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Vulcanization of rubber compounds with peroxide curing systems

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DOI: 10.5254/rct.16.83758

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 VULCANIZATION OF RUBBER COMPOUNDS WITH PEROXIDE CURING
SYSTEMS

JÁN KRUŽELÁK,* RICHARD SÝKORA, IVAN HUDEC

DEPARTMENT OF PLASTICS AND RUBBER, INSTITUTE OF POLYMER MATERIALS, FACULTY OF CHEMICAL AND FOOD
TECHNOLOGY, SLOVAK UNIVERSITY OF TECHNOLOGY, RADLINSKÉHO 9, 812 37 BRATISLAVA, SLOVAKIA

RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

ABSTRACT
Vulcanization or curing is one of the most important processes in rubber technologies. During this process, plastic
rubber compounds by parallel and subsequent physical and mainly chemical reactions change into highly elastic products—
vulcanizates. The fundamental goal of curing is forming chemical cross-links between rubber macromolecules, which leads
to the formation of a three-dimensional network or rubber matrix. A number of curing systems have been introduced in cross-
linking of elastomers; each system has its own characteristics and composition; therefore, vulcanizates with different
properties also can be prepared. We characterize organic peroxides as curing agents and their decomposition mechanisms
and characteristics and bring a detailed view to understanding mechanisms between peroxides and different types of rubber
matrices. Then, we focus on the classification and characterization of co-agents used in peroxide cross-linking and explain
the mutual interactions and reaction mechanisms between peroxide, co-agents, and rubber matrices in relation to the
properties of prepared materials. Finally, the drawbacks and the main features of final cross-linked materials are outlined.
[doi:10.5254/rct.16.83758]

CONTENTS
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
II. Peroxide Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
A. Organic Peroxides as Curing Agents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
B. Mechanism of Peroxide Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
1. Peroxide Cross-Linking of Unsaturated Rubbers . . . . . . . . . . . . . . . . . . . . . . . 70
2. Peroxide Cross-Linking of Saturated Rubbers . . . . . . . . . . . . . . . . . . . . . . . . . 72
C. Side Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
1. Main Chain Scission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2. Disproportionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3. Oxygenation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4. Dehydrohalogenation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5. Radical Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6. Branching of Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7. Acid-Catalyzed Decomposition of Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . 76
D. Co-Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
1. Type I Co-Agents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2. Type II Co-Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
E. Co-Agent Assisted Peroxide Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
F. General Features of Peroxide Cross-Linking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
III. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
IV. Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
V. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

*Corresponding author. Email: Ján Kruželák; jan.kruzelak@stuba.sk

60
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 61

I. INTRODUCTION
Rubbers—vulcanizable elastomers—are unique and versatile materials characterized by their
ability to be reversibly deformed under the influence of external deformation forces. The degree of
deformation depends on the structure and molecular weight of the rubber and external conditions of
deformation; at low deformation strains it can reach from percentages in the hundreds to the
thousands. This property is called elastic or highly elastic deformation. It relies on the ability of
rubber macromolecules to get into more ordered states under the influence of deformation forces,
from the most thermodynamically favorable clew shape into stretched form, without breaking
chemical bonds between rubber chains or deforming bond angles. In the ideal case, when
deformation forces are removed, the rubber chains can return back to their initial positions.
Elastomers thus exhibit elastic or viscoelastic behavior.1
In the amorphous, un–cross-linked elastomers over their glass transition temperature, the
ability to resist deformation is directly proportional to the entaglements of the constituting
macromolecular chains. However, these chain entaglements and bindings are not permanent, and
elastomers are not able to maintain their resistance to deformation. For this reason, the rubber
materials are not suitable for use in applications requiring dimensional stability under prolonged
periods of strain.2 The dimensional stability of elastomers can be achieved during the process of
vulcanization, often called curing or cross-linking among engineers. The foundation of
vulcanization is the formation of chemical cross-links between rubber macromolecules, which
leads to the formation of a three-dimensional network within the rubber matrix, by reactions
between the functional groups of elastomer chains and suitable curing agents. This network can
keep the chains in position after being submitted to the prolonged deformation forces, thus
providing the required stability. Moreover this network improves elasticity, strength, and modulus
and reduces hysteresis and plasticity.3
A number of curing systems have also been developed in order to vulcanize rubber
compounds, such as sulfur, peroxides, metal oxides, phenolic resins, quinones, and so on. The type
of applied curing system determines the structure and the quality of the cross-links. Also, the type of
rubber matrix must be considered when cross-linking elastomers, especially their chemical nature
and the presence of suitable functional groups. Recently, sulfur and peroxide curing systems are the
most frequently used for cross-linking of rubber materials.
The sulfur vulcanization of rubber compounds was first introduced in 1839 by American
Charles Goodyear (patent from 1844) and Englishmen Thomas Hancock in 1842 (patent from
1843), and it is still the most widely used method for cross-linking of unsaturated rubbers.4–6
Despite the fact that sulfur vulcanization has been known for over 150 years, the chemistry of sulfur
vulcanization is very complex and still not clearly understood. Both free radical and ionic
mechanisms relating to the chemical pathways running during sulfur vulcanization have been
suggested and considered.7,8 Application of sulfur curing systems leads to the formation of different
types of sulfidic cross-links between rubber macromolecules. Generally, sulfur cured vulcanizates
exhibit good elastic and dynamic behavior and possess high values of tensile and tear strength.
However, due to the low dissociation energy of sulfidic cross-links, sulfur cured vulcanizates
exhibit poor high temperature properties like aging, for instance.1,9
Cross-linking of rubbers with organic peroxides was first examined by Ostromislensky in
1915.10 Peroxides can be used to vulcanize both unsaturated and saturated elastomers. The latter
cannot be cross-linked with sulfur curing systems. Industrial interest in application of peroxides as
cross-linking agents became more obvious with the introduction of many saturated rubbers, mainly
ethylene-propylene type rubbers (EPM, EPDM), or fluoro elastomers (FKM), and so on.11–13 At
the present time, peroxides are used as cross-linking agents for elastomers to prepare vulcanizates
62 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

with good high temperature aging resistance or to vulcanize blends, which consist of a combination
of saturated and unsaturated elastomers.1

II. PEROXIDE VULCANIZATION

A. ORGANIC PEROXIDES AS CURING AGENTS

Organic peroxides are molecules containing of at least two oxygen atoms connected by a single
bond to organic chemical groups. The general structure of organic peroxide can be described as R–
O–O–R 0 , where R and R 0 represent other chemical groups, which are bonded to peroxy O–O group.
The relatively weak oxygen–oxygen bond (bonding energy ~ 150 kJ/mol) undergoes homolytic
cleavage to form oxygen centered alkoxy radicals (R–O) as their primary decomposition
products.14–16 The breakage of the labile O–O bond is usually triggered by heat.
According to the chemical composition, organic peroxides introduced in cross-linking of
elastomers belong to the aliphatic, aromatic, and mixed peroxides, and some of them can have more
than one peroxy group. In addition to symmetrical peroxides, those with asymmetrical or polymeric
structure are applied, too.17 Depending on the chemical nature, peroxides used in cross-linking of
rubber compounds can be classified into six groups:18,19
 dialkylperoxides, R–O–O–R; R, alkyl group
 alkyl–aralkyl peroxides, R–O–O–R 0 ; R, alkyl group, R 0 , aryl group
 diaralkyl peroxides, R 0 –O–O–R 0 ; R 0 , aryl group
 diacylperoxides, R–C(O)–O–O–(O)C–R 0 ; R, R 0 , alkyl and/or aryl groups
 peroxyketals, R–O–O–(R)C(R 0 )–O–O–R 0 ; R, R 0 , alkyl and/or aryl groups
 peroxyesters, R–C(O)–O–O–R 0 ; R, R 0 , alkyl and/or aryl groups

In addition to the ability of peroxides to perform efficient cross-linking of the rubber matrix,
there are also some other requirements for the selection of a suitable peroxide: it must be stable
during preparation, processing, and storage of rubber compounds; it should decompose fast at
vulcanization temperature; and the concentration of active radical fragments must be sufficiently
high to generate an adequate cross-link network structure within the rubber matrix.20–22 These
requirements are fulfilled mainly by peroxides with peroxy group fixed to the tertiary carbon.
Peroxides with peroxy group bonded to the primary or secondary carbon are less stable.17 Generally
dialkyl, alkyl-aralkyl, and diaralkyl peroxides belong to the most thermally stable class of
peroxides. Their thermal decomposition leads to the formation of R–O and/or O–R 0 free radicals.
Diacylperoxides exhibit limited thermal stability, decomposing at relatively low temperatures into
R–C(O)–O and O–(O)C–R 0 radicals. Similarly peroxyketals (also known as perketals) and
peroxyesters (peresters) are thermally less stable compounds, forming R–O–O–(R)C(R 0 )–O and
OR 0 radicals in the case of peroxyketals, and R–C(O)–O and O–R 0 free radical fragments in the
case of peroxyesters when heating. Owing to the low thermal stability, the use of these peroxides in
cross-linking of rubber compounds is fairly restricted.23 For example, diacylperoxides are primarily
used as cross-linking agents for some types of silicone rubbers.1 Peroxides applied as cross-linking
agents for rubber compounds should also be nonvolatile, nontoxic, nonirritating, and safe to handle.
The most important characteristics of the peroxide used for cross-linking is its decomposition
rate generally expressed by half-life time or half-life temperature.23–25 The half-life time (t1/2) is
defined as the time required to decompose one half of the initial amount of the peroxide at a certain
temperature. Correspondingly, the half-life temperature is the temperature at which one half of the
initial amount of the peroxide is decomposed in a given time. The correlation between the number of
half-lives and the percentage of peroxide decomposition is shown in Table I.26 This means that after
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 63

TABLE I
HALF-LIVES VS PERCENTAGE OF PEROXIDE DECOMPOSITION26

Number of half-lives Peroxide decomposition (%)

0 0
1 50
2 75
3 87.5
4 93.75
5 96.9
6 98.4
7 99.2
8 99.6
9 99.8
10 99.9

one half-time, 50% of the peroxide is decomposed, 75% after two half-times, 87.5% after three half-
times, while almost total decomposition of the peroxide occurs after 10 half-times.
The rate of cross-linking initiated by the peroxide is determined by its rate of thermal
decomposition. Half-life data are important in the selection of the optimal peroxide for specific
time/temperature applications. The peroxide stability is often expressed in terms of 1 minute, 1
hour, and 10 hour half-life temperatures, which are the temperatures at which one half of the
peroxide is decomposed in 1 minute, 1 hour, and 10 hours, respectively.
The cross-linking is directly proportional to the amount of the peroxide decomposed; therefore
at least 6 to 10 half-lives of the peroxide decomposition are suggested for cross-linking reactions.
For a typical peroxide, the half-life time falls by one-third of its value for each 10 8C rise in
temperature.14,27
The half-life is usually evaluated by using differential scanning calorimetry–thermal activity
monitoring (DSC-TAM) of a dilute solution of the peroxide in monochlorbenzene.28–30
Theoretically, the dependence of the half-life on temperature can be described by an Arrhenius
equation;25
Ea
kd ¼ AeRT ð1Þ

ln2
t1=2 ¼ ð2Þ
kd
where kd ¼ rate constant for the peroxide decomposition (s1)

A ¼ Arrhenius frequency factor (s1)

Ea ¼ activation energy for the peroxide decomposition (J/mol)
R ¼ 8.314 J/mol K, gas constant
T ¼ temperature (K)
t1/2 ¼ half-life time (s)

Some of the peroxides used as cross-linking agents for rubber compounds are mentioned in
Table II, while Table III reveals their half-life temperatures at certain times and their typical cross-
linking temperatures.
64 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

TABLE II
PEROXIDES APPLIED IN CROSS-LINKING OF ELASTOMERS

Types of peroxides Examples

Dialkyl peroxides 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (DTBPH)

2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 (DTBPHY)
Di-tert-butyl peroxide (DTBP)
Alkyl-aralkyl peroxides Tert-butyl cumyl peroxide (TBCP)
Di(tert-butylperoxyisopropyl)benzene (DTBPIB)
Diaralkyl peroxides Dicumyl peroxide (DCP)
Diacyl peroxides Dibenzoyl peroxide (BPO)
Peroxyketals 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane (DTBPTC)
Butyl 4,4-di(tert-butylperoxy)valerate (BDTBPV)
Peroxyesters Tert-butyl peroxybenzoate (TBPB)

B. MECHANISM OF PEROXIDE VULCANIZATION

Generally, it is supposed that cross-linking of rubbers with peroxides has radical character in
substance. In the first step, peroxide molecules undergo homolytic cleavage to form primary alkoxy
radicals by breaking the labile oxygen–oxygen bond, which is usually triggered by heat. The O–O
bond strength depends on the chemical nature of the hydrocarbon group attached and the polarity of
the substrate in which peroxide is dispersed. The influence of the chemical nature of the
hydrocarbon group depends on structural effects such as resonance stabilization of the free radicals
generated upon decomposition of the peroxide, respectively steric and inductive effects.23 The
primary radicals can be a source for secondary alkyl or aryl radicals, which are formed by b-scission
of primary radicals.2,31–35 b-scission reaction of alkoxy radicals is strongly temperature dependent.
Higher temperatures promote tert-alkoxy radicals to undergo b-scission over either abstraction or
addition and abstraction over addition. b-scission is usually related to cleavage of the weakest C–C
bond. Bonds to tertiary carbon are broken rather than bonds to primary (acetylenic) or secondary
(aromatic, olefinic) carbons. Bonds to higher alkyl chains are scissioned in preference to those to

TABLE III
HALF-LIFE TEMPERATURES OF PEROXIDES AT GIVEN TIMES

T (8C) for t1/2a

0.1 h 1h 10 h Cross-linking temperature (8C)

DTBPH 156 134 115 180

DTBPHY 164 141 120 180
DTBP 164 141 121 180–190
TBCP 159 136 115 180
DTBPIB 156 134 114 180
DCP 154 132 112 170
BPO 113 91 71 100–110
DTBPTC 128 105 85 150
BDTBPV 143 121 102 160
TBPB 142 122 103 140
a
Data of half-life provided by AkzoNobel Polymer Chemistry; solution—chlorobenzene.
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 65

SCHEME 1. — Decomposition mechanism of dicumylperoxide.37

methyl radicals.36 These new radicals can be more or less reactive compared with initial radicals,
which is usually reflected in the cross-linking efficiency. Therefore the choice of peroxides
introduced in vulcanization of elastomers must be well considered.
The decomposition of dialkyl, diaralkyl, and alkyl-aralkyl peroxides gives primary alkoxy and
secondary alkyl (or aryl) radicals. For example, when using dicumyl peroxide (DCP), one of the
most used cross-linking peroxides, the decomposition yields cumyloxy radicals, which are
subsequently fragmented into secondary methyl radicals and acetophenone as byproduct (Scheme
1). Both radicals can be active in cross-linking reactions of elastomers. By applying peroxides with
more than one peroxy group, for instance di(tert-butylperoxyisopropyl)benzene (DTBPIB), cross-
linking occurs by tert-butoxy and di-(hydroxy-i-propyl)-benzene as primary radicals and secondary
methyl radicals (Scheme 2).31,37–40
Diacylperoxides are sources of primary acyloxy radicals that undergo b-scission to generate
corresponding alkyl (or aryl) radicals and carbon dioxide, although this decomposition reaction is
temperature dependent (Scheme 3).2,36 Peroxyesters are decomposed to provide primary acyloxy
and alkoxy radicals and secondary alkyl and aryl radicals (Scheme 4).2,36,41,42 The decomposition
mechanisms of peroxyketals are rather complex; they can vary with specific structures and are also
temperature dependent (Scheme 5).43
A list of the most common radicals formed from thermal decomposition of peroxides is
presented in Figure 1, while the relative amounts of decomposition products from some peroxides
in pentadecane are shown in Table IV. Based upon these data, an indication of the types and
quantities of radicals formed from peroxide decomposition can be provided.31,38
The chemical nature of the free radical species formed from peroxide decomposition plays an
important role in determining the resulting properties. Generally, peroxide radicals that act
predominantly as hydrogen abstractors are more convenient for peroxide cross-linking when
compared with radicals whose primary mechanism is addition to double bonds of unsaturated
66 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

SCHEME 2. — Decomposition mechanism of di(tert-butylperoxyisopropyl)benzene.38

rubbers.23,44 The relative reactivity or stability of the free radicals generated is related to the
hydrogen bond dissociation energy of the parent compound.23 Based upon the values of bond
dissociation energy, it can be concluded that methyl, phenyl, tert-butoxy, and other alkoxy radicals
are highly reactive and are good hydrogen abstractors. By contrast, ethyl, tert-butyl, and isopropyl
radicals have lower energy and are poor hydrogen abstractors or prefer addition to the double bonds
of elastomers.22,23,36,45
The reactivity of peroxide radicals depends not only on their structure but also on their size.
Secondary methyl radicals are smaller, and therefore they are less sterically hindered than the initial
alkoxy radicals.3,22,44 At the same time they are more accessible to reactive centers of elastomers,
and thus they provide good cross-linking activity. Most of the peroxides used in cross-linking of
elastomers generate tert-butoxy radicals, which can be subsequently scissioned into methyl radicals

SCHEME 3. — Decomposition mechanism of dibenzoyl peroxide.2

 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 67

SCHEME 4. — Decomposition mechanism of tert-butyl peroxybenzoate.36

SCHEME 5. — Decomposition mechanism of 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane.32

68 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

FIG. 1. — The most common radicals derived from homolytic cleavage of peroxides.

and other products. The sum of the relative amounts of methane and tert-butanol per peroxide shows
a good indication of the peroxide to perform cross-linking reactions by hydrogen abstraction.23
The peroxide decomposition step follows first order rate reaction kinetics; therefore, the
dissociation of the peroxide molecule is adequate to the peroxide concentration at any time. This
step is also the rate determining step of the overall reaction.14,20,44 Subsequent reactions between
peroxide radicals and functional groups of elastomers lead to the formation of cross-linked network

TABLE IV
RELATIVE AMOUNTS OF DECOMPOSITION PRODUCTS FROM VARIOUS PEROXIDES IN PENTADECANE38

Experimental Relative amount

Peroxide temperature (8C) Decomposition products (mol/mol peroxide)

DCP 160 methane 0.91

acetotophenone 0.91
2-phenylpropanol-2 1.06
a-methylstyrene 0.01
water 0.01
DTBPIB 155 tert-butanol 1.83
acetone 0.13
methane 1.10
di-(hydroxyl-i-propyl) benzene 0.30
acetyl hydroxy-i-propyl benzene 0.54
diacetyl benzene 0.14
DTBPH 145 methane 0.31
ethane 0.40
acetone 1.62
tert-butanol 1.65
tert-amylalcohol 0.23
DTBPHY 180 methane 0.57
carbon dioxide 0.02
acetone 0.57
tert-butanol 1.39
2,5-dimethyl-2,5-dihydroxyhexyne-3 0.79
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 69

FIG. 2. — Order of hydrogen stability.44

structure. As already outlined, peroxide free radical species could potentially react with elastomers
by two mechanisms:

1. by abstraction of hydrogen atoms from elastomer chains or

2. by addition to the double bonds of unsaturated rubbers

Both mechanisms lead to the formation of radical centers on elastomer chains (macroradicals),
which usually mutually recombine to form carbon–carbon cross-links.46–51
The ability of hydrogen atom transfer is dependent not only on the type and properties of
abstracting radical, but also on the structure of hydrogen donor. The sequence displayed in Figure
244,52 shows the facility that radicals can be formed via abstraction of a hydrogen atom from
different chemical groups, while C–H bond strength of the presented groups is listed in Table V.2 It
must be noted that peroxide derived radicals can abstract hydrogen not only from elastomer chains,
but also from other accessible sources. Resonance stabilization of allylic and benzylic structures
makes these positions better hydrogen donors than corresponding alkyl groups.2 Owing to high
abstractibility of benzylic and allylic hydrogen atoms, the use of aromatic oils and some types of
antidegradants in rubber compounding should be restricted in order to avoid the consumption of
peroxide radicals, which could negatively influence the cross-linking efficiency.53
The second mechanism by which elastomer radicals can be formed is addition of peroxide
radical species to the double bonds of unsaturated rubbers. The double bonds situated at the end of
elastomer chains (terminal) or in the side-chain groups (vinyl) are less sterically hindered when
compared with in-chain double bonds (cis/trans). Therefore they are more amenable and more
likely take part in addition reactions.7,54
Both reaction types, hydrogen abstraction and addition reactions, may proceed simultaneously
to form elastomer radicals.54 The balance of both mechanisms is influenced by the elastomer
structure, peroxide type, and concentration and reaction temperature. Higher peroxide
concentrations and higher temperatures shift toward addition reactions.3,55

TABLE V
BOND STRENGTH OF VARIOUS TYPES OF C–H BONDS2

Type of C–H bond C–H bond strength (kJ/mol)

benzylic 368
allylic 368
tertiary 380
secondary 405
primary 435
vinyl 464
phenyl 468
70 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

TABLE VI
RELATIVE CROSS-LINKING EFFICIENCIES OF SOME ELASTOMERS CURED
WITH DCP

Elastomer Cross-linking efficiency

BR 10
SBR 10
NBR 1
NR 1
EPM 0.1–0.8
CR 0.5
IIR 0

The number of moles of chemical cross-links that are formed from a mole of reacted peroxide is
called peroxide efficiency or cross-linking efficiency. In the abstraction mechanism, the peroxide
efficiency equals 1, since 1 mole of peroxide is able to form only 1 mole of cross-link. In addition
reactions, the peroxide efficiency is thought to be much higher, because one radical can initiate the
formation of several chemical bonds.46,56 The relative cross-linking efficiencies of some elastomers
cured with dicumylperoxide are mentioned in Table VI.7,23,46
1. Peroxide Cross-Linking of Unsaturated Rubbers. — The general scheme for peroxide cross-
linking mechanism of natural rubber (NR) is illustrated in Scheme 6. The primary mechanism is
abstraction of allylic hydrogen from the elastomer backbone by peroxide radical species.3,57 The
abstraction reaction is supported by the presence of high amounts of easily abstractable allylic
hydrogens in the chemical structure of NR. The addition reactions are much less pronounced,
probably due to the sterically hindered in-chain double bonds and of course due to the quantum of
allylic H-atoms. Two elastomer radicals subsequently recombine to form a cross-link. From an
analysis of the stoichiometry for peroxide cross-linking of natural rubber using DTBP and DCP, it
was concluded that these peroxides form one mole of cross-links per mole of peroxide, that is, they
are quantitative cross-linking agents.7 But some other experimental works58,59 showed that
addition reactions should also be under consideration. The peroxide cross-linking efficiency then
would be higher than one. It is supposed that addition reactions occur mainly at higher peroxide
concentrations and higher temperatures.3
The amount of addition reactions becomes more significant when cross-linking butadiene type
rubbers such as butadiene rubber (BR) and styrene-butadiene rubber (SBR), mainly those with
higher amounts of 1,2-butadiene structural units.49,60–62 When peroxide cross-linking of BR and
SBR, it is expected that peroxide radicals can react by hydrogen abstraction, at which more reactive
macroradicals than in the case of NR are formed, and also by addition reactions to the double bonds.
The formed macroradicals, in addition to mutual recombination reactions, can also participate in
addition reactions to the double bonds in elastomer chains (Scheme 7). The chain character of
addition reactions results in high cross-linking efficiency, that is, 10–50 depending on the
microstructure of polybutadiene. High cross-linking efficiency can be observed mainly by peroxide
cross-linking of butadiene type rubbers with high amounts of 1,2-butadiene units, suggesting that
the side-chain vinyl units participate in addition reactions more easily than in-chain double
bonds.1,7
The cross-linking efficiency of acrylonitrile butadiene rubber (NBR) was reported to be 1,
which indicates that the abstraction mechanism is prevailing. The addition mechanism is of minor
importance, arguably due to the electron withdrawing nitrile groups, which make double bonds in
the structure of NBR less reactive.56 Although this statement is generally accepted, factors such as
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 71

SCHEME 6. — Peroxide cross-linking of NR.

the amount of acrylonitrile structural units (ACN) in the structure of NBR, peroxide concentration,
and cross-linking temperature must be considered. The higher the amount of ACN, the lower the
cross-link density, suggesting that the abstraction reaction is predominant. By contrast, decreasing
the amount of acrylonitrile and increasing the amount of butadiene results in an increase in the
cross-link density. The increase in cross-linking degree of NBR is also promoted with the increase
in peroxide concentrations, while both higher peroxide concentrations and higher cross-linking
temperatures favor an increase in cross-linking degree of NBR with lower ACN content (higher
butadiene content).46 Based upon that, it is suggested that peroxide radicals can, in addition to
abstraction of hydrogen atoms from elastomer chains, initiate the additional reaction to the double
bonds, which makes the cross-linking process more efficient. The addition mechanism needs
suitable orientation of double bonds to be attacked by radicals, and this can be supported by
increasing the temperature to improve the mobility of elastomer chains.46,56
Ethylene-propylene-diene terpolymer (EPDM) is an elastomer with a saturated polymer
backbone with pendant unsaturation of randomly distributed non-conjugated diene monomers.
5-Ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), or dicyklopentadiene
(DCPD) are the most common monomers introduced in commercially manufactured EPDM.63
Peroxide cross-linking efficiency of EPDM is relatively high, involving both hydrogen
abstraction and addition mechanisms (Scheme 8).64–68 The second pathway is more promoted
when the double bond is terminal, while the internal double bond is converted more via
hydrogen abstraction.69 Peroxide free radical species abstract hydrogen atoms from EPDM
elastomer, both at the CH2 and CH units in the EPM main chain and at the allylic positions of
the diene unit, yielding EPDM alkyl and allyl macroradicals, in an approximately 1:1 ratio.70
The allylic H-atoms of the diene monomer have a higher intrinsic reactivity for hydrogen
abstraction than the aliphatic H-atoms of the EPM chain. However, hydrogen abstraction also
occurs from the elastomer backbone as a result of the large molar excess of aliphatic H-atoms
in comparison with allylic hydrogens in EPDM. Cross-linking can proceed via two pathways.
First, termination of two EPDM macroradicals via combination yields ~25% alkyl/alkyl,
~25% allyl/allyl, and ~50% alkyl/allyl combination cross-links with 0, 1, and 2 diene units
and with 0, 1, and 2 unsaturations in the actual cross-link between the two elastomer chains.
Second, an EPDM macroradical adds to an EPDM unsaturation. For steric reasons the
macroradical thus formed will probably not propagate with a second diene unsaturation. It
72 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

SCHEME 7. — Peroxide cross-linking of BR.1

likely terminates via H-transfer, forming allyl/alkene and alkyl/alkene cross-links with 2 and 1
diene units and with 1 and 0 unsaturation in the actual cross-link. The total amount of cross-
links formed via combination is constant and independent of the EPDM structure. The total
number of cross-links formed via addition reactions increases with increasing diene content
and in the sequence ENB ~ DCPD , VNB. Typical diene conversions are ~25% for ENB
and DCPD and ~50% for VNB.69,71,72 High reactivity of EPDM with VNB in its structure
can be explained by low steric hindrance of the terminal VNB unsaturation.73
2. Peroxide Cross-Linking of Saturated Rubbers. — In the case of fully saturated rubbers, the
abstraction of hydrogen from their chains by peroxide reactive species is the only mechanism for
elastomer radical formation. Cross-link formation between elastomer chains is performed only by
recombination of macroradicals.1,2,44,74,75 When cross-linking saturated elastomers, the cross-
linking efficiency is usually low. In the case of ethylene-propylene rubber (EPM), the abstraction of
hydrogen occurs on both ethylene and propylene structural units. But while cross-linking of an
ethylene phase leads to the cross-linking and increase in molecular weight, the abstraction of
hydrogen from propylene structural units leads to the formation of tertiary radicals, which are more
prone to scission reactions, causing usually the opposite effect connected with a decrease in
molecular weight (Scheme 9).14,21,76,77 Abstraction of hydrogen from chlorinated polyethylene
(CM) and chlorsulfonated polyethylene (CSM) occurs at the carbon adjacent to the halogenated
site. For ethylenevinylacetate elastomers (EVM), methyl hydrogen is the most likely site for
abstraction. Fluoroelastomers are also peroxide curable, but C–F bonds are very strong, and
fluorine is therefore much more difficult to abstract than hydrogen, resulting in reduced cross-
linking efficiency. For that reason copolymerization or terpolymerization of some types of
fluoroelastomers are performed in the presence of small amounts of other monomers with reactive
groups able to participate in cross-linking reactions.25 Peroxide curing systems can also be used for
some types of silicone rubbers (Q), where peroxide radicals can abstract hydrogen form methyl
substituents or add to vinyl substituents (Scheme 10).78
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 73

SCHEME 8. — Peroxide cross-linking of EPDM with ENB as third monomer.69

C. SIDE REACTIONS

Peroxide cross-linking of elastomers is usually accompanied by a number of side reactions,

which compete with the main cross-linking process and very often reduce vulcanization yield. The
most common undesirable side reactions include main chain scission, disproportionation,
oxygenation, dehydrohalogenation, radical transfer, acid-catalyzed decomposition of the peroxide,
or branching of elastomers.25,79–81 The proportion of each reaction depends mainly on the nature of
elastomers, but also on the type and concentration of the peroxide applied and on the cross-linking
conditions.
1. Main Chain Scission. — Main chain scission is one of the most frequent undesirable side
reactions leading to the lowering of cross-linking efficiency.38,82 The elastomer chain breaks to
form a double bond and a radical. The scission of the elastomer backbone is usually promoted by
tertiary radicals. The primary and secondary radicals are much less prone to scission reactions and
more readily undergo coupling reactions than tertiary ones.60 Therefore elastomers with the
74 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

SCHEME 9. — Cross-linking and scission in peroxide curing of EPM.

presence of tertiary carbon atoms, like EPM, are more prone to scission reactions. As already
mentioned in the section above, the peroxide cross-linking of EPM can be understood as a mixture
of cross-linking of an ethylene phase and scission of a propylene phase, the so called b-scission
(Scheme 9).75,83 EPDM is also sensitive to b-scission, which also most likely occurs at the
propylene units.14,84,85 The ethylene/propylene ratio, type, and amount of diene monomer;
randomness of monomer distribution; elastomer molecular weight; and molecular weight
distribution have been proposed to be the main factors influencing the peroxide cross-linking
efficiency of EPM and EPDM.21,23,86 The higher the ethylene/propylene ratio, the higher the cross-
linking efficiency. Increasing randomness of diene monomer distribution helps to minimize
scission reactions.14,27 Van Duin and Dikland73 studied the effect of the type and content of diene
monomer on the cross-linking efficiency of EPDM cured with peroxide by identification of the
products formed from peroxide decomposition in low molecular weight model substrates (alkanes,
alkenes) by employing gas chromatography with mass spectroscopy detection (GC-MS). The
research revealed that EPDMs having diene monomers with terminal unsaturations are more
reactive than those with internal unsaturations (for instance VNB).
The tertiary carbon atoms are also present in the structure of NR and markedly contribute to the
poor peroxide cross-linking performance of natural rubber.60 The competition between cross-
linking and scission is also influenced by the temperature and peroxide concentration. Scission
predominates at higher temperatures and lower peroxide concentrations.75,82,87 The excessive main
chain scissions prevail also by peroxide curing of isobutylene isoprene rubber (IIR) and lead to the
degradation of elastomer backbone (Scheme 11).1,88 Therefore this type of rubber can not be cured
with peroxides.
2. Disproportionation. — Disproportionation is another very common side reaction also
promoted by the presence of tertiary radicals.14,44,89 The ratio of the rates of disproportionation ktd
to combination ktc for some radical species is listed in Table VII.2 It becomes evident that allylic
radicals prefer to terminate purely via combination, probably due to the presence of unsaturation.
Benzylic and primary alkyl radicals also prefer to terminate via combination but not exclusively,
while tertiary alkyl radicals prefer disproportionation. Although this type of reaction does not cause
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 75

SCHEME 10. — Peroxide cross-linking of silicon rubbers.78

a decrease in molecular weight of the elastomer, it reduces the efficiency of the peroxide used
because reactive radical centers on elastomer backbone are unfavorably terminated (Scheme 12).
3. Oxygenation. — The presence of oxygen in the cured mixture might cause coupling of
oxygen molecules to the radical in the elastomer chain to form hydroperoxide radicals, which leads
to rubber degradation instead of cross-linking (Scheme 13). Typical accompanying manifestation
of this negative phenomenon is surface tackiness.44,90
4. Dehydrohalogenation. — Dehydrohalogenation typically reduces the cross-linking
efficiency of halogenated elastomers. During this reaction the radical centers on elastomer
backbones are terminated by forming a double bond while releasing a halogen radical (Scheme
14).3,91

SCHEME 11. — Degradation of IIR in the presence of peroxides.1

76 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

TABLE VII
RATIO OF DISPROPORTIONATION TO COMBINATION OF RADICALS IN
SOLUTION2

Radicals ktd/ktc

2CH3CH2 0.15a

2(CH3)2CH 1.2a

2(CH3)3C 7.2a

2CH2¼CHC (CH3)2 ~0b

2C6H5CH CH3 0.14c
a
308C in n-pentane.
b
498C in o-dichlorobenzene.
c
1058C in benzene.

5. Radical Transfer. — Radical transfer often occurs between macroradicals or peroxide

radicals and chemicals that contain easily abstractable H-atoms, such as some antidegradants
(mainly amine and phenolic types) or aromatic and naphthenic oils (Scheme 15).14,91 As a result,
the concentration of reactive radical sites is reduced because the radicals formed from
antidegradants and oils are stable with little reactivity.1,3,77 Therefore the use of such chemicals
should be avoided in rubber formulations cured with peroxides.
6. Branching of Elastomers. — Reactions of radicals in the elastomer backbone with radicals
formed at the end of macromolecular chains often lead to the branching of elastomers instead of
forming cross-links (Scheme 16).81
7. Acid-Catalyzed Decomposition of Peroxides. — If acidic substances are present during
vulcanization, they can cause ionic or heterolytic decomposition of peroxides (Scheme 17). As a
result no radicals are formed, so cross-linking does not take place.3,44,52,92 In order to prevent this
problem, acidic substances, for example acidic carbon black, should be excluded from rubber
compounding.

D. CO-AGENTS

Cross-linking of elastomers with peroxides can be effectively improved by using co-agents93–103

Co-agents are multifunctional organic molecules that are highly reactive toward free radicals9,22,88,104
The efficiency of peroxide curing in the absence of co-agents is sometimes rather low due to the
occurrence of side reactions, which consume radicals. Co-agents are able to boost peroxide efficiency
by suppressing side reactions to a large extent, like chain scission and disproportionation.14,23,105 But
it is believed that the main reason that co-agents increase cross-linking efficiency is mainly because of
the formation of co-agent bridges between rubber chains as extra cross-links.44,69,104,106 They are
used both to increase the cross-linking efficiency of the vulcanization process and to increase the
cross-link density of final vulcanizates 47,107,108 Several advantages have been reported for the rubber
compounds cured with peroxides and co-agents in comparison with those cured in the absence of co-
agents:1,23,44,104,109,110

SCHEME 12. — Disproportionation of elastomer radicals.44

 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 77

SCHEME 13. — Oxygenation of elastomer chains.

 improved peroxide efficiency

 higher tensile and tear strength
 higher modulus
 higher hardness
 higher resilience
 improved dynamic properties
 improved compression set
 improved abrasion and tear resistance
 improved heat aging
 improved resistance to oils and fuels
 improved adhesion to polar substrates (in the case of zinc salts)

Depending on their chemical structure, co-agents can react in the peroxide vulcanization of
unsaturated elastomers by addition and hydrogen abstraction or by addition reactions only. In the
case of saturated elastomers, mainly addition reactions take place.44,69 This was confirmed by
studies in which the consumption of co-agent unsaturation during the peroxide curing process was
spotted.2,69,111 According to their contribution to the vulcanization process, co-agents are divided
into two basic groups: type I and type II.9,14,23,25,44,98,108,112–114
1. Type I Co-Agents. — Type I co-agents are typically polar, low molecular weight
multifunctional compounds with activated double bonds. Most of them contain easily accessible
unsaturation without allylic hydrogens, and therefore they react primarily through addition
reactions. They are highly reactive toward radicals, so the induction period of the vulcanization
process is usually very short. By using this type of co-agent, not only is the rate of cure increased, but
the cross-link density or state of cure is also increased. Since they are rather polar materials, their
miscibility and compatibility with nonpolar rubber matrices can be limited. Type I co-agents
include multifunctional acrylates, methacrylates, bismaleimides, or zinc salts of acrylic and
methacrylic acid.
2. Type II Co-Agents. — Type II Co-Agents are, in general, less polar molecules that form more
stable free radicals, so the induction period is not as short as in the previous case. Most of the co-
agents of this type contain both readily accessible vinyl unsaturation sites for radical addition as
well as easily abstractable allylic hydrogen atoms. Addition is their most important mechanism, but
hydrogen abstraction is also considered to participate in reactions. The use of these co-agents leads
to the increase in cross-link density of vulcanizates, but in contrast to type I co-agents, they are not

SCHEME 14. — Dehydrohalogenation of elastomer chains.

78 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

SCHEME 15. — Radical transfer.

able to increase the cure rate. Owing to their low polarity, these co-agents have good compatibility
with most elastomers. Phthalates, cyanurates and isocyanurates, homopolymers of dienes and
copolymers of dienes, and vinyl aromatics belong to this class. Some of the commonly used co-
agents are presented in Table VIII.
The ideal representation of the multifunctional co-agent is shown in Figure 3. The number or
the functionality of chemical groups through which reaction with rubber chains can occur can alter.
This structure mainly represents type I co-agents, but also most type II co-agents (non-polymeric)
can be illustrated by this model. The reactive groups can differ in form from simple allylic and
pendant vinyl structures to maleimides, methacrylates, and acrylates. The functionality can range
from one (monofunctional) to five (pentafunctional) or greater. The properties of final vulcanizates
can also be affected by the structure of the bridging group. This group can have the form of a straight
chain (difunctional) or a branch structure (multifunctional), or it can consist of a cyclic alkyl or
aromatic ring. Linear structures can be either nonpolar (alkyl) or polar (polyether) and of varying
length, providing proximal or widely separated reactive groups. The bridge may also include highly
ionic bonds (metal salts, such as zinc acrylate and zinc methacrylate) or other bonds with weaker
dissociation energies.96
Since many of the commercially available co-agents are liquid in their form, they can reduce
the viscosity of rubber mixtures. Co-agents with low molecular weight act, more or less, as
plasticizers and can make processing of rubber compounds easier.69 Additionally, by introducing
co-agents, the amount of peroxide can be reduced while maintaining or even increasing the cross-
link density of cured elastomers.

E. CO-AGENT ASSISTED PEROXIDE VULCANIZATION

The reaction mechanisms of co-agents in peroxide vulcanization of elastomers have been a

subject of ongoing research, and several reaction pathways have been suggested for particular
types of co-agents. As outlined, type I and II co-agents differ in their chemical nature and
reactivity, and subsequently various reaction mechanisms also have been under consideration.
Most type I co-agents can homopolymerize and/or graft to macroradicals forming effective cross-
links through radical addition reactions (Scheme 18).101,114–119 Some type II co-agents with
easily extractable allylic hydrogens have been demonstrated to take part in intermolecular
propagation reactions as well as intramolecular cyclization reactions.93,120 Trifunctional allylic
co-agents, such as triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC), can form cross-

SCHEME 16. — Branching of elastomers.

 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 79

SCHEME 17. — Acid-catalyzed decomposition of dicumylperoxide.3

links through the cyclopolymerization products as well as grafting through pendant allyl groups
(Scheme 19). The polymeric co-agents, mainly high-vinyl polybutadienes (HVPBD), just
increase the concentration of side-chain unsaturated units, which are very reactive toward
addition reactions and thus propagate cross-linking.54,96,121 Co-agents like zinc acrylate (ZDA)
and zinc methacrylate (ZDMA) have been shown to form ionic cross-links when applied in cross-

TABLE VIII
TYPE I AND II CO-AGENTS APPLIED IN PEROXIDE VULCANIZATION OF ELASTOMERS

Type I Type II

Ethylene glycol dimethacrylate (EGDMA) Diallyl phthalate (DAP)

Zinc acrylate (ZDA) Triallyl isocyanurate (TAIC)
Zinc methacrylate (ZDMA) Triallyl cyanurate (TAC)
N,N 0 -m-phenylenedimaleimide (PDM) Divinylbenzene (DVB)
Trimethylolpropane trimethacrylate (TMPTMA) Triallylphosphate (TAP)
Pentaerythritol triacrylate (PETRA) High-vinyl 1,2-polybutadiene (HVPBD)
80 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

FIG. 3. — Idealized representation of multifunctional co-agent.96

linking of elastomers, which leads to the enhancement in the mechanical properties of cured
rubber materials and improves the adhesion between elastomer and metal substrates.94,99,104 Lu
et al.109 proposed a model of rubber/ZDMA interactions. They reported that the in situ radical
polymerization of ZDMA takes place during the curing process of the rubber matrix with
peroxide. Poly-ZDMA generated by this reaction aggregates to form the granular nanoparticles,
which can be physically adsorbed or chemically grafted onto rubber chains. These structures can
be considered the chemical or physical cross-linking points of the composites. Additionally, the
formation of ionic clusters through static electronic attractions with the contribution of zinc ions
from co-agent molecules was also observed. Covalent cross-links were also formed between
elastomer chain segments as a result of peroxide cross-linking. Rubber composites with this type
of morphology reveal the ability for stress relaxation, due to rubber chain slippage on the ionic
cluster surface and reformation of ionic bonds upon external deformation of the sample.
Network enhancement through the grafting of co-agents between elastomer
chains,44,96,121 the formation of an interpenetrating network of homopolymerized co-
agents,114,122,123 and the formation of higher modulus filler-like domains of thermoset co-
agent54,115,124,125 have been suggested. In general, co-agents are rather polar materials,
mainly those of type I; therefore, they are not very miscible with nonpolar elastomers and
may tend to phase separate and homopolymerize.51,69,95 The homopolymerized co-agent
domains can be co-vulcanized with the rubber matrix and behave as filler particles.14,44,69,109
Even if polymerized co-agent molecules are not grafted to elastomer chains, they can
improve mechanical properties of vulcanizates since they act as reinforcing fillers formed in

SCHEME 18. — Reaction mechanism of certain type I co-agents with elastomers.118

 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 81

SCHEME 19. — Reaction mechanism of certain type II co-agents with elastomers.120

situ during vulcanization. Moreover, polymerized co-agent domains can act as centers of
stress redistribution in vulcanizates upon external strain.104 The polymeric type II co-agents
are typically much more soluble in the rubber matrix, since the difference in solubility
parameters is much less pronounced. Therefore domain formation is usually not
expected.54,96
The effect of co-agent domains on mechanical properties of vulcanizates depends on the
rigidity of co-agent molecules. The domains with high rigidity (for instance domains formed
from co-agents containing rigid aromatic structures) partially contribute to the transfer of
stresses in the rubber network. The stress concentration near the hard co-agent domains upon
deformation may deteriorate the mechanical properties of the cured elastomers.126
Improvement in the mechanical properties can be achieved using co-agents with more
flexible structures to form soft domains of lower stiffness during the curing process. These
domains can deform more readily under the influence of an external stress similar to the
network formed by reinforcing filler particles.44,127
A lot of factors determine the reaction pathways and distribution of co-agents in the
rubber matrix, such as co-agent loading, the difference in polarity between the co-agent and
the rubber matrix (solubility), adequacy of mixing, and the relative reactivity of the co-agent
compared with the rubber.22,93,121 Figure 4 illustrates an idealized network structure of
elastomer formed from peroxide curing in the presence of co-agents.

F. GENERAL FEATURES OF PEROXIDE CROSS-LINKING

The peroxide vulcanization process is usually performed at temperatures 140–180 8C, and not
only unsaturated but also saturated elastomers and their blends can be cured with peroxides (Table
IX). The application of peroxide curing systems in cross-linking of elastomers leads to the
formation of covalent carbon–carbon cross-links between elastomer chain segments. C–C bonds
have higher dissociation energy in comparison with sulfidic cross-links, which are formed between
82 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

FIG. 4. — Cross-linked network structure of rubber matrix cured with peroxide in the presence of co-agent.54

elastomer chains by applying sulfur curing systems. Therefore the main features of peroxide cured
elastomers are high thermal stability and good resistance to thermo-oxidative aging. The general
advantages of peroxide cross-linking systems can be summarized as follows:1,22,25,38,44,113,128
 good heat-aging stability of vulcanizates
 good electrical properties of vulcanizates
 low compression set of vulcanizates at elevated temperatures
 ability to cross-link unsaturated as well as saturated rubbers and their blends
 simple formulation of rubber compounds
 rapid vulcanization without reversion
 no staining or discoloration of the finished parts
 possible to prepare transparent products

TABLE IX
ELASTOMERS AND BLENDS THAT CAN BE CURED WITH PEROXIDE CURING SYSTEMS

Elastomers Blends

Natural rubber (NR) NBR/EPDM

Isoprene rubber (IR) SBR/EPDM
Butadiene rubber (BR) PE/EPDM
Styrene-butadiene rubber (SBR) PP/EPDM
Acrylonitrile-butadiene rubber (NBR) PP/NR
Hydrogenated acrylonitrile-butadiene rubber (HNBR)
Ethylene-propylene rubber (EPM)
Ethylene-propylene-diene rubber (EPDM)
Chlorinated polyethylene rubber (CM)
Chlorsulfonated polyethylene rubber (CSM)
Silicone rubbers (Q)
Fluoroelastomers (FKM)
Polysulfide rubbers (TM)
Urethane rubbers (U)
 CURING RUBBER COMPOUNDS WITH PEROXIDE SYSTEMS 83

However, the main disadvantages of peroxide cross-linking in comparison with sulfur curing
systems are as follows:1,23,44,113,128
 worse tensile, elastic, and dynamic properties of vulcanizates
 lower abrasion resistance of vulcanizates
 low scorch safety
 sensitivity to elemental oxygen during curing, which can lead to surface tackiness
 certain components of rubber compounds, such as antidegradants or oils, may consume
free radicals
 decomposition products from peroxides are more or less volatile, provide typical smell,
show blooming effect, or can be extracted from vulcanizates by solvents
 generally higher cost

One of the biggest problems of peroxide curing systems is the complicated regulation of
scorch safety. It is determined mainly by type of peroxide and its ability to dissociate into free
radicals at the vulcanization temperature. Peroxide free radicals then rapidly react with
macromolecules of rubber to form cross-links. The regulation of scorch time, but also the whole
vulcanization process, can hardly be influenced by concentration of peroxides or by using
inhibitors of radical reactions, because their presence in rubber compounds usually leads to the
lowering of cross-linking efficiency. The problem can be partially overcome by using scorch
retardants or scorch protectants. A number of scorch retardants have been developed and applied
commercially, each working on different principles. Some scorch retardant systems have been
reported in the literature in more detail, like multifunctional acrylic monomers, phenolic
antioxidants, or functional nitroxyls.44,110,129–134 The most studied include 2,6-di-tert-butyl-4-
methylphenol (BHT) or 2,4-diphenyl-4-methyl-1-pentene (methyl styrene dimer,
MSD).44,131,135 Others include 1,1-diphenylethylene (DPE),129,136 (2,2,6,6-tetramethyl-piper-
idin-1-yl)oxyl (TEMPO),137,138 bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (bis-TEM-
PO),133 or acrylate-functionalized TEMPO, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-N-
oxyl (AOTEMPO).139

III. CONCLUSION
Since the discovery of cross-linking in elastomers with organic peroxides by Russian chemist
Ostromislensky in 1915, this process has been a subject of continual increasing interest by a lot of
engineers and scientists. Attributes such as high temperature aging stability and high resistance to
thermo-oxidative degradation make peroxide cured articles suitable for special applications
required mainly for good environmental stability. Although in general, the mechanical properties of
peroxide cured elastomers are worse when compared with sulfur vulcanizates, these disadvantages
can be to a certain extent eliminated by the proper selection of peroxide, but mainly by the suitable
choice of co-agent type and content. Therefore it is believed that the research relating to the peroxide
vulcanization and cross-linking of rubber compounds will be oriented mainly toward the
examination and testing of new types of co-agents and their reaction mechanisms with different
types of organic peroxides.

IV. ACKNOWLEDGEMENT
This work was supported by the Slovak Research and Development Agency under the contract
No. APVV069412
84 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 1, pp. 60–88 (2017)

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[Received June 2016, Revised September 2016]

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