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Chemistry of EPDM cross-linking

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 ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS

EPDM
Cross-linking
Vulcaniza-

tion
Sulphur
Peroxide
Resol

Chemical mechanism
Review
Chemistry of EPDM Cross-linking1
Most EPDM applications require M. van Duin, Geleen, (The Netherlands)
cross-linking, which is commonly
achieved via accelerated sulphur
vulcanization. Co-agent-assisted
peroxide cure is applied for improv-
ing the thermal stability and/or the
compression set of EPDM. Acti-
vated resol cure is only used for the
dynamic vulcanization of PP/EPDM EPDM cross-linking rate is rather low in comparison with poly-
blends, i.e. for the production of diene elastomers and, therefore, a rela-
TPVs. In this paper an overview is Random copolymers of ethylene and pro- tively large amount of accelerators is
given of the chemical structures of pylene (EPM) with medium ethylene con- needed. Because of the large difference
the intermediates, the end products tents are amorphous or semi-crystalline in polarity between the polar accelerators
and the side products formed upon elastomers. As a result of the absence and the apolar EPDM elastomer, the so-
cross-linking of EPDM. In addition, of unsaturation, EPM cannot be vulca- lubility of the accelerators is limited and
reaction mechanisms are presented, nized with sulphur and is not very reactive usually a mixture of up to 5 accelerators
explaining the various structures towards peroxide curing. To increase the is applied.
formed. (Dis)advantages of the three reactivity for cross-linking a diene is poly- Saturated EPM can be cross-linked
cross-linking systems are ad- merized in combination with ethylene and with peroxide, but unsaturated EPDM is
dressed. propylene [1 ± 3]. The resulting EPDM ter- cured much more efficiently. The share
polymer combines a saturated polymer of peroxide-cured EPDM is gradually in-
backbone with residual unsaturation in creasing at the expense of sulphur-vulca-
Chemie der EPDM-Vernetzung side groups. A large variety of dienes nized EPDM, because of the high thermal
has been studied [4], but 5-ethylidene- stability of the C-C cross-links formed in
EPDM
Vernetzung
Vulkanisation

2-norbornene (up to 10 wt.% ENB), dicy- peroxide-cured EPDM in combination
Schwefel
Peroxid
Resol
chemi-
clopentadiene (up to 5 wt.% DCPD) and with the increasing high-temperature de-
scher Mechanismus
UÈberblick
5-vinylidene-2-norbornene (less than 1 mands of end-users. However, sulphur-
wt.%) are currently the only dienes vulcanized EPDM is superior with respect
Die meisten EPDM-Anwendungen
used in commercial EPDMs. to ultimate mechanical and dynamic
erfordern eine Vernetzung, die uÈbli-
As a result of its saturated polymer properties.
cherweise durch eine beschleunigte
backbone, EPDM is more resistant to Resols are commercially used for the
Schwefel-Vulkanisation erreicht
oxygen, ozone, UV and heat than low- cross-linking of EPDM in the production
wird. Zur Verbesserung der thermi-
cost commodity elastomers, such as of TPVs. Resols provide a high thermal
schen BestaÈndigkeit und/oder der
NR, BR and SBR. This makes EPDM stability of the cross-linked rubber disper-
Druckverformung von EPDM wird
the preferred elastomer for outdoor (auto- sion without affecting the PP matrix, as
eine ko-agens-unterstuÈtzte Peroxid-
motive sealing systems, building profiles will occur when peroxides are used for
HaÈrtung angewendet. Eine aktivierte
and roof sheeting) and under-the-hood TPV production. Other cross-linking
Resol-HaÈrtung wird nur fuÈr die dy-
applications. The main drawback of agents, such as bismaleimides, quinone
namische Vulkanisation von PP/
EPDM is its poor resistance to swelling dioximes, bisthiols, bisazides etc., are
EPDM-Mischungen durchgefuÈhrt,
in apolar fluids, such as oil. Over the merely of academic interest.
d. h. fuÈr die Herstellung von TPVs.
last decade TPVs, produced via dynamic
Diese Abhandlung enthaÈlt eine
vulcanization of PP/EPDM blends, have
UÈbersicht uÈber die chemischen
been commercialized, combining rubber
Strukturen der Zwischenprodukte, Techniques for studying EPDM
elasticity with thermoplastic processabil-
der Endprodukte und der Neben- cross-linking
ity [5, 6].
produkte, die bei der Vernetzung
Most EPDM applications require cross- When studying the chemistry of rubber
von EPDM entstehen. Auûerdem
linking, which is commonly ( 85%) cross-linking, two experimental ap-
werden die Reaktionsmechanismen
achieved via accelerated sulphur vulcani- proaches can be distinguished: the ana-
fuÈr die verschiedenen gebildeten
zation. As a result of the small amount of lysis of the cross-linked rubbers them-
Strukturen dargelegt. Ferner werden
unsaturation of EPDM, its vulcanization selves and the so-called low-molecular-
die Vor- und Nachteile dieser drei
Vernetzungssysteme beschrieben. weight model studies. Analysis of the
cross-linked rubbers is a direct approach
1 and is, therefore, preferred. However, a
Presented during the Kautschuk-Herbst-Kollo-
quium 2000, Deutsches Institut fuÈr Kautschuk- large number of practical problems had
technologie, Hannover November (2000) to be overcome before spectroscopic

150 KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 4/2002

 Chemistry of EPDM Cross-linking

techniques such as IR, Raman and solid Sulphur vulcanization ethylidene unit and the formation of sul-
state NMR spectroscopy could be ap- phidic species with 1 up to 5 S-atoms
plied for studying rubber cross-linking Sulphur vulcanization of EPDM and other a large number of cross-link structures
[7, 8]. elastomers is usually performed in the ( 40) is finally produced.
As a result, most progress with respect presence of activators (ZnO and stearic At elevated temperature desulphura-
to the understanding of rubber cross- acid) and accelerators (MBT, TMTD, tion occurs, resulting in shorter sulphur
linking chemistry was originally made ZDMC etc.). Although no dedicated stu- bridges [12, 18, 27, 28] and in the forma-
by ªcross-linkingº low-molecular-weight dies have been performed, it is expected tion of a thiophene-like structure [18].
model olefins [9, 10]. Because of their that the mechanism of sulphur vulcaniza- Side reactions as frequently observed
low molecular weight the corresponding tion of EPDM (Fig. 1) is similar to the me- for polydiene elastomers, such as cis-
model cross-links are soluble and some- chanism that is generally accepted for trans isomerization, allylic rearrangement
times volatile, allowing chromatographic polydiene elastomers [25, 26]. and/or the formation of conjugated
techniques such as GC and LC to be Accelerated sulphur vulcanization of dienes and trienes, do not occur during
used for separation and liquid state EPDM results in the substitution of the la- vulcanization of ENB-containing EPDM,
NMR and MS for identification. 2-Ethyli- bile allylic H-atoms by sulphur bridges, because of the stability of the tris-alkyl
dene norbornane (ENBH) has frequently yielding alkenyl sulphides [8, 11 ± substituted unsaturation in ENB and its
been used as a model for ENB-contain- 13, 17, 18]. The pendent ENB unsatura- isolation from other ENB units. The for-
ing EPDM [11 ± 15]. It is noted that several tion is not consumed, but activates the mation of carbonyls at C-5 and/or C-8
practical pitfalls relating to the use of low- allylic positions. Initially, accelerator resi- of ENB-EPDM due to oxidation was
molecular-weight models have been en- dues are attached to the allylic positions shown to be linked to accelerated sul-
countered in the past [9]. ªTranslationº of via a sulphur bridge, yielding cross-link phur vulcanization of EPDM [18]. As a re-
the results to the polymer system may precursors. Subsequently, the actual sul- sult of the thermal instability of sulphides,
also be a source of errors. phur cross-links are formed. Sulphur- sulphur vulcanized EPDM can be devul-
Due to the low unsaturation content, substitution of ENB occurs at C-3exo, canized in the presence of diaryldisul-
direct cross-linking studies of EPDM C-3endo and C-9 (not at bridge head phides and/or amines at temperatures
have suffered from analytical sensitivity C-1). In combination with the Entge- above 300 8C [29].
problems, which were only overcome in gen/Zusammen-isomerism of the ENB
the last decade. With respect to sulphur
vulcanization of EPDM only a few optical
spectroscopy studies have been pub-
lished [8, 16, 17], whereas the first 13C so-
lid-state NMR study required 13C-enrich-
ment of the ENB unsaturation [18]. With
respect to peroxide cure of EPDM, FT-IR
has been of great value for determining
the conversion of the unsaturation and
elucidating the role of the co-agent
[16, 19 ± 23]. Finally, with respect to resol
cure only a few model studies have been
published [14, 15] and only recently the
first 13C solid-state NMR study using
13
C-enriched EPDM was performed [24].

Scope
The goal of this paper is to present an up-
to-date overview of the chemistry of
EPDM cross-linking with accelerated sul-
phur, co-agent-assisted peroxide and ac-
tivated resol systems. The emphasis will
be on the chemical structure of the
cross-links, but in the case of peroxide
and resol cure also on the reaction path-
ways. ENB and DCPD as the main com-
mercial third monomers of EPDM have
received most attention and are, there-
fore, used as examples throughout the Fig. 1. Products and reaction mechanism of accelerated sulphur vulcanization of EPDM
(X ˆ accelerator residue); note: sulphur-substitution at C-3exo and C-9 is just given as an
review. The effect of the diene structure example; the reaction mechanism shown is generally accepted for sulphur vulcanization
will be discussed where appropriate. of polydiene elastomers [25, 26]

KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 4/2002 151

 Chemistry of EPDM Cross-linking

For the ISO 4097 vulcanization recipe

(1.5 phr S8, 0.5 phr MBT and 1 phr
TMTD) the ENB conversion is 300 to
350 mmol ENB per kg of EPDM
[8, 17, 30]. Depending on the ENB con-
tent of the EPDM used, this corresponds
to 15 to 85 % of the ENB present. The
ENB conversion and cross-link density
are linear functions of the sulphur content
if the sulphur/accelerator ratio is kept
constant. For EPDMs with a low ENB
content (< 4 wt.%) [31] or at relatively
large sulphur and accelerators contents
[8, 17] the ENB conversion can be com-
plete. For fully-cross-linked (again ISO
4097 recipe) gum-stock EPDM the molar
ratio of ENB conversion to cross-link for-
mation is precisely 2.0 mol/mol, so dial-
kenyl sulphidic structures are predomi-
nant and cross-link precursors and cyclic
structures are hardly present [8]. The
average length of the sulphur bridge for
the ISO 4097 recipe is 2.7 S-atoms. It
is independent of the EPDM type, but de-
pendent of the sulphur/accelerators ratio.
Although the presence of allylic H-
atoms is essential for sulphur vulcaniza-
tion of EPDM [32], the vulcanization
speed is not simply determined by the
number of allylic H-atoms. Despite the
fact that  100 dienes have been tested
as EPDM third monomer [4], the relation-
ships between the structure of the resi-
dual diene unsaturation and the reactivity
for sulphur vulcanization have not yet
been elucidated. ENB seems to be the
best choice from an industrial point of
view. Fig. 2. Products and reaction mechanism of peroxide cure of EP(D)M; note: the formation of
tertiary free radicals is chosen arbitrarily

Peroxide cure
The mechanism of peroxide cure of macro-radicals and the cross-link density [19, 32]. Since an aliphatic EPM macro-
EPDM (Fig. 2) is less intricate than that is determined by the amount of peroxide radical is attacking the alkyl-substituted
of sulphur vulcanization. Cross-linking is added. Theoretically, the cross-link den- unsaturation of the EPDM third monomer,
initiated by the thermal decomposition sity equals the peroxide dosage, but in polar effects are absent and the reactivity
of a peroxide, which is the overall cure- practice it is smaller as a result of side re- is completely determined by steric hin-
rate-determining step. Next, the free radi- actions yielding inert species. In the case drance from a- and b-substituents adja-
cals formed abstract H-atoms from of EPDM cross-links are also formed via cent to the unsaturation [34]. As a result,
EPDM chains to form macro-radicals. addition of an EPM macro-radical to the VNB with a mono-substituted terminal
The allylic H-atoms of the incorporated pendent unsaturation of the third mono- unsaturation is more reactive towards
third monomer have a somewhat higher mer. The resulting macro-radical does peroxide cure than 5-methylidene-2-nor-
intrinsic reactivity for H-abstraction than probably not continue to propagate bornene (MNB) with an a,a 0 -disubsti-
the aliphatic H-atoms of the EPM chain. with other third monomers for steric tuted terminal unsaturation and much
However, H-abstraction occurs probably reasons, but terminates via H-transfer. more reactive than either ENB or DCPD
from the EPM backbone as a result of the The contribution of the latter route to both with internal unsaturations [16, 32].
large excess of aliphatic versus allylic H- the total cross-link density of peroxide The number of cross-links for peroxide
atoms in EPDM [33]. cured EPDM is determined by the third cured EPDM can thus be significantly lar-
In EPM the final elastic network is monomer's susceptibility to free radical ger than the peroxide dosage. The final
formed by the combination of two addition and the third monomer content cross-link density of peroxide cured

152 KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 4/2002

 Chemistry of EPDM Cross-linking

Resol cure

Resols are alkylphenol-formaldehyde

condensation products, characterized
by dimethylene ether bridges and pro-
duced under alkaline conditions [40]. Re-
sol cure of ENB-containing EPDM results
in a mixture of cross-link precursors,
cross-links and side products with either
an unsaturated methylene bridged struc-
ture (attached to ENB at C-8) or a satu-
rated chroman ring (attached to ENB at
C-5 and C-8) (Fig. 4) [14, 15, 24]. The dif-
ference compared with other unsaturated
species, where mainly chroman ring
cross-links are formed [41], was recently
shown to be due to differences in the de-
gree of substitution of the unsaturation
[15, 42]. In the presence of the usual
acidic activators the oligomeric structure
of the resol is completely lost.
Cross-link precursors consist of phe-
nolic units attached on one side to ENB
and on the other side to reactive dimethy-
lene ether units or methylol end groups.
Finally, cross-links are obtained, consist-
ing mainly of mono-phenol units are ob-
tained, which are linked to two ENB moi-
eties via one chroman ring and one
methylene bridge [24]. As a result of
the presence of methylene bridges be-
sides the dimethylene ether bridges in
the original resol, precursors and cross-
links with di-phenolic and tri-phenolic
structures are also formed.
Fig. 3. Products and reaction mechanism of co-agent-assisted peroxide cure of EP(D)M
Although there is no direct experimen-
tal evidence, it is assumed that activated
EPDM is the sum of the cross-link densi- sulting in small vitrified thermoset parti- resol cure proceeds via a carbo-cationic
ties from macro-radical combination and cles [20 ± 22]. These particles act as mul- mechanism. Only in the presence of
addition reactions [19]. Note that during ti-functional cross-link nodes, linking a acids, especially stannous chloride dihy-
peroxide cure of EPDM the unsaturation large number of EP(D)M chains (Fig. 3). drate or chemicals that produce such
is consumed, in contrast to sulphur vul- In a way, the effect of co-agents is very acids (PVC, CR or brominated resol) in
canization of EPDM. similar to the effect of third monomers, combination with zinc oxide, sufficiently
Co-agents, such as triallyl(iso)cyanu- i. e. the pendent unsaturation of third high cure rates and degrees of cross-link-
rate, trimethylolpropanetrimethacrylate monomer acts as a co-agent and, actu- ing are achieved [15, 43]. It is well-known
or m-phenylenebismaleimide, are multi- ally, competes with it for reacting with that acids catalyse the degradation of
unsaturated compounds, which are EPM macro-radicals. ethers [44].
used to enhance the peroxide cross-link- Classical explanations that co-agents The reactivity for resol cure seems to
ing efficiency of EP(D)M [35]. Co-agents enhance the peroxide cross-linking be mainly determined by the stability of
are actually built into the elastic EP(D)M efficiency by suppressing chain scission the intermediate carbocation [15, 42].
network [20, 21, 36, 37] in contrast to or termination via disproportionation of The larger the number of alkyl substitu-
the peroxide, which ªonlyº initiates the EPM macro-radicals have been falsified ents on the unsaturation, the greater
cross-linking reaction. As a result of their [39]. Finally, scorch retarders, such as the stability of the cation and the higher
high polarity most co-agents do not 2,6-di-tert-butylcresol (BHT), scavenge the reactivity (ENB >> DCPD  1,4-hex-
(completely) dissolve in the apolar macro-radicals by fast H-transfer and adiene). A significant amount of an unsa-
EP(D)M [38]. Upon peroxide decomposi- are finally attached to the EPDM net- turated side product is formed as a result
tion these co-agent domains are rapidly work via combination of EPDM macro-ra- of cationic isomerization of ENB [24]. Fi-
cross-linked via free radical addition dicals with benzylic BHT-derived radicals nally, a large variety of other side products
and cyclo-polymerization reactions, re- [23]. has been demonstrated, such as inert

KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 4/2002 153

 Chemistry of EPDM Cross-linking

technological point of view recycling

and devulcanization, nitrosamine-free
compound recipes, sulphur vulcanization
with reduced Zn levels or no Zn at all will
be future issues for EPDM as well as for
other elastomers. Typical EPDM trends
are the development of compounds
with enhanced ageing resistance, faster
cross-linking and improved co-vulcaniza-
tion in blends with polydiene elastomers.
For EPM and the metallocene-based
EOM copolymers, improving the cross-
linking efficiency to the levels established
for EPDM will be an important issue. Cost
reduction at similar performance is the
main driver in the rubber market at the
moment. Clearly, in all these issues the
chemistry of EP(D)M cross-linking plays
a role. May be other cross-linking sys-
tems than those applied today have to
be developed. For instance, intrinsically
thermally reversible cross-linking of rub-
bers (including EPDM) is an intrigueing
concept.
From an academic point of view the
chemistry of gum-stock EPDM cross-
linking is sufficiently well understood,
although insight into the effect of the
diene structure on the reactivity for sul-
phur vulcanization is still lacking. The ki-
netics of EPDM cross-linking is usually
studied with rheometers, but still needs
to be interpreted in terms of standard
chemical reaction kinetics. The relation-
ships between network structure and
mechanical, elastic and dynamic pro-
perties need further elaboration. The ef-
fects of additives, such as extender oil,
fillers and other chemicals, used in large
amounts in most practical EPDM applica-
tions on EPDM cross-linking chemistry
and structure-properties relationships
Fig. 4. Products and reaction mechanism of activated resol cure of EPDM; note: the final need to be explored in much more detail.
cross-links, consisting of mono-phenolic units attached to two ENB moieties via one methy-
lene bridge and one chroman ring, are formed via subsequent reactions similar to the for-
mation of the reactive cross-link precursors
References
[1] The Vanderbilt Rubber Handbook, R.F. Ohm
(Ed.), R.T. Vanderbilt Company Inc., Norwalk
cross-link-precursor-like structures with a and applications. Differences between (1990), 13th ed., p. 123.
[2] W. Hofmann, Rubber Technology Handbook,
H-atom or a methyl or methaldehyde sulphur, peroxide and resol cross-linking Hanser Publishers, Munich (1989), ch. 3.3.8.
group instead of a reactive methylol of EPDM and the (dis)advantages of each [3] J.A. Brydson, Rubbery Materials and their Com-
group. cross-linking system are indicated. pounds, Elsevier, London (1988), ch. 7.
[4] S. Cesca, J. Polym. Sci., Macromol. Rev., 10
EPDM is currently the largest non-tire (1975) 1.
Future trends elastomer and the EPDM market is ex- [5] A.Y. Coran and R.P. Patel, Thermoplastic Elas-
tomers based on Dynamically Vulcanized Elas-
pected to grow at a rate of  4% per an- tomer-Thermoplastic Blends, in Thermoplastic
In Tab. 1a summary is given of the main num in the coming years. It is expected Elastomers, G. Holden, N.R. Legge, R.P. Quirk
aspects of EPDM cross-linking, not only that at the end of this decade a major and H.E. Schroeder (Eds.), Hanser Publishers,
Munich (1996), 2nd ed., ch. 7.
from a chemical point of view, but also part of the EPDM produced will be sold [6] D.J. Synnott, D.F. Sheridan and E.G. Kontos,
with respect to technological issues as part of a TPV composition. From a EPDM-Polypropylene Blends, in Thermoplastic

154 KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 4/2002

 Chemistry of EPDM Cross-linking

KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 4/2002 155

 Chemistry of EPDM Cross-linking

Tab. 1. Characteristics of EPDM cross-linking chemistry and technology

Accelerated sulphur vulcanization Co-agent-assisted peroxide cure Activated resol cure
Cross-link structure dialkenylmono/di/polysulphides EPM-EP(D)M C-C bonds, multifunctional methylene bridge/chroman, mainly
cured co-agent domains mono-phenolic
Intermediates activated sulphur complex, pendent EPM
and EPM-EPDM
free radicals benzyl cation ? methylol end group
sulphur, polysulphide
Side products cyclic sulphides, accelerator residues, peroxide decomposition products novolak structures, methyl, methalde-
oxidation products hyde and H end groups
Mechanism ionic and concerted free radical cationic ?
Network heterogeneity homogeneous heterogeneous homogeneous
Cross-linking rate k[Acc]‰rS8 Š‰ENBŠn , two-step ? ‰ROORŠ0 f1 exp k0 :exp‰EA =RTŠ:t†g slow
Temperature increase desulphuration, devulcanization EPM chain degradation decreased efficiency
Beneficial chemicals accelerators, activators, retarders, car- co-agents, scorch retarders acidic activators
bon black
Detrimental chemicals strong acids, carbon black aromatic oil, oxygen, acids alkaline chemicals and fillers
Devulcanization diaryldisulphides and amines, elevated not feasible not feasible
temperature
Costs (euro/kg) S8 : 0.5 ± 2 peroxides:  10 resol: 2
accelerators: 2.5 ± 15 co-agents: 5 ± 10 SnCl2 :2H2 O : 10
Applications automotive sealants, window gaskets, high temperature applications, low TPV production
dynamic applications compression set, EPM/EOM
Safety, health and toxicity, nitrosamine, Zn heavy metal, explosion safety, stench Sn heavy metal, phenolic derivatives,
environment blooming, stench chloride
Advantages traditional, inexpensive, good ultimate high thermal stability, applicable for EPM/ thermal stability, non-free radical
mechanical and dynamic properties EOM
Disadvantages many chemicals, thermal instability, explosion safety, stench, expensive discoloration, moisture uptake
blooming, not applicable for EPM/EOM,
nitrosamine

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[13] E.F.J. Duynstee, Kautsch. Gummi Kunstst., 40 ACS Rubber Division meeting, Nashville (1998); The author
(1987) 205. accepted by Rubber Chem. Technol.
[14] M. van Duin and A. Souphanthong, Rubber [30] V.M. Litvinov, W. Barendswaard and M. van Martin van Duin is Research Fellow at DSM Re-
Chem. Technol., 68 (1995) 717. Duin, Rubber Chem. Technol., 71 (1998) 105. search. His fields of expertise are rubber cross-link-
[15] M. van Duin, Rubber Chem. Technol., 73 (2000) [31] M. van Duin, Rubber Chem. Technol. 74 (2001) ing, polymer blends including thermoplastic vulcani-
706. 138; Gummi Fasern Kunstst., 54 (2001) 366. zates and polymer modification including reactive
[16] K. Fujimoto and S. Nakade, J. Appl. Polym. Sci., [32] F.P. Baldwin, P. Borzel, C.A. Cohen, H.S. Ma- extrusion.
13 (1969) 1509. koswki and J.F. van de Castle, Rubber Chem.
[17] M. van Duin et al., to be submitted to Rubber Technol., 43 (1970) 522. Corresponding author
Chem. Technol. [33] M. van Duin and B. Coussens, (Re)evaluation of Dr. Martin van Duin
[18] R. Winters, W. Heinen, M.A.L. Verbruggen, J. the Importance of Hydrogen Abstraction during DSM Research
Lugtenburg, M. van Duin and H.J.M. de Groot, Radical Grafting of Polyolefins, Polymer Proces- Polyolefins: Catalysts and chemistry
accepted by Macromolecules. sing Society meeting 11, Stuttgart (1995). P.O. Box 18
[19] H.G. Dikland, Kautsch. Gummi Kunstst., 49 NL-6160 MD Geleen, Netherlands
(1996) 410. [email protected]

156 KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 4/2002

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