; EUROPEAN UNION;
DICYCLOPENTADIENE AS VULCANISING NETHERLANDS; SOUTH AFRICA; WESTERN EUROPE
AGENTS FOR UNSATURATED RUBBERS Accession no.671090
Okhotina N A; Liakumovich A G; Samuilov Y D;
Avramenko Y P; Maksimov T V; Filippova A G;
Yamalieva L N; Mannanova F G Item 225
Kazan,State Technological University Revue Generale des Caoutchoucs et Plastiques
No.752, Sept.1996, p.69-72
A study was made of the conditions of copolymerisation French
of gaseous sulphur with dicyclopentadiene and its use as LATEST GENERATION OF ACCELERATORS
a vulcanising agent in the production of unsaturated Rebours B; Krans J
rubbers. The mechanism of the copolymerisation is DSM France; DSM Elastomers Europe
explained, and properties of rubber mixes of metal-cord
breaker containing sulphur Kristeks and copolymeric Studies were made of nitrosamine formation by a number
sulphur are tabulated. 3 refs. (Full translation of KIZ, of accelerators in EPDM compounds, and of the effects
No.3, 1997, p.33) of nitrosamine-free accelerators on cure characteristics
and heat resistance and compression set of vulcanisates.
Accession no.676327
The results showed the possibility of reducing cure times
and compression set values through the use of
Item 223 combinations of different nitrosamine-free accelerators.
Patent Number: EP 829508 A1 19980318 EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;
SULPHUR VULCANISABLE RUBBER NETHERLANDS; WESTERN EUROPE
CONTAINING HYDRATED THIOSULPHATE Accession no.670803
D’Sidocky R M; Cowling T B
Goodyear Tire & Rubber Co.
Item 226
The vulcanisation rate of a sulphur rubber composition is Kautchuk und Gummi Kunststoffe
increased by heating the rubber composition to a 51, No.2, Feb.1998, p.83-7
temperature ranging from 100 to 200C. The rubber NEW INTERPRETATION OF CROSSLINKING
composition contains a sulphur vulcanisable rubber, a MECHANISM OF NR WITH DICUMYL
sulphenamide compound and a hydrated thiosulphate, the PEROXIDE
latter two compounds significantly increasing the Gonzalez L; Rodrigez A; Marcos A; Chamorro C
vulcanisation rate of the rubber.
USA
The peroxide curing of NR is described. At high
temperature and high DCP loading, changes in the
Accession no.672221
crosslinking mechanism are observed. The results confirm
that the crosslink efficiency might be less than 1. Under
Item 224 these conditions both mechanisms, abstraction of an
Rubber Chemistry and Technology allylic hydrogen and addition to the double bond can take
70, No.3, July/Aug.1997, p.368-429 place. H1 NMR, fracture analysis and tensile stress data
THIURAM- AND DITHIOCARBAMATE- reveal that the compound with 3 phr DCP crosslinked at
ACCELERATED SULFUR VULCANIZATION 116 deg.C presents a non-uniform distribution of the
FROM THE CHEMIST’S PERSPECTIVE; crosslinks in the network. 21 refs.
METHODS, MATERIALS AND MECHANISMS EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;
REVIEWED WESTERN EUROPE
Nieuwenhuizen P J; Reedijk J; Van Duin M; McGill W J Accession no.670428
and the presence of silica did not affect the ability of ageing properties. The dithiophosphate system allowed
TiBTM to enhance the cure rates and scorch times of the higher curing temperatures and shorter cure times while
sulphenamide accelerators. Trends in the mechanical maintaining the desired mechanical properties. 5 refs.
properties of vulcanisates were similar to those occurring EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
in straight sulphenamide cured systems. The reversion USA; WESTERN EUROPE
resistance of NR vulcanisates was improved by TiBTM. Accession no.659549
6 refs.
USA
Item 246
Accession no.659551 IRC ’97. Conference proceedings.
Kuala Lumpur, 6th-9th Oct.1997, p.382-6. 012
Item 244 NEW CURING SYSTEM OF EPOXIDISED
152nd ACS Rubber Division Meeting, Fall 1997. NATURAL RUBBER (ENR) BY DI-O-
Conference Preprints. TOLYLGUANIDINE SALT OF DICATECHOL
Cleveland, Oh., 21st-24th Oct.1997, Paper 107, pp.26. 012 BORATE
FORMULATING FOR OPTIMIZED Nishi K; Kodama S; Kawasaki H
PROPERTIES USING REVERSION Okayama Prefecture Industrial Technology Center
RESISTANCE CHEMICALS (Rubber Research Institute of Malaysia)
Ignatz-Hoover F; Maender O; Datta R N The curing behaviour of epoxidised NR (ENR) with di-
Flexsys America LP; Flexsys BV orthotolylguanidine salt of dicatechol borate (DTGS), and
(ACS,Rubber Div.) the physical properties of the vulcanisate, are investigated.
A combination of two anti-reversion agents, The vulcanisate, which shows better tensile properties,
biscitraconimidomethylbenzene and hexamethylene-1,6- lower resilience and better performance of compression
bisthiosulphate disodium dihydrate, was used to improve set than peroxide-cured ENR, is obtained without other
the reversion resistance and tensile and tear properties curing agent. The vulcanisate containing high amount of
of sulphur vulcanised NR compounds. Experimental DTGS is found to be more rigid than that of the sulphur-
design and response surface methodology were used to cured ENR at room temperature, because its glass transition
arrive at a formulation providing an optimum balance temperature (Tg) is higher than room temperature. This
of properties for tyre applications. Vulcanisates having suggests that the crosslinking reaction involving the ring-
excellent retention of modulus on overcure or high opening reaction of epoxy group in the rubber leads to an
temperature cure were obtained. Tear strength was increase in the Tg of the vulcanisate. 6 refs.
maintained even at high retention of modulus in room JAPAN
temperature and hot tear tests. 5 refs. Accession no.658907
EUROPEAN COMMUNITY; EUROPEAN UNION;
NETHERLANDS; USA; WESTERN EUROPE
Accession no.659550 Item 247
IRC ’97. Conference proceedings.
Kuala Lumpur, 6th-9th Oct.1997, p.379-81. 012
Item 245 ROLE OF STEARIC ACID IN ACCELERATED
152nd ACS Rubber Division Meeting, Fall 1997. SULPHUR VULCANISATION
Conference Preprints. McGill W J; Mallon P E; Shelver S R
Cleveland, Oh., 21st-24th Oct.1997, Paper 106, pp.45. 012 Port Elizabeth,University
IMPROVED REVERSION RESISTANCE BY (Rubber Research Institute of Malaysia)
USING DITHIOPHOSPHATE VULCANIZATION
SYSTEMS IN THICK-SECTION MOLDED It is shown that the role of zinc stearate in vulcanisation
PARTS BASED ON NR formulations is to promote the reaction of accelerator
Johansson A H; Frueh T terminated polysulphidic pendant groups with
Rhein Chemie Corp.; Rhein Chemie Rheinau GmbH neighbouring polymer chains, thereby resulting in higher
(ACS,Rubber Div.) crosslink densities. Cyclisation reactions may also be
reduced, thus increasing stress induced crystallisation
Rhenocure SDT (Rhein Chemie), a dialkyl under load and thereby further enhancing the physical
dithiophosphate polysulphide sulphur donor, was properties of the vulcanisate. 6 refs.
evaluated in curing systems for the vulcanisation of thick
SOUTH AFRICA
NR parts. It was found that a curing system based on a
dithiophosphate accelerator and the dithiophosphate Accession no.658906
sulphur donor was superior to a system based on a
sulphenamide and dithiodimorpholine. A substantially Item 248
higher amount of short sulphur bridges was generated, IRC ’97. Conference proceedings.
leading to improved reversion resistance and superior heat Kuala Lumpur, 6th-9th Oct.1997, p.65-70. 012
acceleration, which can give improved modulus and degradation which may be determined by a rheometer
compression set values. or by modulus measurements after heat ageing. It
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; appears that amines, which are formed during the
USA; WESTERN EUROPE vulcanisation process as the decomposition products of
Accession no.658282 accelerators, are able to catalyse this reversion. If this
is the case, the reversion should be much reduced by
the use of accelerators which do not release amines
Item 256
during the curing process. 9 refs.
Rubber Technology International
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
1997, p.64-8
USA; WESTERN EUROPE
THIADIAZOLES FOR CROSSLINKING
HALOGEN-CONTAINING POLYMERS Accession no.657011
Ohm R F
Vanderbilt R.T.,Co. Item 259
Rubber and Plastics News
Di- and poly-functional mercaptans have been used for
26, No.23, 30th June 1997, p.30-2
many years to crosslink polymers with mobile halogens
ACRYLIC COAGENTS FOR RADIATOR HOSE
(chlorine or bromine). 2,5-Dimercapto-7,3,4-thiodiazole
USE
(DMTD) is one such crosslinking agent that displays
Burak L; Nagel W
relatively fast cures but poor scorch safety. Improved
Sartomer Co.
scorch safety can be achieved by derivatising one or both
mercapto groups. Several derivatives of DMTD have been It is explained that acrylic coagents can improve
developed in recent years for this purpose. Proper processability and vulcanisation of elastomers used in
selection of the thiodiazole derivative and associated automotive applications, and that “Saret” coagents from
accelerator is often a key to successful use in a given Sartomer Co. of the USA provide scorch-retarding
halogen-containing polymer compound. 3 refs. properties along with improved radiator hose properties
USA for all curing situations. This article describes tests
Accession no.657643 comparing several coagents in ethylene propylene diene
monomer radiator hose formulations. Results are
presented and discussed.
Item 257 USA
Patent Number: US 5616279 A 19970401
Accession no.653452
RUBBER VULCANISATION COMPOSITION
CONTAINING TETRABENZYLTHIURAM
DISULPHIDE, A BISMALEIMIDE, A Item 260
SULPHENAMIDE COMPOUND AND SULPHUR, Rubber World
A SULPHUR DONOR OR MIXTURES THEREOF 216, No.5, Aug.1997, p.24-7
D’Sidocky R M; Maly N A OPTIMISING TYRE COMPOUND REVERSION
Goodyear Tire & Rubber Co. RESISTANCE WITHOUT SACRIFICING
PERFORMANCE CHARACTERISTICS
Rubber vulcanisates obtained using the above compounds
Datta R N; Helt W F
exhibit superior physical properties and reversion
Flexsys BV
resistance.
USA Reversion is the thermal degradation of sulphidic
Accession no.657314 crosslinks leading to a reduction of crosslink density, a
change in the distribution of crosslink types and an
introduction of main-chain modifications. It leads to a
Item 258 decline in compound physical properties such as modulus,
International Polymer Science and Technology tensile and elongation, and in performance characteristics
24, No.4, 1997, p.T/1-11 such as tear, fatigue and hysteresis. Over the last few years,
REVERSION RESISTANCE OF NATURAL Flexsys has introduced two new rubber chemicals which
RUBBER MIXES WITH USE OF provide two different ways to improve the thermal ageing
DITHIOPHOSPHATE CURING SYSTEMS resistance of sulphur-based vulcanisates as compared to
Graf H J; Johansson A J existing technology. 5 refs.
Rhein-Chemie Rheinau GmbH; Rhein Chemie Corp. BELGIUM; EUROPEAN COMMUNITY; EUROPEAN UNION;
NR cured with standard accelerators shows signs of WESTERN EUROPE
reversion when exposed to heat ageing. The addition of Accession no.652374
an organic acid in addition to stearic acid decreases this
tendency towards reversion. Different types of Item 261
accelerator cause different degrees of crosslink Patent Number: EP 794219 A1 19970910
retarder) can be determined on the basis of the degradation accelerator residue. The vulcanisation process for EPDM
products of sulphur-linked material. Evolved gas analysis rubber was examined on the basis of the relationships
(EGA) and pyrolysis gas chromatography with adequate between the peak intensities of the characteristic products
detectors (mass spectrometer, flame emission detector) and cure time. 18 refs.
prove to be very successful as chemical-analytical JAPAN
methods for such investigations. 43 refs. Accession no.631060
SWITZERLAND; WESTERN EUROPE
Accession no.631938 Item 294
Rubber and Plastics News
Item 292 26, No.13, 10th Feb.1997, p.13-14
Journal of Polymer Science : Polymer Physics Edition APPROACHES TO IMPROVE REVERSION
35, No.5, 15th April 1997, p.725-34 RESISTANCE
SORPTION AND DIFFUSION OF ALIPHATIC Datta R N; Helt W F
HYDROCARBONS INTO CROSSLINKED Flexsys BV
NATURAL RUBBER Edited by: Herzlich H
Unnikrishnan G; Thomas S
Reversion and the associated changes in rubber compound
Mahatma Gandhi,University
performance properties is reported to continue to be a
The sorption and transport of four aliphatic hydrocarbons major concern for manufacturers of thick rubber products.
(n-hexane, n-heptane, n-octane and n-nonane) into NR It is becoming increasingly difficult to balance the need
crosslinked using conventional, efficient, dicumyl for improved product service life, particularly as service
peroxide(DCP) and mixed sulphur/peroxide vulcanisation temperatures rise, with increased product productivity and
systems were investigated at temp. of 28 to 60C. The NR using higher curing and/or processing temperatures
vulcanised by DCP exhibited the lowest penetrant uptake without realising some loss in physical performance
of the systems studied. It was observed that the kinetics characteristics through the cross section of these thick
of liquid sorption in every case deviated from the regular rubber articles. During the last few years two new rubber
Fickian trend, characteristic of sorption of liquids by chemicals - 1,3-bis (citraconimidomethyl) benzene
rubbers. The diffusion coefficient, activation energy of (Perkalink 900) and hexamethylene-1,6-bisthiosulphate
sorption, enthalpy, entropy and rubber-solvent interaction disodium salt dihydrate (Duralink HTS) - have been
parameter were evaluated for the four systems from the introduced to the rubber industry to provide unique
swelling data. 30 refs. approaches for improving reversion resistance without
INDIA sacrificing performance properties. The use and benefits
Accession no.631112 of these materials in thick rubber articles are described,
providing a comparison with traditional approaches
utilising lower sulphur/higher accelerator levels.
Item 293 USA
Kobunshi Ronbunshu
Accession no.630975
54, No.2, 1997, p.108-14
Japanese
STRUCTURAL CHARACTERIZATION BY Item 295
PYROLYSIS GAS CHROMATOGRAPHY OF International Polymer Science and Technology
ETHYLENE-PROPYLENE-DIENE RUBBERS 23, No.11, 1996, p.T/78-83
CURED WITH SULPHUR/THIAZOLE MELAMINE IN THE RUBBER INDUSTRY
ACCELERATOR Afanas’ev S V
Okumoto T; Yamada T; Tsuge S; Ohtani H
A survey is made of applications of melamine derivatives
Toyota Technical Institute; Toyoda Gosei Co.Ltd.;
in the rubber industry, with particular reference to their
Nagoya,University
uses as adhesion promoters, accelerators and scorch
EPDM rubbers cured with sulphur and accelerators were retarders. 43 refs. (Translation of Kauchuk i Rezina, No.4,
characterised by high resolution pyrolysis gas 1996, p.45).
chromatography with both a flame ionisation detector and RUSSIA
a sulphur-selective flame photometric detector. For curing Accession no.629932
with sulphur and 2-mercaptobenzothiazole accelerator,
two types of sulphur-containing products, such as
cyclopentathiophene and benzothiazole, were typically Item 296
observed in the pyrogram. The former was supposed to Rubber Chemistry and Technology
be formed from sulphur bridges to ethylidene norbornene 69, No. 4, Sept.-Oct.1996, p.577-90
residue in the polymer chain through cyclisation, while STRENGTH OF SULFUR-LINKED
the latter was considered to be derived from the pendant ELASTOMERS
being actively addressed by the rubber industry. R.T. influenced the resistance of the vulcanisates to
Vanderbilt has developed two new commercially degradation. 3 refs.
available ultra accelerators that provide an excellent EUROPEAN COMMUNITY; EUROPEAN UNION;
balance of low toxicity, low nitrosamine formation, good NETHERLANDS; WESTERN EUROPE
technical properties, and cost effectiveness. The Accession no.621093
technology was discovered by B.F. Goodrich and is
patented. The unique combination of properties offered
Item 303
by the new ultra accelerators based on diisobutylamine
Journal of Applied Polymer Science
is discussed. 3 refs.
63, No.2, 10th Jan.1997, p.233-7
GOODRICH B.F.,CO. KINETIC AND RHEOMETRIC INVESTIGATION
USA
OF HEXAMETHYLOL MELAMINE
Accession no.626517 DERIVATIVE ON THE CURE OF NATURAL
RUBBER COMPOUNDS
Item 301 Konar B B
Journal of Applied Polymer Science Calcutta,University
63, No.10, 7th March 1997, p.1353-9
APPLICATIONS OF AN AZIDE SULPHONYL Hexamethylol melamine (HMM) was characterised by
SILANE AS ELASTOMER CROSSLINKING AND FTIR spectroscopy. The optimum dose of HMM in the
COUPLING AGENT presence of a sulphur accelerator in a NR-filled compound
Gonzalez L; Rodriguez A; de Benito J L; Marcos- was determined. The cure rate and kinetics of crosslink
Fernandez A formation indicated that HMM enhanced the first-order
Instituto de Ciencia y Tecnologia de Polimeros rate of vulcanisation in an NR compound. The results
revealed good mechanical properties of an HMM-based
N-3-triethoxysilylpropyl-N’-p-benzene sulphonyl azide
NR carbon black-filled vulcanisate. 15 refs.
urea was synthesised and evaluated as a coupling agent
INDIA
in unfilled and silica filled SBR compounds and in unfilled
EPM compounds. The mechanical properties and Accession no.618929
crosslink density of vulcanisates were investigated. The
trialkoxysilane moiety of the coupling agent was capable Item 304
of reacting with the filler surface, and the azide group China Rubber Industry
reacted with the polymer matrix. In addition, alkoxy 43, No.11, 1996, p.658-62
groups hydrolysed in the presence of moisture to form Chinese
silanols which subsequently condensed into Si-O-Si and ACTIVATION OF CRUMB RUBBER WITH RD-F
formed an intermolecular crosslink. 12 refs. MECHANICAL-CHEMICAL METHOD
EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN; Wen Z; Suhe Z; Guochun B; Yanhao Z; Yanhui Z;
WESTERN EUROPE
Qiuhua L
Accession no.624426 Beijing,University of Chemical Technology
An activator is uniformly applied to the surface of crumb
Item 302
rubber with a high speed agitator, the strong shearing
Industria della Gomma
and fine grinding effect is applied to the crumb rubber
39, No.10, Oct.1995, p.16-20
Italian by an open mill to facilitate the bonding between
ELECTROCHEMICAL DEGRADATION OF activator and crumb rubber. The activator is composed
EPDM COOLER HOSES of curing agent, peptiser, antioxidant and phenolic resin.
Vroomen G; Verhoef H The curing agent is used to increase the crosslink density
DSM Elastomers Europe; DSM Research BV at the interface between crumb rubber and rubber matrix;
the antioxidant is used to increase the dynamic properties
Results are presented of studies by DSM of the mechanism of the compound; the phenolic resin is used to increase
of electrochemical degradation of EPDM automotive
the adhesion at the interface between crumb rubber and
cooler hoses in contact with water/ethylene glycol
rubber matrix. The RD-F activator system includes
coolants, and of the cracking occurring after different
antioxidant RD 1, phenolic resin 1,420 oil 1.5,
exposure times. The resistance to electrochemical
accelerator H 0.4, sulphur 0.5, accelerator CZ 0.5, vinyl
corrosion was influenced by the composition of the EPDM
compounds. Vulcanisates in which electrical conductivity tar 8. The wear resistance of tyre tread can be
was reduced by partly replacing carbon black with calcium significantly improved by using the crumb rubber
carbonate were resistant for longer periods than activated with the RD-F activator system.
vulcanisates filled with carbon black alone. The degree CHINA
of crosslinking and type of curing agent used also Accession no.617536
62, No.7, 14th Nov.1996, p.1057-66 The phenomenon of reversion which occurs in a NR
TETRAMETHYLTHIURAM compound when vulcanised using a conventional cure (CV)
DISULPHIDE(TMTD) AND 2- system is well known. Reversion leads to the impairment
MERCAPTOBENZOTHIAZOLE(MBT) AS of vulcanisate properties such as modulus, compression
BINARY ACCELERATORS IN SULPHUR set and heat generation. Efficient vulcanisation (EV)
VULCANISATION. III. VULCANISATION OF systems significantly reduce reversion and heat generation,
POLYISOPRENE IN THE ABSENCE OF ZINC and improve ageing resistance of NR vulcanisates. The
OXIDE improvement obtained, however, is achieved at the expense
Giuliani B V K M; McGill W J of flex and related strength properties. This is an important
Port Elizabeth,University consideration when rubber is used under dynamic
conditions. As a compromise between CV and EV, the
Polyisoprene was vulcanised with the binary accelerator
industry has adopted the so-called semi-efficient
system TMTD-MBT in the absence of zinc oxide. Samples
vulcanisation (SEV) system. For years, developments have
were heated in a DSC at a programmed rate, the reaction
been directed to enhance reversion resistance without
was stopped at points along the thermal curve and the
sacrificing flex and dynamic properties. The effects of a
system was analysed. Extractable curing agents and
new chemical, 1,3 bis(citraconimidomethyl)benzene (BCI-
reaction intermediates were analysed by high-performance
MX), are discussed, with respect to its mechanism of
liquid chromatography and the crosslink density of samples
actions and applications. The use of this chemical will allow
measured by swelling. Two crosslinking reaction sequences
rubber compounders to take advantage of the CV cure
were identified, the first being initiated by polysulphides
system with regard to flex/fatigue properties whilst
of the mixed accelerator N,N-dimethyldithiocarbamyl-
improving reversion resistance. 17 refs.
benzothiazole disulphide and the second by MBT. All the
EUROPEAN COMMUNITY; EUROPEAN UNION;
TMTD was consumed in the first reaction sequence. The
NETHERLANDS; WESTERN EUROPE
synergism of the reaction is discussed in terms of recent
studies detailing a reaction mechanism for TMPTD- Accession no.610056
accelerated vulcanisation. 17 refs.
SOUTH AFRICA Item 319
Accession no.610748 IRC ’96. International Rubber Conference. Conference
proceedings.
Manchester, 17th-21st June 1996, paper 37. 012
Item 317 RESISTANCE TO REVERSION OF NATURAL
IRC ’96. International Rubber Conference. Conference RUBBER WITH THE HELP OF
proceedings. THIOPHOSPHATE CURE SYSTEMS
Manchester, 17th-21st June 1996, paper 75. 012 Graf H-J; Johansson A H
NITROSAMINES IN RUBBER - LEGISLATIVE Rhein Chemie Rheinau GmbH; Rhein Chemie Corp.
TRENDS (Institute of Materials)
Loadman M J R
Malaysian Rubber Producers’ Research Assn. NR cured with common accelerators shows reversion if
(Institute of Materials) heat aged. Addition of an organic acid in addition to the
use of stearic acid decreases the tendency toward reversion.
Before considering any legislative trends relating to Different accelerators cause different degrees of crosslink
nitrosamine regulations, it is helpful to know what degradation as seen with a rheometer or evidenced by lower
legislation currently exists and how this position has modulus values upon heat ageing. It can be concluded that
evolved. An insight is provided into the thinking which amines available during vulcanisation as decomposition
has produced the current situation, with the aim of products from accelerators will catalyse this reversion. If
applying it to a future scenario. 22 refs. that is truly the case, then much less reversion can be
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; expected if an accelerator system is used that does not form
WESTERN EUROPE; WORLD
amines during curing. Standard, semi-efficient and efficient
Accession no.610139 cure systems were developed using sulphur, zinc
dithiophosphate and dithiophosphate tetrasulphide
Item 318 accelerator systems. After heat ageing, the retention of
IRC ’96. International Rubber Conference. Conference modulus and all other physical properties were much
proceedings. better than the control. After ageing seven days at 90
Manchester, 17th-21st June 1996, paper 40. 012 deg.C, vulcanisates cured with the efficient cure system
REVISITING THE CONVENTIONAL CURE: without free sulphur displayed outstanding reversion
NOVEL WAY TO CONTROL HEAT BUILD-UP resistance. 9 refs.
Datta R N; Talma A G; Wagenmakers J C EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
Flexsys BV USA; WESTERN EUROPE
(Institute of Materials) Accession no.610053
Item 326 It is shown that this additive can improve the thermal
150th ACS Rubber Division Meeting. Fall 1996. stability of the sulphur network, allowing for the use of
Conference Preprints. higher mould temperatures to decrease cure time and
Louisville, Ky., 8th-11th Oct.1996, Paper 5, pp.32. 012 extensive overcures without loss of mechanical properties.
REVERSION RESISTANT CURES FOR RUBBER Some applications of NR and NR/polybutadiene blends
COMPOUNDS BASED ON BIMS (BROMINATED which take advantage of this improved thermal stability
ISOBUTYLENE-PARAMETHYLSTYRENE) are described. 8 refs.
McElrath K O; Measmer M B USA
Exxon Chemical Co. Accession no.609303
(ACS,Rubber Div.)
Brominated isobutylene-paramethylstyrene copolymer Item 329
compounds were vulcanised using a variety of curing International Polymer Science and Technology
systems. Cure characteristics, reversion resistance and 23, No.5, 1996, p.T/70-2
vulcanisate mechanical properties were investigated, and VULCANISATION CHARACTERISTICS OF
the effects of stearic acid variations in a zinc oxide/zinc MIXES BASED ON SYNTHETIC
diethyldithiocarbamate curing system, glycols, POLYISOPRENE AND CONTAINING
hydrotalcite and copolymer composition were evaluated. BIOLOGICALLY ACTIVE COMPOUNDS
Studies of high severity heat ageing showed that certain Goncharova Y E; Sakharova E V; Potapov E E
composition and curing system combinations could yield Results are presented of an investigation of the influence
compounds retaining some mechanical properties even of phospholipids and/or proteins (components of NR) of
up to 70 hours at 200C. 6 refs. different compositions on the kinetics of vulcanisation
USA of mixes based on SKI-3 synthetic polyisoprene.
Accession no.609306 Phospholipids, which are highly effective surface-active
compounds, are shown to ensure better dispersion of the
Item 327 protein and components of the traditional vulcanising
150th ACS Rubber Division Meeting. Fall 1996. group in the elastomer matrix. Nitrogen-containing
Conference Preprints. phospholipids also have a significant accelerating effect
Louisville, Ky., 8th-11th Oct.1996, Paper 4, pp.19. 012 during sulphur vulcanisation. 7 refs. (Full translation of
NEW APPROACHES TO IMPROVE REVERSION Kauch.i Rezina, No.6, 1995, p.17)
RESISTANCE OF THICK SECTIONED RUBBER CIS; COMMONWEALTH OF INDEPENDENT STATES
ARTICLES Accession no.608104
Datta R N; Helt W F
Flexsys BV; Flexsys LP Item 330
(ACS,Rubber Div.) China Rubber Industry
43, No.9, 1996, p.536-8
Biscitraconimidomethylbenzene and hexamethylene
Chinese
bisthiosulphate disodium dihydrate, alone and in
THERMAL STABILITY OF EPDM
combination, were evaluated as anti-reversion agents in
VULCANISATES
thick sectioned NR articles cured at high and low
Chen Y; Ma X
temperatures. Effects on cure characteristics and the
Beijing,Research & Design Inst.of Rubber Ind.
mechanical properties of vulcanisates were investigated.
EUROPEAN COMMUNITY; EUROPEAN UNION; Comparisons are given of thermal stabilities of EPDM
NETHERLANDS; USA; WESTERN EUROPE vulcanisation cured with peroxide, sulphur, sulphur-
Accession no.609305 containing compounds, and two different blend curing
systems. 2 refs.
CHINA
Item 328
150th ACS Rubber Division Meeting. Fall 1996. Accession no.606835
Conference Preprints.
Louisville, Ky., 8th-11th Oct.1996, Paper 2, pp.11. 012 Item 331
ZINC SOAPS FOR IMPROVED Patent Number: WO 9519390 A1 19950720
VULCANISATES. II. RUBBER COMPOSITIONS COMPRISING A
Vander Kooi J POLYMERIC AMINE CO-ACTIVATOR
Struktol Co.of America Coran A Y; Tremont S J; Davis L H; Ignatz-Hoover F;
(ACS,Rubber Div.) McGrath M P
Monsanto Co.
The effects of an aryl zinc soap (Activator 73) on the
curing and reversion kinetics of rubber compounds and Vulcanisable rubber compositions are disclosed which
the mechanical properties of vulcanisates are examined. contain a vulcanisation co-activator which is a polymeric
amine, i.e. a hydrocarbon polymer with pendant alkyl Swedish Pulp & Paper Research Institute;
amine groups. The co-activators impart increased rates Stockholm,University
of vulcanisation with little decrease in scorch delay and
The viscoelastic properties of various crosslinked NRs
very little increase in the modulus of the cured
were studied by mechanical spectroscopy. The Tg was
compositions. No increase in heat build-up or decrease
found to be dependent on both crosslink density and
in flex-fatigue life is shown. Typical polymers forming
crosslink type. Higher values of Tg were obtained for
the backbone of the co-activators include EPDM rubber
sulphur-crosslinked NR than for peroxide-crosslinked NR
and polymers from butadiene or isoprene, with optional
at the same crosslink density. An increase in the
co-monomers.
accelerator level for the sulphur vulcanisate resulted in
USA
an increased crosslink density, but it had only a slight
Accession no.606614 effect on the viscoelastic properties. Polysulphidic
crosslinks, distinguished by carbon-13 NMR solid-state
Item 332 spectroscopy, were obtained at higher sulphur contents,
Patent Number: EP 735083 A1 19961002 i.e. lower accelerator/sulphur ratios, and they had a greater
ENAMINES AS VULCANISATION influence on Tg than monosulphidic and C-C crosslinks.
ACCELERATORS FOR NATURAL OR The rubbery tensile modulus was found to be dependent
SYNTHETIC RUBBERS on the crosslink density but almost independent of the
Broussard F; Adovasio M; Roncalli J; Taroni G; crosslink type. The crosslink density estimated from
Callierotti C modulus values was higher than estimates from swelling
Great Lakes Chemical Italia Srl measurements or from stress-strain data, probably due to
the time dependence of disentangling. 26 refs.
A general formula for these enamines is given.
SCANDINAVIA; SWEDEN; WESTERN EUROPE
EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;
WESTERN EUROPE Accession no.604383
Accession no.606213
Item 335
Journal of Applied Polymer Science
Item 333
61, No.9, 29th Aug.1996, p.1515-23
Journal of Applied Polymer Science
SULPHUR VULCANISATION OF
61, No.8, 22nd Aug.1996, p.1239-44
POLYISOPRENE ACCELERATED BY
ELASTOMERS WITH TWO CROSSLINKING
BENZOTHIAZOLE DERIVATIVES. IV.
SYSTEMS OF DIFFERENT LENGTHS VIEWED
REACTION OF POLYISOPRENE WITH N-
AS BIMODAL NETWORKS
CYCLOHEXYLBENZOTHIAZOLE
Madkour T M; Hamdi M S
SULPHENAMIDE(CBS), SULPHUR AND ZINC
Helwan,University
OXIDE
Elastomers cured with two crosslinking systems such as Gradwell M H S; McGill W J
sulphur and the polymerisation products of p- Port Elizabeth,University
benzoquinone are shown to have much improved overall
Polyisoprene was vulcanised using CBS, sulphur and zinc
mechanical properties. Non-Gaussian behaviour of
oxide by heating in a differential scanning calorimeter at
quinone polymer crosslinked elastomers viewed as
a programmed rate to given temps. The decomposition
bimodal networks was studied. The study focused on the
of CBS in the rubber was studied and the formation of
effect of ageing time on the reduced stress values of the
extractable reaction intermediates prior to and during
networks in relation to the elongation of the samples. The
crosslinking was investigated. The data were used to
study is also extended to cover the possible effect of these
propose a mechanism for the delayed action observed with
bound antioxidants on the onset of the vulcanisation
CBS and to explain the roles of sulphur, 2-
process and the hardness values of the elastomeric
bisbenzothiazole-2,2'-disulphide, 2-mercaptobenzo-
networks. 15 refs.
thiazole and zinc oxide in the reaction sequence. 24 refs.
EGYPT
SOUTH AFRICA
Accession no.604743
Accession no.604288
Item 334
Item 336
Journal of Polymer Science : Polymer Physics Edition
Rubber Chemistry and Technology
34, No.12, 15th Sept.1996, p.1997-2006
69, No.2, May/June 1996, p.273-6
EFFECTS OF THE TYPE OF CROSSLINK ON
STYRENE-BUTADIENE RUBBER FILLED WITH
VISCOELASTIC PROPERTIES OF NATURAL
FLUORINATED CARBON BLACK. II. EFFECT
RUBBER
OF CURATIVE LEVEL
Hagen R; Salmen L; Stenberg B
Ames K; Gibala DS; Hamed G R
Akron,University Chinese
The cure and tensile properties of sulphur vulcanised VULCANISATION BEHAVIOUR OF M OR DM
styrene-butadiene rubber filled with a conventional ACCELERATOR CONTAINING COMPOUNDS
furnace black or a fluorinated black have been determined. Xu J; Fu Y
Compositions with the fluorinated black and normal Jiangsu Danhua Group Corp.; Beijing,Research &
curative levels exhibit retarded cure compared to Design Inst.of Rubber Ind.
corresponding ones with the furnace black. This is due to The vulcanisation behaviour of NR compounds containing
a reaction between the sulphenamide accelerator and the M or DM accelerators was studied. Their effects on the
fluorinated black. Notwithstanding, a fluoro-filled processability and physical properties were investigated
composition with no curatives substantially crosslinks in detail. Data are given for tensile strength, modulus, tear
when moulded at 150 deg.C. Thus, fluoro-black filled resistance, rebound resilience, and heat ageing resistance.
specimens have competing effects toward crosslinking. CHINA
On the one hand, crosslinking is inhibited by reaction
Accession no.603235
with the accelerator, while on the other, the fluoro-black
itself can cause crosslinking. 2 refs.
Item 339
USA
Kautchuk und Gummi Kunststoffe
Accession no.603441 49, No.7-8, July/Aug.1996, p.532-7
German
Item 337 ANALYSIS OF N-NITROSAMINES IN RUBBER
Rubber Chemistry and Technology AND VULCANISATES - INFLUENCE OF
69, No.2, May/June 1996, p.180-202 INHIBITORS
NOVEL SULPHUR VULCANISATION Blume A; Giese U; Schuster R H
ACCELERATORS BASED ON MERCAPTO- Deutsches Institut fuer Kautschuktechnologie eV
PYRIDINE, -PYRAZINE, AND -PYRIMIDINE
Rostek C J; Lin H-J; Sikora D J; Katritzky A R; N-Nitrosamines are generally detected in rubber and
Kuzmierkiewicz W; Shobana N vulcanisates by methanol extraction and subsequent
Monsanto Co.; Florida,University detection by gas chromatography/thermal energy analysis
(TEA). The use of ascorbic acid as an inhibitor of
Sulphur vulcanisation accelerators derived from 2-
nitrosation during extraction has a negative effect on the
mercaptobenzothiazole (MBT) have been a staple for the
quality of the analysis. Interferences in the chromatogram
rubber processing industry for over 65 years. Most
hinder the classification and determination of N-nitroso
noteworthy are the sulphenamide derivatives, which
dimethylamine, N-nitroso diethylamine and N-nitroso
provide various combinations of scorch delay and cure
dipropylamine. The mechanism of the ascorbic acid
rate, depending upon the basicity and steric nature of the
interference is considered and it is shown that alpha-
sulphenamide N-substituent(s). While the effect of the
hydroxy acids decay at the temp. of the chromatographic
amine moiety on benzothiazole sulphenamide accelerator
columns by generating carbon monoxide which will give
performance has been well documented, the effect of the
a signal like NO at the TEA detector. The use of
S-linked heterocyclic moiety of the sulphenamide has
hydroquinone instead of ascorbic acid is shown to avoid
been investigated to a much lesser extent. Thus, to gain a
this problem, thus significantly improving the
better understanding of the role of the lieterocycle, a
determination of the above N-nitrosamines. 26 refs.
variety of novel disulphides and sulphenamides based on
EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
pyridine is synthesised and tested. The performance of WESTERN EUROPE
the pyridine based accelerators are compared to each other
Accession no.602882
and to the various benzothiazole analogues. Until recently,
the corresponding sulphenimides seem to have received
little attention in the rubber industry. Sulphenimides based Item 340
on pyridine, pyrazine and pyrimidine are therefore also Patent Number: EP 726255 A2 19960814
synthesised and tested. The differences in preparation and 3-PYRIDAZINE DERIVATIVES AND THEIR USE
vulcanisation activity for the benzothiazole sulphenimides IN RUBBER
and sulphenamides are described, as well as some Lin H-J; Rostek C J; Sikora D J
rudimentary differences which have appeared in the early Monsanto Co.
stages of mechanistic work. 35 refs. Thiols, disulphides and sulphenamides of certain
USA pyridazines are effective accelerators in the sulphur
Accession no.603433 vulcanisation of rubber. They exhibit improved rates of
vulcanisation and states of cure compared with known
Item 338 sulphenamide accelerators.
China Rubber Industry USA
43, No.8, 1996, p.478-81 Accession no.597919
Indian Association for the Cultivation of Science 60, No.3, 18th April 1996, p.425-30
THIURAM ACCELERATED SULPHUR
Investigations were carried out with the binary
VULCANISATION. I. THE FORMATION OF THE
combinations of each of bis(N-methylpiperazino)thiuram
ACTIVE SULPHURATING AGENT
disulphide, tetrabenzylthiuram disulphide, and
Geyser M; McGill W J
tetramethylthiuram disulphide, separately with N-
Port Elizabeth,University
cyclohexyl-2-benzothiazole sulphenamide, 2-
mercaptobenzothiazole, and 2-mercaptobenzothiazyl Mixtures of tetramethylthiuram disulphide(TMTD)/zinc
disulphide in the combinations studied. 19 refs. oxide and TMTD/sulphur/zinc oxide were heated in a
INDIA DSC to various temperatures. Zinc dimethyldithio-
Accession no.588288 carbamate formed only in undried TMTD/zinc oxide
mixes, the reaction being catalysed by water on the zinc
Item 356 oxide surface. The presence of zinc oxide delayed the
Rubber World decomposition of TMTD by absorbing thiuram sulphenyl
213, No.5, Feb.1996, p.34-6 radicals, which were needed to initiate tetramethylthiuram
QUATERNARY AMMONIUM SALTS: NEW monosulphide and tetramethylthiuram polysulphide
CURATIVES FOR VULCANISATION OF formation. 29 refs.
NATURAL RUBBER SOUTH AFRICA
Mathur R; Biswas A; Chandra A K; Mukhopadhyay R Accession no.586940
Sukhadia,University; Singhania Elastomer & Tyre
Research Institute
Item 359
This article describes preliminary work carried out to Rubber and Plastics News
evaluate the efficiency of triethylbenzylammonium 25, No.17, 11th March 1996, p.14-7
chloride (TEBA) in curing NR under different conditions. COAGENTS FOR RUBBER-TO-METAL
The study indicates that TEBA acts as a booster ADHESION
accelerator and produces a synergistic action with other Costin R; Nagel W R
primary accelerators to improve cure characteristics and Sartomer Co.
physical properties. The scorch safety properties of TEBA
Metallic coagent-peroxide systems were shown to provide
were compared with other combinations of synergistic
the best properties of peroxide and sulphur cures, yielding
accelerators.9 refs.
high tensile and tear strength, good heat-aged properties
INDIA
with the benefit of good adhesion. The use of Saret
Accession no.587356 metallic coagent systems, in particular, Saret 633, an
anhydrous zinc diacrylate containing a non-nitroso scorch
Item 357 retarder and Saret 634, an anhydrous zinc dimethacrylate
Journal of Applied Polymer Science are demonstrated to improve performance properties for
60, No.3, 18th April 1996, p.439-47 adhesive application. They eliminate the need for external
THIURAM ACCELERATED SULPHUR adhesives and a separate curing step, developing bonds
VULCANISATION. III. THE FORMATION OF at the rubber-metal interface during the curing step, and
CROSSLINKS producing crosslinks in the rubber during curing.
Geyser M; McGill W J
USA
Port Elizabeth,University
Accession no.586794
2,3-Dimethyl-2-butene (TME) was used as a model for
polyisoprene in studying the formation of crosslinks in
tetramethylthiuram disulphide (TMTD)-accelerated Item 360
sulphur vulcanisation. Mixtures of TME with TMTD, Rubber Chemistry and Technology
sulphur and zinc oxide were heated in sealed tubes at 130 68, No.5, Nov-Dec.1995, p.794-803
C for various times and the contents analysed by HPLC. SOLUBILITY OF SULPHUR AND
In the absence of zinc oxide crosslinking is delayed until DITHIOCARBAMATES IN NATURAL RUBBER
most of the TMTD was consumed. Crosslinking resulted Morris M D; Thomas A G
from the interaction of thiuram and dimethylammonium Malaysian Rubber Producers’ Research Assn.;
pendent groups, tetramethylthiourea being formed as a London,University,Queen Mary & Westfield College
by-product. 21 refs. Immersion of 1 mm thick sheets of peroxide-vulcanised
SOUTH AFRICA NR in both liquid and, more surprisingly, powdered solid
Accession no.586942 curing agents was shown to be an adequate method for
measuring solubilities. The same experimental method
Item 358 also enabled some diffusion data to be obtained.
Journal of Applied Polymer Science Solubilities of sulphur, zinc diethyldithiocarbamate and
zinc butyl dithiocarbamate were determined at various presence of residual unsaturation and hydroxyl groups,
temps. between 23 and 135C. The experimental results apart from chroman linked structure. 31 refs.
were not in good agreement with the theory which had EASTERN EUROPE; EUROPEAN COMMUNITY; EUROPEAN
previously been found to describe the solubility of waxes UNION; HUNGARY; NETHERLANDS; WESTERN EUROPE
in NR. This theory, which was a combination of the Flory- Accession no.586549
Huggins equation with an expression for the latent heat
of fusion, was modified to take into account the Item 363
dependence of the interaction parameter on temp. and on IRC ’95 Kobe International Rubber Conference.
degree of swelling. The new expression gave much better Conference proceedings.
agreement with the experimental results for all three Kobe, 23rd-27th Oct.1995, p.555-8. 012
compounds. 26 refs. (ACS Rubber Div., Spring Meeting, STUDY OF THE VULCANISATION
Philadelphia, May 1995) MECHANISM OF DIFFERENT ELASTOMERS
EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USING DSC AND FTIR
WESTERN EUROPE Gupta S D; Deuri A S; Mukhopadhyay R
Accession no.586556 Hari shankar Singhania Elastomer & Tyre Res.Inst.
(Japan,Society of Rubber Industry)
Item 361 Accelerated sulphur vulcanisation of rubber proceeds
Rubber Chemistry and Technology through an intermediate complex formulation between
68, No.5, Nov.-Dec.1995, p.746-56 accelerator and activator (zinc ion), the mechanism of
SULPHUR/OLEFIN COPOLYMERS AS which is yet to be fully understood. An attempt is made
VULCANISING AGENTS FOR RUBBER to understand the effect of different accelerators on
Colvin H; Bull C complex formation by different analytical techniques. The
Goodyear Tire & Rubber Co. results contribute to an elucidation of complex formation
A suspension process for the preparation of sulphur/ mechanism with different accelerators. 5 refs.
dicyclopentadiene and sulphur/dicyclopentadiene/styrene INDIA
copolymers, for use as vulcanising agents for rubber, was Accession no.586268
developed. The relationship between the sulphur/olefin
copolymer and vulcanisate properties was investigated Item 364
in terms of the structure of the copolymer and other IRC ’95 Kobe International Rubber Conference.
reaction products. 21 refs. Conference proceedings.
USA Kobe, 23rd-27th Oct.1995, p.543-6. 012
Accession no.586552 SUBSTITUTION OF TMTD IN DIENE RUBBER
COMPOUNDS
Graf H-J; Issel H-M
Item 362 Rhein-Chemie Rheinau GmbH
Rubber Chemistry and Technology (Japan,Society of Rubber Industry)
68, No.5, Nov.-Dec.1995, p.717-27
CHEMISTRY OF PHENOL-FORMALDEHYDE Thiurams are problematic from the point of ecology and
RESIN VULCANISATION OF EPDM. I. health care. Changing from thiuram-based systems to
EVIDENCE FOR METHYLENE CROSSLINKS alternative curing systems, especially TMTD, proves to
Van Duin M; Souphanthong A be a very powerful accelerating sulphur donor which is
DSM Research; Taurus Hungarian Rubber Works hard to replace. Dithiophosphoryl combinations as
The reaction products in phenol-formaldehyde resin alternatives for TMTD are described. 2 refs.
curing of EPDM, containing 2-ethylidene norbornene as EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
WESTERN EUROPE
the third monomer, were studied, using 2-ethylidene
norbornane(ENBH) as a low molec.wt. model for EPDM. Accession no.586265
The reaction of ENBH and a resole resulted in scission
of the dimethylene ether bridges, i.e. in degradation of Item 365
the resole into mono-, bis- and terisooctylphenol units. IRC ’95 Kobe International Rubber Conference.
These were consequently converted into products Conference proceedings.
consisting of two ENBH molecules linked by mono-, bis- Kobe, 23rd-27th Oct.1995, p.539-42. 012
and terisooctylphenyl units. The results supported the use HIGH TEMPERATURE CURING OF NATURAL
of 2-hydroxymethylphenol(HMP) as a low molec.wt. RUBBER COMPOUNDS BY USING 1,3
model for the resole. The reaction products of ENBH with BIS(CITRACONIMIDOMETHYL) BENZENE
both the resole and HMP were shown to contain Datta R N; Wilbrink J H
methylene-linked structures, as demonstrated by the Flexsys BV
formation of monoisooctylphenol crosslinks and the (Japan,Society of Rubber Industry)
assembled. Peel tests showed that failure was interfacial in STUDY ON COMPRESSION SET OF NBR AT
all cases and the reasons for this were discussed. 4 refs. ELEVATED TEMPERATURE
EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; Liu Yuzhen; Guo Yong; Li Zhenming; Xiao Jianbin
WESTERN EUROPE Qingdao,Institute of Chemical Technology
Accession no.584902 The influence of different curing systems and inorganic
fillers on the compression set of NBR N41 at 100 C was
Item 371 studied. The results show that DTDM EV system was the
148th ACS Rubber Division Meeting. Fall 1995. most effective in terms of minimum compression set of
Conference Preprints. the vulcanisate; DCP was more effective; CZ EV system
Cleveland, Oh., 17th-20th Oct.1995, Paper 110, pp.38. was poor; and sulphur curing system was the most poor.
012 Among the inorganic fillers, the quartz filler was the most
BLACK TYRE SIDEWALL COMPOUNDS BASED favourable to the minimum compression set of the
ON BROMINATED POLYISOBUTYLENE-CO-P- vulcanisate, and the compression set would change little
METHYLSTYRENE ELASTOMER AND with the increase of the quartz filler level; the other
ACCELERATED WITH 1,6-HEXAMETHYLENE favourable inorganic fillers were put in order of iron oxide
BISSODIUM THIOSULPHATE red, super-fine calcium carbonate and silica 233N and
Ignatz-Hoover F; Newman N F 255N. 2 refs.
Flexsys America LP; Exxon Chemical Co.
CHINA
(ACS,Rubber Div.)
Accession no.580967
The disodium salt of hexamethylene bisthiosulphate
(HTS) was evaluated as an accelerator in the zinc oxide
Item 374
mediated vulcanisation of tyre sidewall compounds
Tyretech ’95. 21st Century Technology: Evolution or
containing a brominated isobutylene-p-methylstyrene
Revolution? Conference proceedings.
copolymer. Rheometer profiles of blends with
Turin, 16th-17th Oct.1995, paper 17, pp.8. 6T
polybutadiene cured with sulphenamide, sulphur, zinc PERKALINK 900 NEW POSSIBILITIES FOR
oxide and HTS showed a characteristic delayed action HIGH TEMPERATURE CURING OF NATURAL
fast cure kinetic profile, while the same blends cured RUBBER COMPOUNDS
without HTS exhibited undesirable cure characteristics, Datta R N; Wilbrink J H
with long early cure and fast late cure. Many vulcanisation Flexsys BV
characteristics and vulcanisate properties were largely (Rapra Technology Ltd.; European Rubber Journal)
dominated by a single cure component. State of cure was
dominated by sulphur level, scorch delay and early cure This paper presents information in some detail on the use
time by HTS loading, and the time to reach t90 by the of a unique chemical to increase the curing temperature
sulphenamide level. Time of flight secondary ion mass of natural rubber compounds. Developed by Flexsys BV
spectroscopy imaging showed that HTS favourably of The Netherlands, Perkalink 900 1,3-bis(citraconimido-
affected the distribution of curatives in blends with SBR. methyl)benzene is said to be effective in the improvement
of reversion behaviour of systems containing diene
11 refs.
rubbers. It is thought that using this curing agent will
USA
reduce mould times, thereby aiding productivity in tyre
Accession no.583033 manufacturing. 10 refs.
EUROPEAN COMMUNITY; EUROPEAN UNION;
Item 372 NETHERLANDS; WESTERN EUROPE
China Rubber Industry Accession no.580914
43, No.2, 1996, p.95-8
Chinese
COMPARISON BETWEEN PROPERTIES OF Item 375
RADIATION CURED SBR VULCANISATE AND 148th ACS Rubber Division Meeting. Fall 1995.
SULPHUR CURED ONE Conference Preprints.
Xu Yunshu; Youssef H A Cleveland, Oh., 17th-20th Oct.1995, Paper 97, pp.31.
012
7 refs. SELECTING THE OPTIMUM COAGENT FOR
CHINA SEVERAL RUBBER APPLICATIONS
Accession no.580973 Costin R; Nagel W
Sartomer Co.Inc.
Item 373 (ACS,Rubber Div.)
China Rubber Industry Saret acrylic and methacrylic acid salts (Sartomer) were
43, No.2, 1996, p.67-71 compared with triallyl cyanurate as co-curing agents in the
Chinese peroxide vulcanisation of EPDM compounds for a number
of applications, including building profiles, radiator hose, TMTM combination, giving equivalent or better
moulded goods, cables, roll covers and sealants. Effects vulcanisation and vulcanisate properties. 4 refs.
on curing characteristics, mechanical properties and rubber- USA
to-metal adhesion were studied. 1 ref. Accession no.580275
USA
Accession no.580278 Item 378
148th ACS Rubber Division Meeting. Fall 1995.
Item 376 Conference Preprints.
148th ACS Rubber Division Meeting. Fall 1995. Cleveland, Oh., 17th-20th Oct.1995, Paper 75, pp.21.
Conference Preprints. 012
Cleveland, Oh., 17th-20th Oct.1995, Paper 95, pp.17. DCBS: A PREFERRED ACCELERATOR FOR
012 ADHESION COMPOUNDS AND OTHER TYRE
HYBRID, SEMI-EV CURE SYSTEM DESIGN APPLICATIONS
FOR GREATER PHYSICAL AND DYNAMIC Kleiner T; Ruetz L
PROPERTIES STABILITY IN A NATURAL Bayer AG
RUBBER BUSHING COMPOUND (ACS,Rubber Div.)
Cole W F; Scheufler D An examination is made of the performance of
Flexsys America LP; Clevite Elastomers Inc. dicyclohexyl benzothiazole sulphenamide (DCBS) as an
(ACS,Rubber Div.) accelerator in tyre compounds. Cure characteristics,
Optimised NR bushing compounds were developed using adhesion and flow properties are discussed, and it is shown
semi-efficient cure systems in which N-tert-butyl-2- that DCBS does not form carcinogenic N-nitrosamines.
benzothiazole was used as the primary accelerator, zinc 8 refs.
dibutyldithiophosphate as the secondary accelerator, N- EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;
cyclohexyl thiophthalimide as retarder, and hexamethylene USA; WESTERN EUROPE
bisthiosulphate disodium dihydrate as a stabilising hybrid Accession no.580258
crosslinker. These cure systems gave compounds with
improved stability of mechanical and dynamic mechanical Item 379
properties and shortened mould cycle times. 148th ACS Rubber Division Meeting. Fall 1995.
USA Conference Preprints.
Accession no.580276 Cleveland, Oh., 17th-20th Oct.1995, Paper 68, pp.17.
012
EFFECT OF 1,6-HEXAMETHYLENE
Item 377
BISSODIUM THIOSULPHATE ON CURE
148th ACS Rubber Division Meeting. Fall 1995.
KINETICS OF ACCELERATED SULPHUR
Conference Preprints.
VULCANISATION
Cleveland, Oh., 17th-20th Oct.1995, Paper 94, pp.15.
Ignatz-Hoover F; Dick J S; Maender O W
012
Flexsys America LP
TETRAISOBUTYLTHIURAM MONOSULPHIDE
(ACS,Rubber Div.)
(TIBTM): A UNIQUE RETARDER/KICKER IN
ONE MOLECULE Duralink HTS 1,6-hexamethylene bissodium thiosulphate
Chasar D W (Flexsys America) was used as a post-vulcanisation
Goodrich B.F.,Co. stabiliser in the sulphur vulcanisation of an NR compound.
(ACS,Rubber Div.) The effects of this additive on the cure characteristics and
on the tensile properties and tear strength of vulcanisates
Tetraisobutylthiuram monosulphide (TiBTM) was were investigated. The improved reversion resistance,
evaluated as a retarder and secondary accelerator for both network sulphur rank analysis on overcure and the
N-t-butyl-2-benzothiazole sulphenamide and N- stoichiometric dependence of activation energy on HTS
cyclohexyl-2-benzothiazole sulphenamide in SBR/ level supported the conclusion that the active sulphurating
polybutadiene and NR compounds. TiBTM was also species was altered. Improvements in tear strength at equal
compared in these systems to the retarder N-cyclohexyl modulus were consistent with the formation of a bimodal
thiophthalimide (CTP) and the secondary accelerator network. 16 refs.
tetramethylthiuram monosulphide (TMTM). When used
USA
at low levels with sulphenamide accelerators, TiBTM
could extend the scorch time by 2-3 minutes and then Accession no.580251
increase the cure rate beyond that of the primary
accelerator. The extent of these effects was influenced by Item 380
the types of rubber and sulphenamide. At low levels 148th ACS Rubber Division Meeting. Fall 1995.
TiBTM performed as an equivalent substitute for a CTP/ Conference Preprints.
characteristics of the vulcanisates were improved when The chemistry of vulcanisation and the technological
the aromatic nucleus of the catechol was bonded to properties of the vulcanisates obtained by the different cure
sulphur. Dicatechol sulphides (XX-125) derived from systems available are discussed. Sulphur vulcanisation,
catechol and sulphur chloride gave improved vulcanisate crosslinking reactions involving free radicals, electron
thermal stability. Curing properties of XX-125 seemed deficient species, ionic addition, ene-addition and diels-
enhanced by use with TMTD, and a variety of accelerators alder addition and vulcanisation by dehalogenation and
was developed by blending XX-125 with TMTD at the dehydrohalogenation are described. 429 refs.
weight ratio to obtain the desired cure rates and physical Accession no.132405
properties. These accelerators were suitable substitutes
for 2-mercaptoimidazoline (NA-22) in curing
polychloroprene. 8 refs. Item 410
Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i
Accession no.222561
Khimicheskaya Teknologiya
21, No.3,1978, p.433-6
Item 407 Russian
Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i CAUSES OF LOW STRENGTH IN RUBBERS
Khimicheskaya Teknologiya FROM SKI-3 WITH
23,No.5,1980,p.619-21 BISCHLOROMETHYLXYLENE
Russian SAL’NIKOVA V I; CHEKANOVA A A; ZAKHAROV
INFLUENCE OF METAL OXIDES ON N D; KOSTRYKINA G I; LITVINOVA L T
VULCANISATION OF RUBBERS BY BENZENE
The causes for the low strength values of ski-3 (cis-1,4-
DISULPHOCHLORIDE (BD)
polyisoprene) vulcanisates with bischloromethylxylene
Chekanova A A; Kostrykina G I; Zakharov N D;
are studied. The basic reason for the low strength for non-
Degtyarev E V
sulphur vulcanisates in comparison with sulphur-
A study was made of the vulcanisation of SKMS-30 ARK containing vulcanisates is the low degree of crosslinking
(70:30 butadiene-styrene copolymer) and SKN-26M and the high degree of non-uniformity in the vulcanisation
(butadiene-acrylonitrile copolymer, nominal AN content network, and the resulting low rate of orientation
27-30%) by BD, using ZnO, CaO or Al2O3 as activators. crystallisation. 11 refs.
The activating capacity of the oxides was shown to depend Accession no.123332
on their reactivity to Cl in ionic or radical form, and on
the role of vulcanisation of the metal chlorides formed in
the reaction. 9 refs. Item 411
Kauchuk i Rezina (USSR)
Accession no.168210
No.9,1975, p.15-8
Russian
Item 408 EFFECT OF ‘EFFECTIVE’ CURING SYSTEMS
SCIENCE & TECHNOLOGY OF RUBBER; ED.BY AND CURING TEMPERATURE ON TYPE OF
F.R.EIRICH NEW YORK,ACADEMIC PRESS,1978, CROSSLINK AND PROPERTIES OF
p.292-338. R.ROOM. 012 POLYISOPRENE RUBBER VULCANISATES
VULCANISATION SHAPKIN A N; TOLSTUKHINA F S; LAPSHOVA A
CORAN A Y A; FEDOROV A G
Vulcanisation of elastomers is discussed with special A study was made of the effect of ‘effective’ curing
reference to the following types of curing: sulphur and systems on the properties of sk1-3 vulcanisates, cured
accelerated sulphur vulcanisation; vulcanisation by normally (at 143c) and at elevated temperatures (180c).
phenolic resins, quinone derivatives and maleimides; The curing agents used were n,n’- dithiodimorpholine and
vulcanisation by metal oxides; curing with peroxides; and n,n’- tetrathiodimorpholine. Differences in the type of
crosslinking by chain extension reactions. Details on crosslink formed at different temperatures by ordinary
thermoplastic elastomers are included. 108 refs. and ‘effective’ curing systems were investigated. The ratio
Accession no.134706 between the different types of crosslink was correlated
with the properties of the vulcanisates. The advantages
of using the more effective sulphur donor (n,n’-
Item 409 tetrathiodimorpholine) are demonstrated. 9 refs.
PLASTICS & RUBBER INSTITUTE. PROGRESS OF
Accession no.55324
RUBBER TECHNOLOGY. VOL.41 LONDON,1978,
p.61-95. R.ROOM. 012
CURRENT STATUS OF ELASTOMER Item 412
VULCANISATION Journal of Applied Polymer Science
KIRKHAM M C 19, No.3,MARCH 1975, p.865-77
Subject Index
A ALKYL HYDROXIDE, 132 155 ASCORBIC ACID, 339
194 212 AUTOMOTIVE APPLICATION,
ABRASION RESISTANCE, 12 28 ALKYLPHENOL DISULFIDE, 40 83 84 85 89 108 121 140
42 62 107 144 146 159 204 210 283 142 143 216 259 302 313 324
251 267 282 304 307 318 323 ALUMINIUM HYDROXIDE, 216 376
325 375 380 398 AMIDE DISULFIDE, 201 AUTOMOTIVE HOSE, 142 143
ABSORPTION, 225 306 AMIDINOTHIOUREA, 60 388 216 302 313 324 375
ABSTRACTION, 59 AMINE, 2 31 38 52 76 86 89 101 AZIDE, 301
ACCELERATED AGEING, 333 118 130 155 161 168 180 211 AZIDOSULFONYLSILANE, 301
ACCELERATED TEST, 302 212 215 218 225 245 258 262 AZOMETHINE, 295
ACCELERATOR BLEND, 141 286 300 308 339 352 371 376
175 178 199 208 225 323 378 414
393 404 406 AMINOPHOSPHITE, 76
B
ACID ACCEPTOR, 273 324 401 AMMONIA, 113 149 BELT, 36 107 142 143 295 307 325
ACRYLIC ELASTOMER, 61 274 AMMONIUM ACETATE, 306 BENZENE, 132 155 306 365
367 401 AMMONIUM BENZOATE, 367 BENZENE DISULFOCHLORIDE,
ACRYLONITRILE-BUTADIENE AMMONIUM ETHYLENE 407
COPOLYMER, 179 186 BISDITHIOCARBAMATE, 91 BENZENESULFONYL
ACTIVATION, 116 146 233 355 AMMONIUM IODIDE, 148 CHLORIDE, 301
384 385 ANAEROBIC, 37 157 260 267 392 BENZOPHENONE, 212
ACTIVATION ENERGY, 23 24 47 ANALYSIS, 18 23 24 56 77 88 89 BENZOQUINONE, 333 383
65 241 244 292 328 338 379 94 98 99 100 125 126 132 140 BENZOQUINONEDIOXIME
ACTIVATOR, 23 46 54 56 58 89 141 142 144 155 164 182 225 ETHER, 343
95 159 170 236 237 238 247 244 245 248 249 255 268 273 BENZOTHIAZOLE, 56 99 137
266 274 277 297 304 328 331 278 280 281 282 283 291 301 161 243 250 293 321 335 337
356 371 407 414 302 306 307 311 312 313 326 390
ADHESION, 5 42 70 75 90 101 327 328 339 341 357 358 371 BENZOTHIAZOLE DISULFIDE,
107 111 124 129 142 157 171 375 376 377 378 379 380 386 99
229 281 282 283 295 304 309 390 393 396 398 404 BENZOTHIAZOLE GROUP, 299
313 324 359 370 375 376 378 ANTHRAQUINONE, 212 BENZOTHIAZOLE
380 392 395 ANTI-AGEING AGENT, 22 169 SULFENAMIDE, 31 141 243
ADHESION PROMOTER, 129 ANTI-REVERSION AGENT, 14 250 311 377
142 295 375 19 26 42 119 135 157 181 203 BENZOTHIAZOLYL
ADHESIVE, 127 171 295 315 375 205 210 244 267 284 288 307 DISULFIDE, 335
AEROSIL, 91 326 327 379 380 BENZOTHIAZOLYLDITHIO
AGEING, 14 15 18 30 37 38 42 60 ANTI-SCORCH AGENT, 25 132 COMPOUND, 230
65 82 87 121 132 142 143 144 142 156 192 243 255 271 295 BENZOTHIAZYL
148 153 162 163 183 184 190 311 326 375 376 377 393 401 DIALKYLTHIOCARBAMYL
202 204 207 244 245 259 260 ANTIDEGRADANT, 42 123 143 SULFIDE, 311
267 273 281 282 290 295 305 381 BENZOTHIAZYL DISULFIDE, 9
306 307 310 312 313 319 323 ANTIFREEZE, 302 BENZOYL PEROXIDE, 150
324 325 326 327 333 348 366 ANTIOXIDANT, 72 117 132 143 BENZYL BISMALEIMIDE, 65
369 374 375 376 380 387 392 169 172 262 370 376 403 BENZYLAMINE, 42 310 393
393 395 398 406 ANTIOZONANT, 36 42 130 132 BISAMINE DISULFIDE, 201
AGEING RESISTANCE, 9 67 76 229 BISBENZOTHIAZOLE
90 146 157 158 159 244 245 APPEARANCE, 282 DISULFIDE, 125 154
324 325 326 327 369 376 380 APPLICATION, 14 28 32 40 70 84 BISCITRACONIMIDE, 147 263
AIR CONDITIONING, 21 85 89 90 108 116 121 140 142 380
AIR HOSE, 143 143 177 190 212 216 259 295 BISCITRACONIMIDOMETHYL-
AIR SAMPLING, 89 155 298 302 313 324 381 394 398 BENZENE, 14 19 26 42 119
AIRCRAFT TYRE, 203 AROMATIC, 255 406 135 157 160 185 210 232 244
ALCOHOL, 132 155 194 212 AROMATIC OIL, 152 306 312 323 251 267 284 307 309 327 374
ALCOHOLAMINE, 217 ARRHENIUS’S LAW, 23 380
ALKYL DITHIOCARBAMIC ARTIFICIAL SALIVA, 89 BISDIALKYLTHIO-
ACID, 86 ARYL AZIDE, 301 PHOSPHORYL SULFIDE, 253
CO-CURING, 47 400 288 301 328 CUT GROWTH, 143 204 280 281
CO-CURING AGENT, 15 30 32 88 COVULCANISATION, 75 76 144 282 325
142 144 207 273 313 375 282 323 381 CYCLOHEXYL
COAGENT, 5 47 64 65 67 70 117 CRACKING, 144 281 282 283 302 BENZOTHIAZOLE
129 142 143 144 146 259 273 313 324 325 366 SULFENAMIDE, 10 20 27 164
313 359 375 381 387 CROSSLINK DENSITY, 1 9 10 12 335 355 404
COBALT DIETHYLDITHIO- 14 16 17 23 24 25 37 38 39 41 CYCLOHEXYL
CARBAMATE, 285 59 62 63 64 65 68 79 85 110 BENZOTHIAZYL
COBALT NAPHTHENATE, 199 113 126 128 133 134 135 139 SULFENAMIDE, 3 24 56 60
380 140 141 142 143 144 148 152 62 77 112 133 139 141
COMPLEX MODULUS, 5 282 156 160 166 170 173 197 205 CYCLOHEXYL
307 323 392 225 226 232 243 244 245 247 BENZOTRIAZOLE
COMPLIANCE, 112 307 380 392 250 255 260 264 274 280 282 SULFENAMIDE, 68
COMPOSITE, 7 126 142 153 176 286 295 296 301 304 307 308 CYCLOHEXYL BENZTHIAZYL
177 179 234 279 300 301 302 316 318 319 323 325 327 334 SULFENAMIDE, 3 60 112 133
322 378 380 345 351 356 378 379 380 387 139
COMPOUND, 14 23 43 140 141 390 392 400 CYCLOHEXYL
142 144 146 216 225 243 244 CROSSLINKING AGENT, 1 6 40 THIOPHTHALIMIDE, 125 132
245 255 278 279 280 281 282 45 58 59 64 65 71 73 90 98 128 255 376 377 393
283 301 307 310 313 323 324 138 148 166 179 188 194 229 CYCLOHEXYLAMINE, 101
326 327 341 371 376 377 378 231 249 275 296 333 350 CYCLOHEXYLAMINE
393 CROSSLINKING EFFICIENCY, BENZOTHIAZOLE, 96
COMPOUNDING, 22 23 40 72 69 273 312
116 118 127 132 140 141 144 CROSSLINKING PHENOMENA,
198 206 220 243 244 273 280 1 10 56 69 72 101 145 148 175
D
281 282 283 284 301 311 312 176 179 181 182 183 188 190 DECOMPOSITION, 21 41 56 71
313 318 323 324 325 326 327 194 201 208 209 260 289 399 72 73 89 140 146 180 204 228
328 338 359 367 368 371 375 401 410 301 335 358
377 378 381 392 393 395 398 CROSSLINKING RATE, 1 10 145 DECOMPOSITION PRODUCT,
COMPRESSION, 24 229 273 312 148 182 45 245
COMPRESSION MOULDING, 24 CRYSTALLINITY, 16 17 53 139 DEFORMATION, 113 221 244 282
144 326 268 DEGRADATION, 14 15 18 30 38
COMPRESSION PROPERTIES, CRYSTALLISATION, 16 17 229 42 60 65 82 84 87 108 121 127
307 322 244 282 380 398 410 132 134 142 143 144 146 148
COMPRESSION SET, 5 12 33 38 CUMYL PEROXIDE, 146 153 162 163 184 190 191 202
47 67 70 72 85 123 127 140 CURE RATE, 4 9 23 24 28 31 38 207 228 244 245 258 259 267
142 143 144 146 159 161 202 47 54 56 69 89 102 103 108 115 273 278 281 282 290 295 302
204 225 254 255 259 273 277 116 118 123 132 140 141 142 305 306 307 310 312 313 319
284 302 310 312 313 326 328 143 144 161 178 189 195 200 323 324 325 326 327 344 355
373 375 376 381 387 392 399 212 225 243 244 245 255 260 395 398
406 281 282 283 288 295 300 303 DEGRADATION RESISTANCE,
COMPRESSION STRESS, 307 311 313 324 326 327 328 329 80
376 340 351 355 359 368 371 375 DEGREE OF CROSSLINKING,
CONDOM, 158 376 377 378 379 380 387 389 10 34 90 91 273 302 312 370
CONDUCTIVE RUBBER, 22 324 393 401 406 410
CONTINUOUS CUREMETER, 20 130 DEGREE OF CURE, 17 301 306
VULCANISATION, 225 255 CURING BAG, 40 379 400
CONTRACEPTIVE, 89 158 CURING REACTION, 23 167 241 DELAYED ACTION, 250 335 371
CONVEYOR BELT, 307 325 277 289 389 392 DEMOULD, 375
COOLER HOSE, 142 143 302 CURING TEMPERATURE, 4 23 DESIGN, 33 124 215 225 244 277
COPPER 24 44 56 70 99 117 119 140 141 319
CYCLOHEXYLDITHIO- 142 144 146 154 164 166 180 DESIGN OF EXPERIMENTS, 225
CARBAMATE, 285 200 205 223 225 229 233 241 244 280 371 376
COPPER DIETHYLDITHIO- 243 244 245 255 267 273 280 DESORPTION, 89 155
CARBAMATE, 285 294 295 301 307 312 313 323 DESULFURATION, 23 307 379
COPPER SALICYLALIMINATE, 325 326 327 328 351 355 356 DETECTION LIMIT, 89 155 306
176 370 371 374 375 377 378 379 DEVULCANISATION, 228 264
COUPLING AGENT, 13 26 35 280 380 392 DI-TERT-BUTYL-4-
255 280 302 311 313 318 324 384 395 403 FLEXOMETER, 307 325 376 380
326 327 333 375 376 377 387 ETHYLENE-PROPYLENE- 392
392 406 NORBORNENE FLEXURAL FATIGUE, 143 157
ELONGATION AT BREAK, 12 23 TERPOLYMER, 286 289 323 376 393
63 64 91 144 152 166 221 245 ETHYLENE-VINYL ACETATE FLEXURAL PROPERTIES, 4 5 12
274 280 295 297 301 302 303 COPOLYMER, 6 70 128 146 15 24 30 36 42 110 142 143 144
307 308 323 326 355 379 380 359 159 307 318 324 370 393
381 ETHYLIDENE NORBORNENE FLOW, 159 255 273 295 312 376
EMBRITTLEMENT, 142 313 COPOLYMER, 293 362 378
EMISSION, 2 155 225 310 ETHYLIDENE NORBORNENE FLOW PROPERTIES, 66 109 350
EMULSION POLYMERISATION, TERPOLYMER, 216 225 FLUOROCARBON RUBBER, 61
24 193 367 EXPOSURE LIMIT, 77 155 310 76 143 146 176 179 190 273
ENERGY LOSS, 140 307 380 EXPOSURE TIME, 144 302 274 295 324
ENGINEERING APPLICATION, EXTENDER, 141 144 216 243 244 FOAMING AGENT, 21 41 140
398 281 306 311 312 323 326 381 234 298
ENVIRONMENT, 42 58 77 155 EXTRACTION, 1 56 59 89 132 FOOD-CONTACT
162 172 187 211 364 397 282 306 316 335 339 APPLICATION, 61 89
ENVIRONMENTAL STRESS EXTRUSION, 140 144 146 216 FORMALDEHYDE, 155 295
CRACKING, 302 234 255 283 295 312 323 324 FORMULA, 51 182 261 287 332
EPDM, 3 6 7 9 11 32 41 47 61 64 364 375 FORMULATION, 4 5 12 18 22 33
70 72 75 83 85 107 123 128 EYE IRRITATION, 307 40 47 57 70 79 80 81 93 96 106
139 140 142 143 144 146 148 108 109 112 117 118 121 124
156 165 169 194 202 207 215 127 130 131 160 185 197 198
216 225 234 241 255 259 273
F 202 204 205 210 239 241 246
282 286 290 293 296 302 312 FACTICE, 159 251 252 254 258 259 260 274
313 330 331 345 350 359 362 FAILURE, 127 142 143 144 152 276 277 294 305 337 341 354
364 375 381 384 395 403 267 281 323 325 327 370 380 356 363 365 366 368 387 392
EPICHLOROHYDRIN RUBBER, FAST CURING, 231 395 396
105 401 FATIGUE, 36 42 136 142 143 144 FOURIER TRANSFORM
EPOXIDISED NR, 25 57 198 233 152 157 173 185 229 267 281 INFRARED SPECTROSCOPY,
246 351 282 283 289 295 323 325 327 65 114 153 249 303
EQUILIBRIUM, 114 149 307 370 376 380 392 393 FRACTURE, 66 226 234 370
388 392 FATIGUE RESISTANCE, 40 62 76 FREE RADICAL, 23 146 409
ERASER, 89 136 232 260 282 289 325 327 FREQUENCY, 24 112 132 140 281
ETHANOL, 89 370 376 307 312 392
ETHENE COPOLYMER, 143 273 FATTY ACID, 25 78 159 170 221 FRICTION, 229 398
312 236 266 FUEL HOSE, 143 324
ETHER, 212 325 343 FEEDSTOCK, 236 238 240 FUME, 155
ETHYLENE ACRYLIC RUBBER, FIBRE, 80 89 FUNGICIDE, 90
61 FIBRE-REINFORCED RUBBER, FURNACE BLACK, 66
ETHYLENE COPOLYMER, 143 142 302
273 312 401
ETHYLENE THIOUREA, 112 324
FILLED, 170 253 303 345 370 371 G
404
325 347 FILLER, 3 7 22 25 26 27 39 48 49 GAMMA-IRRADIATION, 117
ETHYLENE-OCTENE 57 66 89 91 112 117 132 143 GAS CHROMATOGRAPHY, 2 56
COPOLYMER, 69 143 273 312 144 153 155 165 177 180 185 89 155 165 276 291 293 306
ETHYLENE-PROPYLENE 195 198 215 216 234 243 244 339
COPOLYMER, 32 35 69 146 266 273 280 281 282 283 288 GAS EMISSION, 225
273 295 301 342 295 301 302 303 312 313 322 GEL CHROMATOGRAPHY, 8 96
ETHYLENE-PROPYLENE- 323 324 326 328 350 370 371 151 249
DIENE TERPOLYMER, 3 6 7 373 376 381 388 389 395 404 GEL CONTENT, 13
9 11 32 41 47 61 64 70 72 75 83 415 GEL PERMEATION
85 107 123 128 139 140 142 FILM, 179 249 286 308 344 CHROMATOGRAPHY, 8 68
143 144 146 148 156 165 169 FLAME IONISATION, 56 293 306 96 151 249
194 202 207 215 216 225 234 FLAMMABILITY, 21 45 73 146 GENOTOXIC, 77
241 255 259 273 282 286 290 216 295 307 GIANT TYRE, 307
293 296 302 312 313 330 331 FLEXIBILITY, 21 142 282 324 GLASS TRANSITION
345 350 359 362 364 375 381 376 TEMPERATURE, 9 24 112 113
149 282 334 HEAT STABILITY, 86 117 122 155 215 317
GLOVE, 298 183 190 277 342 392 INFLATION PRESSURE, 281
GRADE, 41 116 395 HEAT TRANSFER, 140 245 328 INFRARED SPECTROSCOPY, 1
GRAPHITE, 22 HEATING, 99 140 223 225 306 63 65 114 145 249 274 301 303
GREEN STRENGTH, 216 274 281 311 316 324 357 358 390 356 369
324 HEAVY-VEHICLE TYRE, 14 122 INHIBITOR, 11 20 68 125 127 180
GREEN TYRE, 26 131 205 238 267 280 281 299 243 295 339
GUANIDINE, 56 140 323 328 INITIATION, 145 156 212 358
GUM, 404 HEXAMETHOXYMETHYL INITIATOR, 64 72 145 212 217
MELAMINE, 157 295 INJECTION MOULD, 312 328
HEXAMETHYLENE INJECTION MOULDING, 66 156
H BISTHIOSULFATE 255 273 295 350 381 398
HALOBUTYL RUBBER, 19 105 DISODIUM DIHYDRATE, 42 INNER TUBE, 19 163 395
143 325 379 394 395 157 206 232 244 326 327 371 INSOLUBLE, 42 81 109 262 286
HALOGEN-CONTAINING 376 379 386
POLYMER, 105 325 394 HEXAMETHYLENE DIAMINE INSULATION, 21 32
HALOGENATED, 92 188 231 394 CARBAMATE, 61 INTERACTION, 216 243 357 369
395 HEXAMETHYLOL MELAMINE, INTERACTION PARAMETER,
HANDLING, 45 67 71 73 146 349 303 380 24 26 292 360
359 HIGH MODULUS, 116 313 323 INTERFACE, 110 370
HARDNESS, 5 13 25 27 53 64 127 HIGH PERFORMANCE LIQUID INTERFACIAL STRENGTH, 144
140 142 143 144 145 162 197 CHROMATOGRAPHY, 1 56 370
204 221 229 245 255 266 273 68 96 99 100 151 250 265 306 INTERMEDIATE, 42 52 56 99 100
274 277 280 281 283 295 301 311 357 358 390 311
302 303 307 312 313 323 326 HIGH TEMPERATURE, 204 205 INTERNAL MIXING, 282 301
328 333 355 375 376 380 392 225 243 244 262 306 312 327 378
406 365 378 392 IONIC, 24 113 149 356 359 375
HEALTH HAZARD, 2 42 45 56 71 HNBR, 70 142 143 156 182 255 IRRITANT, 307
73 77 89 101 118 155 162 168 273 387 ISOBUTYLENE COPOLYMER,
172 180 186 211 212 215 216 HOSE, 21 36 83 84 85 107 142 143 283 326 371
225 276 277 300 307 308 310 190 216 259 302 313 324 375 ISOBUTYLENE ISOPRENE
317 364 397 HOT AIR AGEING, 94 144 245 COPOLYMER, 59
HEAT AGEING, 3 5 40 42 47 58 282 307 325 326 380 393 ISOCYANATE, 121
67 70 72 76 90 93 94 107 111 HYDRAULIC HOSES, 142 ISOCYANATOBENZENE
123 142 143 144 157 183 191 HYDROGEN ABSTRACTION, 23 SULFONYL AZIDE, 301
244 245 254 273 277 282 295 69 72 212 301 ISOPROPYL PHENYL
307 312 313 315 323 324 325 HYDROGENATED NBR, 70 142 PHENYLENE DIAMINE, 77
326 327 375 376 380 393 406 143 156 182 255 273 387 ISOTHERM, 306 333
HEAT BUILD-UP, 12 13 26 38 42 HYDROLYSIS, 56 76 180 231 301 ISOTHIOCYANATE, 276
58 62 103 111 130 131 142 157 302 371
HYDROPEROXIDE, 153 217 302
159 161 185 205 210 244 251
HYDROQUINONE, 146 271 339
K
260 267 280 284 289 307 318
323 327 328 331 376 380 392 HYDROTALCITE, 326 KAOLIN, 3 155 388
HEAT DEGRADATION, 18 23 43 HYDROXYALKYLPHENONE, KINETIC, 23 146 149 292 306 326
49 65 86 107 183 184 190 191 212 328 329 353 371 379 405
205 206 232 260 282 307 309 HYDROXYBENZENE, 295 KINETICS, 20 23 46 137 221 303
326 327 HYPALON, 394 403 389 390
HEAT GENERATION, 24 149 157 HYSTERESIS, 24 132 195 205
284 307 327 328 392 232 244 260 280 281 307 318
HEAT OF CURING, 328 328 380 392 393 L
HEAT RESISTANCE, 9 19 23 26 LAP JOINT, 142 313 375
32 33 36 40 42 65 71 72 83 90 I LAP SHEAR, 5 359 375
108 109 121 123 142 143 146 LATEX, 58 80 116 179 248 249
152 183 190 191 204 205 225 IIR, 19 49 93 200 281 325 305 308 310 317 344 356 398
244 245 260 278 279 290 295 IMPACT PROPERTIES, 13 295 LAW, 2 77 89 155 317
306 307 314 318 324 325 327 INDUCTION PERIOD, 16 17 23 LEACHING, 58 142 172
328 366 375 56 71 167 241 LEAD, 155
HEAT STABILISER, 36 325 INDUSTRIAL HAZARD, 2 77 89
LEAD OXIDE, 324 MELAMINE, 295 260 273 274 280 281 282 284
LEGISLATION, 2 77 89 155 317 MERCAPTAN, 231 294 301 302 303 307 311 312
378 397 MERCAPTOBENZOTHIAZYL 313 318 323 325 326 327 328
LIMITING OXYGEN INDEX, 216 DISULFIDE, 60 352 355 331 347 348 355 356 371 375
LINER, 395 MERCAPTOBENZTHIAZOLE, 376 377 378 380 382 387 392
LIQUID CHROMATOGRAPHY, 1 46 56 77 100 123 125 132 133 393 406
29 44 56 68 96 99 100 151 250 156 165 225 250 255 293 295 MOLECULAR STRUCTURE, 6 7
265 306 311 316 404 311 316 335 352 355 371 390 24 42 51 56 75 76 87 91 102
LIQUID CURING MEDIUM, 375 MERCAPTOBENZTHIAZOLE 120 150 174 180 188 194 212
LIQUID RUBBER, 323 328 DISULFIDE, 16 17 77 133 156 221 239 244 261 263 264 265
LOADING, 229 281 307 325 183 221 255 283 311 371 388 268 272 277 282 283 285 286
LORRY TYRE, 238 400 289 293 303 309 311 319 328
LOW MODULUS, 116 281 MERCAPTOIMIDAZOLINE, 406 332 352 355 356 361 380 381
LOW ODOUR, 375 MESITYLENE DINITRILE 382 385 392 395 399 403 405
LOW TEMPERATURE, 196 209 OXIDE, 186 196 209 346 MOLECULAR WEIGHT, 69 141
281 312 324 398 METAL, 55 295 302 313 375 380 164 193 216 313 326 375 377
LOW TEMPERATURE CURING, METAL ADHESION, 70 171 229 378 381 385 392 393
327 295 313 359 375 376 380 MONOSULFIDE, 4 62
METAL FIBRE-REINFORCED MONSANTO RHEOMETER, 327
RUBBER, 142 MONTE-CARLO
M METAL INSERT, 376 CALCULATION, 69 220
M-PHENYLENE METAL OXIDE, 24 255 262 325 MOONEY SCORCH, 127 141 243
BISMALEIMIDE, 400 347 354 401 407 408 414 255 273 277 283 310 311 312
MAGNESIA, 112 143 231 255 273 METALLOCENE, 202 312 323 326 337 377 378 379 393
277 325 METAPHENYL 406
MAGNESIUM CAPRYLATE, 401 BISMALEIMIDE, 290 MOONEY VISCOSITY, 24 33 130
MAGNESIUM DIOXIDE, 231 METAPHENYLENE 132 144 196 202 204 216 225
MAGNESIUM HYDROXIDE, 216 BISMALEIMIDE, 143 233 258 259 273 277 280 310
MAGNESIUM OXIDE, 112 143 METHANOL, 61 132 155 339 312 313 323 326 328 371 375
231 255 273 277 325 401 METHYL PYRROLIDINONE, 376 379 387 406
MALEATE, 27 195 MOONEY-RIVLIN CONSTANT,
MALEIMIDE, 408 METHYLBENZENE, 23 166
MANGANESE PEROXIDE, 302 METHYLBENZOTHIAZOLE, 56 MORPHOLINE, 155
MASS SPECTROSCOPY, 29 56 METHYLSTYRENE MORPHOLINODITHIOBENZO-
164 263 276 289 311 371 380 COPOLYMER, 283 326 371 THIAZOLE, 250 299
MASTERBATCH, 40 45 75 109 MICROEXTRACTION, 89 MORPHOLINOTHIOBENZO-
141 142 146 243 244 271 297 MICROWAVE THIAZOLE, 133 250 376
311 313 323 326 327 337 371 VULCANISATION, 140 MORPHOLOGY, 66 153 226 234
375 377 378 379 MIGRATION, 89 132 282 370 282 283
MASTICATION, 313 375 MINERAL FILLER, 216 301 328 MOULD FILLING, 273
MATERIAL REPLACEMENT, 2 MINERAL OIL, 216 MOULD FLOW, 66 123 277 376
27 31 72 101 141 159 162 168 MIXING, 23 74 103 118 121 127 MOULD FOULING, 66 375
239 308 319 364 376 397 132 140 141 144 160 171 185 MOULD TEMPERATURE, 328
MATERIALS HANDLING, 74 215 243 244 273 274 280 281 387
MATERIALS SELECTION, 70 282 283 297 301 311 312 313 MOULDING, 12 24 63 144 245
108 291 323 324 325 326 327 328 356 254 307 313
MBT, 56 77 132 133 156 225 255 367 371 375 377 378 381 386 MOULDING COMPOUND, 159
295 311 371 387 388 393 255
MBTS, 16 17 77 133 156 183 221 MIXING TIME, 132 273 282 MOVING-DIE RHEOMETER, 69
255 283 311 371 388 400 MODEL COMPOUND, 10 29 39 273 326 327 328
MECHANICAL PART, 140 168 52 99 100 120 132 134 135 151 MUTAGENICITY, 77 310
216 298 376 265 283 285 325 362 380
MECHANISM, 1 19 23 24 89 147 MODIFICATION, 24 69 70 75 90 N
148 153 178 180 181 187 215 91 113 132 136 198 246 281
224 244 250 267 302 316 325 283 326 N-BENZYLCITRACONIMIDE,
335 339 355 370 382 385 390 MODULUS, 28 35 53 69 110 116 134 135 289
393 400 401 402 414 123 127 141 142 143 144 156 N-PHENYL MALEIMIDE, 400
MEDICAL APPLICATION, 298 157 204 232 243 244 245 255 NAPHTHYLAMINE, 262
239 240 241 243 244 245 247 143 149 267 280 282 307 312 TEST SPECIMEN, 89 216 327
250 253 255 257 262 264 265 323 328 380 393 TETRABENZYLTHIURAM
268 270 279 282 283 285 288 TEAR RESISTANCE, 13 159 203 DISULFIDE, 4 28 42 103 141
289 291 292 293 302 303 306 232 260 289 299 338 387 213 225 257 355 393
307 311 330 333 334 335 344 TEAR STRENGTH, 12 13 24 25 TETRABUTYL THIURAM
353 354 357 358 360 363 368 27 38 42 85 129 141 142 144 DISULFIDE, 141
370 371 372 373 376 378 379 157 159 161 197 203 204 232 TETRAETHYLTHIURAM
380 382 385 386 388 390 393 243 244 260 266 274 277 280 DISULFIDE, 1 44 77 141 180
398 400 405 406 408 409 412 282 289 294 295 296 297 299 TETRAETHYLTHIURAM
414 301 307 313 318 323 325 327 MONOSULFIDE, 44
SULFUR COMPOUND, 9 29 39 328 359 375 379 380 392 393 TETRAISOBUTYLTHIURAM
50 193 213 279 382 398 411 406 DISULFIDE, 141 311 326
412 TEAT, 89 298 TETRAISOBUTYLTHIURAM
SULFUR CONTENT, 9 53 127 TEMPERATURE, 3 23 24 89 112 MONOSULFIDE, 141 243 311
158 225 243 255 132 133 140 141 144 146 149 377
SULFUR DONOR, 20 23 49 89 154 156 164 215 223 225 229 TETRAKIS(ETHYLHEXYL)-
169 225 232 245 255 283 302 236 241 244 250 255 273 280 THIURAM DISULPHIDE, 189
306 307 392 393 406 281 282 283 292 301 302 306 TETRAMETHYLTHIOUREA, 104
SULFUR VULCANISATION, 11 307 312 324 327 335 351 358 357
22 23 24 34 40 42 46 47 56 60 360 362 370 385 386 390 411 TETRAMETHYLTHIURAM
67 70 72 86 89 99 100 101 132 TEMPERATURE DEPENDENCE, DISULFIDE, 1 3 4 9 16 17 23
141 142 143 144 146 151 156 41 140 183 190 241 283 296 24 28 42 44 80 86 94 118 138
163 167 178 180 185 188 192 322 141 154 155 156 165 215 225
201 204 205 216 223 225 232 TEMPERATURE PROFILE, 140 255 265 281 305 306 316 355
243 244 245 255 260 282 283 327 357 358 385 388 389 393
287 289 296 297 302 306 307 TEMPERATURE RESISTANCE, TETRAMETHYLTHIURAM
311 340 359 370 371 376 378 231 366 MONOSULFIDE, 77 141 358
379 380 389 392 393 395 405 TENSILE PROPERTIES, 5 12 13 377
SURFACE ACTIVE AGENT, 237 16 23 24 25 27 35 53 60 62 63 TETRATHIODIMORPHOLINE,
329 353 64 79 85 91 107 108 113 116 411
SURFACE AREA, 66 153 280 281 126 127 139 140 141 142 144 THERMAL AGEING, 18 37 148
396 152 158 159 166 197 221 232 163 183 206 260
SURFACE PROPERTIES, 41 220 243 244 245 246 255 266 273 THERMAL BLACK, 66
SURFACE TREATMENT, 10 68 274 277 280 282 294 295 297 THERMAL CONDUCTIVITY, 21
110 381 299 301 302 303 307 308 311 328
SWELLING, 23 24 25 39 42 57 64 312 313 323 324 326 327 336 THERMAL DEGRADATION, 3 5
114 137 141 149 166 170 244 338 371 379 399 406 18 21 23 40 42 43 47 49 56 58
245 248 250 282 292 301 316 TENSILE STRENGTH, 12 24 35 65 67 70 72 76 86 89 90 93 94
326 334 356 370 380 388 53 63 64 79 85 91 107 116 126 107 111 123 142 143 144 157
SYNCHRONOUS BELT, 143 140 142 144 159 221 232 243 183 184 190 191 205 206 228
SYNERGISM, 34 99 140 143 151 244 245 273 274 280 282 294 232 244 245 254 260 273 277
167 212 260 274 311 316 352 295 301 302 303 308 311 313 282 295 301 307 309 312 313
355 356 404 406 323 324 326 327 345 355 359 315 323 324 325 326 327 348
SYNTHETIC FIBRE- 369 375 376 377 379 380 381 366 392 412
REINFORCED RUBBER, 142 387 392 THERMAL PROPERTIES, 1 24 40
302 TENSILE STRESS, 127 376 379 109 113 144 149 183 244 245
SYNTHETIC RESIN CURING TENSION SET, 281 282 309 311 322 328 330 338
AGENT, 49 361 362 TERT-BUTYL BENZOTHIAZYL 380
SYNTHETIC RUBBER, 21 35 69 SULFENAMIDE, 133 311 323 THERMAL STABILITY, 9 19 23
78 97 98 114 115 150 196 209 376 377 26 32 33 36 40 42 65 71 72 83
242 259 391 TERT-BUTYL BENZOTHIAZYL 90 108 109 121 123 142 143
SULFENIMIDE, 42 146 152 183 190 191 204 205
TERT-BUTYLAMINE, 101 225 244 245 260 278 279 290
T TEST EQUIPMENT, 202 273 281 295 306 307 314 318 324 325
TACK, 171 281 375 395 325 326 327 328 327 328 330 359 366 368 375
TALC, 3 155 TEST METHOD, 21 34 41 94 98 376 380 393 399 403 406
TALL OIL, 78 236 127 137 161 163 186 205 259 THERMOCHEMICAL CURE, 164
TAN DELTA, 5 24 25 42 132 142 274 277 278 279 310 THERMOGRAVIMETRIC
ANALYSIS, 63 133 164 281 299 304 323 328 378 393 SPECTROSCOPY, 1 274 301
THERMOOXIDATIVE TRIALLYLCYANURATE, 88 146 VINYL ACETATE-ETHYLENE
DEGRADATION, 153 228 368 273 295 313 375 COPOLYMER, 70
THERMOOXIDATIVE TRIAZINE, 295 324 VISCOELASTIC PROPERTIES,
STABILITY, 152 412 TRIENE, 119 134 135 325 380 14 21 24 53 87 132 282 289
THERMOPLASTIC RUBBER, TRIETHANOLAMINE, 48 273 307 323 334 378 380 393
128 145 312 TRIETHOXYSILYLPROPYL VISCOMETRY, 233 273 312 351
THIADIAZOLE, 143 231 256 324 BENZENE SULFONYL 371 376 379
THIAZOLE, 34 42 47 130 144 158 AZIDE UREA, 301 VISCOSITY, 24 119 132 140 144
238 255 262 293 352 355 TRIETHOXYSILYLPROPYL 146 196 207 216 225 234 255
THICK-WALL, 245 307 327 TETRASULFIDE, 280 273 280 283 308 312 313 314
THICKNESS, 216 245 273 281 TRIETHYLALKYLAMMONIUM 319 323 326 328 346 350 371
312 328 BROMIDE, 353 375 376 379
THIOCARBANILIDE, 305 TRIETHYLBENZYL- VOLATILISATION, 56 132
THIONYL CHLORIDE, 301 AMMONIUM CHLORIDE, VOLATILITY, 89 155 300 310 393
THIOPHENE, 293 274 356 396
THIOPHOSPHORYL TRIMETHYLOLMELAMINE, VOLUME RESISTIVITY, 22 302
DISULFIDE, 352 295 324
THIOUREA, 60 86 143 180 277 TRIMETHYLOLPROPANE VULCAMETER, 13
388 TRIMETHACRYLATE, 32 207 VULCANISATION
THIOXANTHONE, 212 313 PHENOMENA, 175 176 182
THIRAM, 1 9 118 138 141 165 TRIMETHYLPROPANE 190 201 208
265 316 TRIACYLATE, 65 VULCANISATION RATE, 62 75
THIURAM, 22 42 47 56 89 130 TRIPHENYLPHOSPHINE, 306 101 156 167 175 182 200 201
141 143 144 151 180 202 255 TROUSER TEAR TEST, 244 323 208 223 288 303 331
262 276 325 357 358 364 393 379 VULCANISATION TIME, 4 23 24
THIURAM DISULFIDE, 28 31 TRUCK TYRE, 14 122 131 205 25 27 56 60 67 99 119 141 142
104 141 143 201 311 355 267 280 281 323 328 393 143 159 175 200 207 225 228
THIURAM POLYSULFIDE, 201 TYRE, 14 19 26 28 38 58 82 90 239 241 244 245 255 273 274
THIURAM SULFIDE, 31 103 141 102 103 119 122 130 131 132 277 280 281 282 287 293 294
224 368 141 157 160 161 163 168 177 297 301 303 307 310 311 312
TIME, 153 236 241 333 362 180 191 203 204 205 232 238 313 323 325 326 327 328
TIMING BELT, 143 243 244 260 267 280 281 282
TIN DICHLORIDE, 49 283 295 298 299 307 323 325
TMTD, 1 3 4 9 16 17 23 24 28 42 328 371 374 378 380 386 392 W
44 86 118 138 141 154 155 156 393 395 398 WASTE, 74 172 177 285
165 215 225 255 265 281 305 TYRE TREAD, 14 82 119 130 131 WATER, 56 89 302 358
306 316 385 388 389 393 406 205 238 251 267 299 304 415 WATER POLLUTION, 58 77
TMTM, 77 141
WATER RESISTANCE, 107 129
TOLUENE, 23 245 385
TOLUENE DIISOCYANATE, 315 U 142 313
TOOTHED BELT, 143 WAX, 323
TORQUE, 23 25 39 57 128 139 ULTRAVIOLET CURING, 171 WEAR, 85 142 210 281 398
140 141 142 144 156 255 266 212 WEAR RESISTANCE, 12 28 42
273 280 282 301 307 312 313 ULTRAVIOLET DEGRADATION, 62 107 144 146 159 204 210
323 327 328 351 355 356 370 80 282 344 251 267 282 304 307 318 323
371 375 376 378 379 392 393 UNDER THE BONNET 325 375
TOXICITY, 2 42 56 77 89 155 168 APPLICATION, 40 83 84 121 WET CURING, 301
180 186 212 215 216 225 300 143 WET GRIP, 132 280
307 308 310 378 384 393 397 UNDERCURE, 245 283 306 327 WIRE COVERING, 32
TOYS, 89 UNVULCANISED, 24 140
TRANS-1,4-POLYISOPRENE, 53 X
TRANSMISSION ELECTRON V
MICROSCOPY, 35 94 170 226 XANTHATE, 12 63 385
283 V-BELT, 142 143 325 413
TRANSPORT APPLICATION, 216 VEGETABLE OIL, 110
392 VIBRATION DAMPER, 216 307 Y
TREAD, 14 58 82 119 130 131 132 328 376 YOUNG’S MODULUS, 23 139
205 238 243 244 251 267 280 VIBRATIONAL 295 307 323 345 387
Z
ZINC BISPENTAMETHYLENE-
DITHIOCARBAMATE, 86
ZINC CARBOXYLATE, 328
ZINC CHLORIDE, 52 59 148
ZINC DIBENZYLDITHIO-
CARBAMATE, 42 326
ZINC DIBUTYLDITHIO-
CARBAMATE, 77 80 225 360
ZINC DIBUTYLDITHIO-
PHOSPHATE, 225 376
ZINC DIETHYL
MERCAPTOBENZO-
THIAZOLE, 80
ZINC DIETHYLDITHIO-
CARBAMATE, 12 44 77 134
180 285 308 326 344 360
ZINC DIISOBUTYLDITHIO-
CARBAMATE, 326
ZINC DIMETHACRYLATE, 64
142 143 313 375
ZINC DIMETHYLDITHIO-
CARBAMATE, 16 120 134 135
358
ZINC DITHIOCARBAMATE, 52
89 276 385
ZINC DITHIOPHOSPHATE, 143
384
ZINC MERCAPTOBENZO-
THIAZOLE, 80 135 158 308
344
ZINC METHACRYLATE, 18 143
ZINC OCTOATE, 371
ZINC OXIDE, 1 20 23 24 41 44 46
49 54 56 59 62 77 79 86 96 99
112 133 140 143 155 180 244
250 255 265 277 283 297 311
313 323 325 326 335 357 358
370 371 393 395 400 403 407
416
ZINC PEROXIDE, 24 113 149
ZINC STEARATE, 59 155 247 326
ZINC SULFIDE, 180 238