RECENT DEVELOPMENTS IN CROSSLINKING OF ELASTOMERS

ABI SANTHOSH APREM

HINDUSTAN LATEX LIMITED, AKKULAM, SREEKARIYAM P.O, TRIVANDRUM, KERALA, INDIA -695017

KURUVILLA JOSEPH
ST. BERCHMANS COLLEGE, CHANGANACHERRY, KERALA, INDIA

SABU THOMAS
SCHOOL OF CHEMICAL SCIENCES, MAHATMA GANDHI UNIVERSITY, P.D. HILLS P.O., KOTTAYAM, KERALA, INDIA-686560

ABSTRACT
The recent developments in the vulcanization of elastomers, major types of crosslinking, and mechanism of crosslinking have been reviewed. Attention has been made to sum up the accelerated vulcanization. Possible mechanisms by which the reaction is taking place are discussed. The role of accelerators, activators, and fillers has been described. The different types of crosslinks and importance of each type on the specific properties of the resulting vulcanizates, etc., are discussed. Various aspects of vulcanization like model compound vulcanization, nitrosamine generation, etc., are discussed. The importance of binary accelerators and possible mechanism of their action have been mentioned. The method of double network formation, which is useful for the improvement in properties, is also described. The different methods for characterization of networks and different methods for estimating crosslink densities are also explained.

CONTENTS I. II. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458 Methods of Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459 A. Peroxide Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460 B. Resin Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461 C. Silane Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462 D. Metal Oxide Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463 E. Radiation Induced Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465 F. High Temperature Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466 G. Dynamic Crosslinking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466 H. Sulfur Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466 Accelerators. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467 Accelerated Sulfur Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469 Role of Activators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476 Sulfur Donor Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477 Influence of Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478 Binary Accelerator Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479 Concept of Double Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482 Characterization of Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485 I. INTRODUCTION The superior properties and low cost of natural rubber accounts for its use in a variety of applications. Originally natural rubber was used in the uncured state, but there were drawbacks
* Corresponding author. Ph: 91-481-2730003; Fax: 091-481-2731002; email: sabut@sancharnet.in

III. IV. V. VI. VII. VIII. IX. X. XI. XII.

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like softening in warm weather and highly increased rigidity in cold weather.1 This led Charles Goodyear in United States and Thomas Hancock in England to the discovery of the process of vulcanization in the years 1839 and 1843, respectively. Hancock was the first to observe that sulfur alone would vulcanize rubber, whereas Goodyear had actually used the first inorganic accelerator, lead oxide. Vulcanization is the key process in the technology of rubbers. It is difficult to come up with an equally old industrial process where the exact chemistry remains unclear. Thus, despite the fact that 160 years have passed since the discovery of vulcanization, the exact mechanism is still far from completely understood. The word vulcanization has English roots and was derived from the name of the Greek and Roman God Vulcanus. Nieuwenhuizen wrote in his review,2 "Vulcanus was the ugliest of all the Gods; this symbolizes the fact that vulcanization is a bad-smelling process. In spite of the ugliness of Vulcanus, due to his talents and character he married Venus the most beautiful of all. Indeed we find that vulcanized rubber is a wonderful product, as measured by its versatility, usefulness and broad application". The use of natural rubber as a material for finished products dates back to the 1830's. Vulcanization is basically the process of introducing crosslinks between hydrocarbon chains. According to the definition of American Society for Testing and Materials (ASTM), Vulcanization is a chemical process in which the long chains of the rubber molecules become crosslinked by reactions with the vulcanizing agent to form three dimensional structure (ASTM D1556). This reaction transforms the soft, weak, plastic-like material into a strong elastic product. The rubber loses its tackiness, becoming insoluble in solvents and more resistant to heat, light and ageing processes. (Scheme 1) Sulfur alone was the vulcanizing agent up to the discovery of organic accelerators in the early part of 20th century. It was quickly realized that the use of accelerators gave improved properties and significantly reduced the required cure times. The first accelerators were aminebased compounds, with other classes of accelerators following quickly. Other compounds used in vulcanization in addition to sulfur and accelerators are zinc oxide and saturated fatty acids such as stearic acid. These materials are termed as activators. Rubber formulations can also include fillers such as silica and carbon black and compounds such as antioxidants. II. METHODS OF VULCANIZATION The formation of network structure is one of the essential conditions for generating the elastomeric properties. Sulfur vulcanization is the most widely used curing technique for rubbers, preferably for unsaturated ones. The other curing methods include peroxide, resin, moisture, urethane, metal oxide and radiation crosslinking.3

Uncrosslinked state

Crosslinked state

SCHEME 1. Elastomer chains in the uncured and cured state.

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Since the 1963 Natural Rubber Producers Research Association (NRPRA) overview on the fundamentals of vulcanization chemistry,4 it has become more and more apparent that, for the purpose of understanding vulcanization on a molecular level, the different vulcanization systems should be treated separately. Even though the different vulcanization systems are broadly similar in reactivity, it can be easily understood that a small change in the reactivity of one chemical may have an important influence on a whole series of chemicals. Indeed during vulcanization different reactions take place at the same time. In fact, rubber technology makes ample use of the knowledge that the different vulcanization systems result in rubber materials having different properties and specifications.
A. PEROXIDE VULCANIZATION

A wide variety of peroxides are used to crosslink most type of elastomers. The crosslinks formed by peroxides are purely carbon-carbon linkages. The importance of peroxides is their ability to crosslink saturated elastomers such as low-density polyethylene, ethylene-propylene rubber, silicone rubber etc., which cannot be crosslinked with other types of vulcanizing agents. The advantages and disadvantages of peroxide crosslinking are given in Table I.
TABLE I ADVANTAGES AND DISADVANTAGES OF PEROXIDE CROSSLINKING5

Advantages Simple compounding Good heat ageing resistance Low tension set and strain No contamination Low compression set Transparent rubbers possible

Disadvantages Expensive crosslinking agent Low mechanical strength Higher curing time Difficult hot-air cure Poor resistance to flex fatigue Need secondary cure of high temperature

In addition to the disadvantages described in Table I, there are several other important limitations for peroxide crosslinking of rubbers. One of them is that antioxidants can react with peroxide generated radicals and can result in reduced crosslinking efficiency.5 Another potential problem is that carbon-centered radicals can react with oxygen. This reaction will produce hydroperoxides and can lead to tacky, unvulcanized surfaces. The mechanism for peroxide crosslinking is shown in Scheme 2. The crosslinking reaction involves the homolytic decomposition of the peroxide to produce alkoxy radicals followed by hydrogen atom abstraction. Studies with model compounds indicate that the hydrocarbon radicals predominantly undergo coupling rather than disproportionation. The coupling reaction forms crosslink between polymer chains. For polydiene elastomers experimental evidence indicates that the primary radical formed by peroxide decomposition abstracts a hydrogen atom from a carbon alpha to the double bond. In the case of natural rubber the methyl group is also reactive towards hydrogen atom abstraction.

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SCHEME 2. Mechanism of peroxide crosslinking (P-H saturated or unsaturated elastomer).3,4

B. RESIN CROSSLINKING

Resin crosslinking was discovered around the 1940's.6 It has been used for curing unsaturated rubbers. Resin curing systems are extensively used with butyl rubber for high temperature applications. Resin cures are slower than accelerated sulfur cures and high temperatures are required; and they can be activated only by zinc oxide and halogen atoms. Low molecular weight resin molecules diffuse into rubber and thereby stiffens the rubber. An example of recipe for butyl rubbers is given in Table II. In this SP-1055 is the phenolic curative. The phenol-resin crosslinking of butyl rubber is accelerated by adding benzocarbonium ions to the double bond, forming a cyclic coumarone structure or a non-cyclic compound as illustrated in the Scheme 3.7 Crosslinking is considered to proceed via a mechanism such that a coumarone ring is produced by a Diels-Alder (4+2)-cyclo-addition reaction of quinomethine. Compared to butyl rubber the resin crosslinking rates of EPDM and nitrile rubber are low. Volintu et al.8 have reported the crosslinking of nitrile rubber with p-octyl-phenol formaldehyde resin.
TABLE II RECIPE FOR VULCANIZATION BY RESINS

Ingredients Amount (phr) Butyl rubber 100 ZnO 5 Stearic acid 1 Resin SP-1055 12 Typical vulcanization conditions Temperature (C) 182 Time (min) 80

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SCHEME 3. Mechanism of resin crosslinking.7

C. SILANE CROSSLINKING

This type of crosslinking is also called moisture crosslinking. Alkoxysilane compounds are used as crosslinking agents together with water. The silanes carry functional groups, which are likely to react with rubbers.

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SCHEME 4. Mechanism of silane crosslinking.9

The moisture crosslinking of polyethylene using vinyl silane is shown in Scheme 4. The crosslinking reaction includes two steps: (i) the reaction of a silane compound with a polymer (grafting); and (ii) the condensation of the silanol groups produced by hydrolysis of the alkoxysilyl groups. This process was used for EPR for the cable industry.10 The major advantage of this type of cure is the applicability at relatively low temperature.
D. METAL OXIDE CROSSLINKING

Chloroprene rubbers are generally vulcanized by the action of metal oxides.11,12 The primary crosslinking agent is zinc oxide, which is used along with magnesium oxide. Lead oxides are sometime used when low water absorption is required. The reaction is thought to involve the vinyl group of the elastomer, which is the result of 1, 2 polymerization. A typical recipe for metal oxide crosslinking is given in Table III. Two routes have been proposed for the curing. One requires the incorporation of zinc atoms into the crosslink [Scheme 5]; the other leads to ether crosslinks [Scheme 6].

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SCHEME 5. Mechanism of crosslinking in 1,2-poly chloroprene involving incorporation of Zn atom.11

SCHEME 6. Mechanism showing crosslinking in 1,2-poly chloroprene through the formation of ether crosslinks.12
TABLE III METAL OXIDE SYSTEMS FOR CHLOROPRENE RUBBER

Ingredients Chloroprene rubber ZnO MgO Calcium stearate Stearic acid TMTM DOTG ETU Sulfur Temperature (C) Time (min)

100 5 4

Amount (phr) 100 5 5.5

100 5 4 1 1 1

0.5 Vulcanization conditions 153 15

0.5 1 153 15 153 15

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E. RADIATION INDUCED CROSSLINKING

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The most recent type of crosslinking is the radiation-induced crosslinking. This includes electron beam crosslinking, photo-crosslinking, microwave crosslinking, ultrasonic crosslinking etc. Radiation induced crosslinking is a physically induced chemical reaction, which is easier and preferable for continuous curing technologies, and thus it has some potential for the future. The radiation dose required for rubber differs. Radiation crosslinking of different rubbers are reported.13-15 Upon irradiation free radicals are formed in rubber molecules. The free radicals can combine to form crosslinks as in the case with peroxide crosslinking. In radiation crosslinking, rubber is pressed at 100-200 C for 5-10 minutes. It is then allowed to cool under pressure and then exposed to radiation. The radiation dose required for proper crosslinking is 90 M rad for NR, 17 M rad for NBR, 40 M rad for CR, 10 M rad for silicone rubber and 10 M rad for CFM. The mechanism is shown in Scheme 7. The use of sensitizers can reduce the required dose and radiation time. Halogen compounds, nitrous oxide, sulfur monochloride, and bases like amine, ammonia etc are used as sensitizers.16 Radiation vulcanization for NR latex, SBR and functional monomers have been reported.17 Radiolysis of NR RH Radiolysis of water H2O

R + H

H + OH

Hydrogen abstraction RH + OH Homopolymerisation nM P R + H2O

Graft polymerisation R + nM Chain transfer P + RH RP + RH R + P M + RP Ternination R + R RP + R RR RPR P + R RP + R RP RP RP

SCHEME 7. Mechanism of radiation vulcanization using sensitizer.18

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F. HIGH TEMPERATURE CROSSLINKING

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This type of crosslinking is also called high velocity crosslinking and is carried out over a temperature range of 170-230 C. Usually tires are cured routinely at temperatures this high. However it is often associated with reversion. Chen and coworkers19 have shown that the phenomenon of reversion seems to appear when two competing reactions occur during vulcanization. These two reactions are crosslinking and desulfuration. The process is associated with the formation of a trans-methine structure (Figure 1) by the desulfuration reaction. Morrison and Porter20 confirmed that the observed reduction in vulcanizate properties is caused by two reactions proceeding in parallel, i.e. desulfurization and decomposition. Loo21 has demonstrated that as the cure temperature rises, the crosslink density drops and the degree of reversion increases. Temperature is thus a major factor than the duration of vulcanization in determining the degree of crosslinking. Loss of properties at elevated temperatures could be avoided by two ways: (i) optimization of the accelerator/sulfur ratio; and (ii) use of an accelerator, which is less sensitive to increased temperatures.

FIG. 1. Structure of trans-methine.

G. DYNAMIC VULCANIZATION

Dynamic vulcanization is the process of vulcanizing the elastomer during the melt-mixing process, with a non-vulcanizable molten thermoplastic.22 One of the most interesting applications of accelerated sulfur vulcanization is in the preparation of thermoplastic elastomers by dynamic vulcanization. In this process, small rubber droplets are vulcanized to give vulcanized rubber particles with stable domain morphology, in which the rubber particles are dispersed in the molten thermoplastic polymer to allow the blend to be fabricated into finished products in thermoplastic processing equipment. The diameters of the elastomer particles are reported to be in the 1-2 m range. Various blends of EPDM with polypropylene were dynamically vulcanized with accelerated vulcanizing systems consisting of sulfur, zinc oxide, stearic acid, tetramethyl thiuram disulfide and benzothiazyl disulfide.23 Peroxides are also used for dynamic vulcanization. Recently, new vulcanizing agents were introduced for dynamic crosslinking of elastomer blends.24 They were found to be efficient in crosslinking and impart good mechanical properties to the resulting vulcanizates.
H. SULFUR VULCANIZATION

Rubber vulcanization by sulfur, without any accelerators takes several hours and is no longer of commercial importance. With the use of accelerators, optimum curing can now be achieved in periods as short as 2-5 min. Sulfur vulcanization can be divided into two categories; unaccelerated and accelerated sulfur vulcanization. Unaccelerated formulations typically consist of sulfur, zinc oxide and a fatty acid while accelerated formulations include an accelerator in the system. Unaccelerated sulfur vulcanization, which is also referred to as sulfur only vulcanization, is the

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oldest form of vulcanization practices. Sulfur only vulcanization chemistry involves many reactions that either do not occur, or occur to much lesser extent than in accelerated systems. It should be noted that un-accelerated sulfur systems are no longer of commercial significance. III. ACCELERATORS The discovery of acceleration of vulcanization using organic compounds in 190625 is next in importance to the discovery of vulcanization itself. In the early days, vulcanization took several hours to get completed. Today it has been reduced to a few minutes. Accelerators reduced the vulcanization time drastically. The temperature can be reduced and in some cases vulcanization can be done at room temperature. Furthermore the proportion of sulfur is reduced from 810 parts to 1-3 parts. The proportion of accelerator is usually 1 part. The lowering of sulfur gives much better oxidation resistance and some accelerators are good antioxidants. The first accelerators were inorganic compounds. Among the basic salts and metals oxides, which are or have been widely used as accelerators, litharge, lime magnesium oxide and zinc oxide are the most important ones. Organic vulcanization accelerators were first utilized in the rubber industry in the beginning of the 20th century.25-31 Oenslager26 in 1906 introduced the organic bases aniline and thiocarbanilide as accelerators in rubber compounds to improve the quality of low-grade rubber and to accelerate the rate of vulcanization. Thus organic bases were the first vulcanization accelerators of rubber.32-34 Other accelerators such as diphenyl guanidine (DPG) diorthotolyl guanidine35-36 (DOTG) and hexamethylene tetramine (HEXA) came in to use around 1910 and were a great relief for the people in the rubber industry because of their relative non-toxic character compared to the former ones. Dithiocarbamates and xanthates were widely used as accelerators. Because of their instability, fast reactivity and poor processing safety they are generally used in low temperature processing and curing and in accelerator combinations. In 1925, Sebrell et al.37-39 and Bruni et al.40 discovered independently that 2-mercapto benzothiazole, its homologues, its disulphides41, 42 and its metal salts are very effective accelerators, which yields vulcanizates of improved physical properties. 2, 2' dithiobenzothiazole (MBTS) was developed to give greater scorch safety at the use of fine furnace blacks, delayed action accelerators like sulphenamide type (e.g. Benzothiazyl derivative of sulphenamide) were developed for long processing safety and satisfactory cure rates. Attempts to modify the extraordinary fast ammonium dithiocarbamates resulted in the zinc dialkyl dithiocarbamates. Further efforts to substitute the mercaptan sulfur in dithiocarbamate resulted in tetra alkyl thiuram disulphides like tetra methyl thiuram disulfide (TMTD), tetra methyl thiuram mono sulphides (TMTM) and thiuram tetra disulphides.43-45 They are used as ultra accelerators and vulcanizing agents themselves. All of these products are currently used in a large scale as accelerators. Thus the discovery of various types of accelerators which differ in their effects on the rate of scorching, ageing, etc., of rubber compounds and on the structure of the resultant vulcanizates which determines the ultimate property have revolutionized the rubber industry. Based on the nature of curing and chemical structure accelerators are classified into several groups. The generalized classification is shown in Table IV.

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TABLE IV PRINCIPAL CLASSES OF ACCELERATORS USED IN THE SULFUR VULCANIZATION OF ELASTOMERS

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RECENT DEVELOPMENTS IN CROSSLINKING OF ELASTOMERS IV. ACCELERATED SULFUR VULCANIZATION

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Accelerated sulfur formulations are the most common vulcanization systems used in commercial and industrial applications. For this reason, a large amount of work is going on in the fundamental and applied aspects of accelerated sulfur vulcanization. The study of accelerated sulfur vulcanization suffers from the problems like the ability of sulfur to undergo both radical and ionic reactions, the intractable nature of cured vulcanizates, how the accelerators and activators interact and how these interactions affect the vulcanization mechanism etc. A major contributing factor to the disagreement over mechanisms is the possible reactions that sulfur and accelerators undergo. Sulfur occurs naturally as an eight membered ring. This ring is capable of both homolytic cleavage to form radicals or heterolytic cleavage to form ions.46 Also, the precise interaction of the accelerator and sulfur in the vulcanization process has not been clearly elucidated. It is known that accelerator complexes are found, but the action of actual sulfurating species has not been determined. This fact and the possible reactions of sulfur and accelerators have made it impractical to eliminate the radical or polar mechanism. Several researchers have concluded that both radical and polar mechanisms are operative,47-53 and that the precise nature is dependent on the formulation. The scorch delay or induction period is where the majority of accelerator chemistry occurs. It should be noted that the scorch delay varies widely between accelerators. In thiuram accelerated systems there is little induction time whereas in MBT accelerated system there is a short induction time. In sulphenamides there is a long scorch delay. During the scorch delay various accelerator complexes are formed. Early workers have proposed54 a variety of conclusions to the exact nature and role of these complexes. Typical cure curves for samples cured with different accelerator systems are given in Figure 2.

FIG. 2. Typical cure curve with different accelerator systems: A) Dithiocarbamates; B) Thiurams; C) Thiazoles; D) Sulphenamides.

While it is clear that specific complexes do form, it is still open for debate whether these complexes are the active sulfurating species or whether an activated intermediate is formed. Accelerated sulfur vulcanization has been found to consume the accelerator in the system at a

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rate far greater than the rate of crosslinking.55 This has led to the proposal that accelerated vulcanization proceeds through an intermediate.56,57 Subsequent research has provided strong evidence for the existence of this species.52,58 Coran58 in his work, isolated a compound and identified it as a complex consisting of the zinc salt of the accelerator stabilized by interaction with stearic acid. He modelled the mechanistic scheme for the formation of this complex and subsequent crosslinking/sulfurization as: A B B Vu A + B B where A = accelerator; B = intermediate; B* = active intermediate (sulfurating agent); Vu = crosslink; and , = constants to adjust stoichiometry. Research by Banerjee and co-workers52,54,59,60 led to the conclusions that both polar and radical mechanisms are operative during vulcanization. Their work indicated that several common accelerators including MBT and TMTD were capable of undergoing both polar and radical reactions. The proposed radical mechanism of accelerated sulfur vulcanization is shown in Scheme 10. The intermediate cleaves to form persulfuryl radicals, which then abstract protons. The rubber radical reacts with another intermediate to form a rubber-bound intermediate. Two rubber bound intermediates then form the actual cross-link. Maturity of the network occurs through sulfur exchange reactions. Isomerization, which is widely observed in vulcanization,61 occurs through alkyl radical.

SCHEME 10. Radical mechanism of accelerated sulfur vulcanization.62

The proposed polar mechanism is shown in Scheme 11. The key step is a concerted reaction of a ring structure leading to the formation of the rubber bound intermediate on the sulfur crosslink. Isomerization occurs by loss of the rubber bound intermediate as an ion.

SCHEME 11. Proposed polar mechanism of accelerated sulfur vulcanization.62

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There are varying opinions on the concentration of the rubber bound intermediate at any given time in the reaction process. The exact nature of accelerated sulfur vulcanization is still a topic of much debate. Recent advances in instrumental techniques have been able to provide more information about the resulting structures, but the actual chemistry involved is still not sufficiently clear. It is probable that both free radical and polar mechanism are operative and that the exact nature of the vulcanization process will vary between different curing systems.62 The chemical structure, molecular weight and conformation of the elastomers affect the efficiency of sulfur vulcanization and the physical properties.63 The sulfur vulcanization with unsaturated rubbers occurs through complicated radical mechanism in terms of mono, di or polysulphidic bridges and sulfur containing intra-cyclization with the polymer molecules. The crosslink density and distribution affect the physical properties and the stability on ageing and are dependent on accelerator type, ratio of accelerator to sulfur, reaction temperature and time.64 Various structures formed in sulfur vulcanized natural rubber is shown in Scheme 12.

SCHEME 12. Generalized structures in sulfur vulcanized natural rubber.65

As the rate of vulcanization is directly related to productivity, it is desirable to increase the rate by raising temperature. However at higher temperature the effectiveness of sulfur cross-links is lower with a sacrifice of the physical properties caused by the dissociation of sulfur bonds and rubber chains. Thus the reactivity was controlled by additional amounts of sulfur and accelerator instead of raising temperature. The increase of sulfur addition leads to increase in crosslink density and the proportion of polysulfidic linkage, causing a decrease in the stability on ageing. With the increase of accelerators the effectiveness of sulfur vulcanization having mono and disulfidic linkages is improved to give stability on ageing.66 The sulfur level determines the overall extension of sulfurization, while the accelerator concentration determines the efficiency of the formulation.67 Layer68 used the unique approach of vulcanizate recurring to probe the role of sulfur and accelerators in the curing and reversion process. He concluded that sulfur determines the overall amount of reaction, but the accelerator determines the length of sulfur chains. He proposed that the key step in the curing reaction was the sulfur exchange reaction.68,69 Model compound vulcanization (MCV) is the vulcanization of a low molecular weight model for the rubber polymer. It is a prime research technique applied to gain information about

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the chemistry of vulcanization. The compound selected for MCV should contain at least one allylic hydrogen, since crosslink formation involves the substitution of allylic hydrogen for a sulfur link.2 The objective of an MCV study is to obtain information regarding the chemistry of the repeating rubber unit, to elucidate the structure of the crosslinked products that are produced during vulcanization and to study the reactions of curatives in a rubber like environment. Ultimately this knowledge would furnish information about the mechanism of the vulcanization reactions.7072 The chemical probe work has allowed characterization and quantification of the number of mono, di and poly sulphidic crosslinks. The model compound work has been useful in providing information for mechanistic studies by allowing comparison of products predicted by a mechanism to the products obtained from model compound work.73 A typical cure curve obtained from a rheometer is shown in the Figure 3. The initial portion of the curve is called the induction or scorch period where much of the accelerator chemistry is involved. As time goes on torque increases and attains a maximum value. This point indicates the maximum torque. The time required to attain 90% of the maximum torque is termed as the optimum cure time (t90) where as the time required to attain 10% of the maximum torque is termed as the scorch time (t10). After attaining a maximum torque the crosslinks formed will be shortened or destroyed. This behavior is different for different compounds and the type of curing.

FIG. 3. Typical rheograph showing different stages on curing.

Depending on the accelerator/sulfur ratio desulfurization or decomposition may occur. An outline of the mechanism is shown in Scheme 13. Depending on the type and nature of vulcanization the cure curves exhibit different nature. After attaining the maximum torque, it may increase further (marching), or decrease (reversion), or levels off (Figure 4).

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SCHEME 13. Generalized mechanism of vulcanization.20

The choice of the accelerator in the process of sulfur vulcanization determines the kind of network structure and consequently, leads to the specific material properties.74-75 The chosen accelerator affects the cure rate and scorch safety, as well as the numerosity and the average length of the formed crosslinks. Both the number and the length of the crosslinks have an influence on physical properties of rubber. Monosulphidic crosslinks are regarded as being unable to exchange, rearrange or break to relieve mechanical stresses without cleaving main chains. Polysulphidic crosslinks on the other hand are able to rearrange under stress, through breaking and reforming and this is partly associated with high mechanical strength. Also, changes during service are determined in considerable measure by the strength of the crosslinks. Shorter mono and disulfide crosslinks contain thermally stronger C-S-C and C-S-S-C bonds, which are associated with superior thermal and oxidative stabilities. Studies have been undertaken on network characterization of natural rubber vulcanizates.76 Based on the amount of accelerator and sulfur present, the vulcanization systems are classified into conventional (CV), semi-efficient (semi-EV) and efficient (EV). The amount of accelerator and sulfur present in these systems are given in Table V.

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TABLE V COMPOSITION OF CONVENTIONAL, SEMI EV AND EV CURE SYSTEMS88

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Type of system Conventional Semi EV EV

Sulfur (phr) 2.0-3.5 1.0-1.7 0.4-0.8

Accelerator (phr) 1.2--0.4 2.5-1.2 5.0-2.0

A/S ratio 0.1-0.6 0.7-2.5 2.5-12

FIG. 4. Rheograph showing different behavior in modulus development.

The properties of the resultant vulcanizates are given in Table VI. As seen from the mechanism of vulcanization given by earlier researchers4,78 the active sulfurating agent is the zinc perthio mercaptide complex. The concentration of this complex determines the type of crosslinks formed. As the CV system has got greater amount of sulfur compared to the accelerator the possibility of forming more polysulphidic linkages is higher for CV system. As the concentration of accelerator increases two reactions viz., desulfurization or decomposition may occur. Desulfurization results in mono and disulphidic linkages while decomposition leads to cyclic sulphides, conjugated dienes, cyclic sulphides etc. When the temperature is increased the polysulphidic linkages break into mono and di sulphidic linkages. This explains the reversion shown at higher temperatures. This leads to low strength and modulus. Properties like compression set and thermal stability are better for EV systems. This is primarily due to the lower amount of polysulphidic linkage in the EV system.

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TABLE VI VULCANIZATES STRUCTURE & PROPERTIES OF THE DIFFERENT SULFUR CURING SYSTEMS88

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Properties Poly and disulphidic crosslinks (%) Monosulphidic crosslinks (%) Cyclic sulphide concentration Low temperature crystallization resistance Heat ageing resistance Reversion resistance Flex fatigue resistance Compression set 22 hours at 70 C (%)

CV 95 5 High High Low Low High 30

Semi EV 50 50 Medium Medium Medium Medium Medium 20

EV 20 80 Low Low High High Low 10

The general nature and amount of crosslinks present in an efficient vulcanizing system and conventional system is given in Figures 5 and 6, respectively. It is seen that the amount of monosulphidic linkages is a maximum in the efficient system and it increases initially and decreases with cure time. At the same time, the amount of polysulphidic and disulphidic linkages decreases with time. The final network formed after the desulfurization and decomposition reactions will be highly crosslinked with mainly monosulphidic bonds and there will be relatively few modifications of the cyclic sulphide or conjugated triene type.4 Such a network is termed efficiently crosslinked.

FIG. 5. Features of NR vulcanizate produced by an efficient crosslinking system.4

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FIG. 6. Features of NR vulcanizate produced by a conventional crosslinking system.4

On the other hand desulfurization process proceeds slowly as in the case of the compound depicted in Figure 6. Here the amount of polysulphidic linkages is higher. There will be opportunities for thermal decomposition, leading to reversion or loss of crosslinks and to networks containing modifications. Further the crosslinks, which do survive, will be di or polysulphidic and hence will be liable to further decomposition. These networks are said to be inefficiently crosslinked. V. ROLE OF ACTIVATORS Fatty acids are generally regarded as indispensable activators in conjunction with zinc oxide. The function of fatty acid activators such as stearic acid, is to solubilize the zinc oxide, a secondary effect is an increase in the amount of zinc sulphide produced. The zinc salts of fatty acids, which are a type of surfactant, also solubilize insoluble accelerators to form the actual catalyst. A general scheme of accelerated sulfur vulcanization that demonstrates the role of zinc oxide, in conjunction with fatty acids is shown in Scheme 15.78

SCHEME 15. Role of ZnO, fatty acid and activator in accelerated sulfur vulcanization.77
X= Accelerator residue; L = Ligand (basic nitrogen or zinc carboxylate).

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Duchacek79 noted that increasing the zinc oxide concentration increased the rate of extent of crosslinking up to a certain zinc oxide concentration; this concentration is believed to be the minimum level of zinc oxide needed to completely convert the accelerator to the zinc-acceleratorsulfur complex. He also noted that the optimum zinc oxide content to minimize reversion was slightly greater than this minimum. Coran58 also noted that the induction time had a dependence on the zinc oxide concentration in excess of that required for formation of the accelerator-zinc complex. This suggests that zinc exerts an influence beyond inclusion in the accelerator complexes. Recently, research work on safe accelerators has gained a lot of interest.80-82 Some of the accelerators are reported to be unsafe due to the formation of carcinogenic compounds such as nitrosamines. It is reported that accelerators derived from secondary amines are usually evolving nitrosamines.80 Avoidance of unfavorable conditions, elimination of secondary amine containing accelerators and elimination of formed nitrosamines are the various possibilities of reducing nitrosamine formation.81 Nitrosamine can be generated during the processing stage of rubber. The faster the amine is produced from cure or the earlier it is produced in the process cycle, the greater the opportunity for nitrosamine formation.82 This makes the synthesis of safe accelerators a field of great interest. VI. SULFUR DONOR SYSTEMS Apart from using free sulfur as a crosslinking agent other materials, which could donate sulfur to the system, are used for curing. Tetramethyl thiuram disulfide is found to act as a crosslinking agent in the absence of sulfur. It is not known whether the reaction involves the intermediate formation of elemental sulfur or whether the disulfide itself is the active agent. It appears that under cure conditions and in the presence of zinc oxide, two thirds of the thiuram disulfide invariably appears eventually as the zinc dithiocarbamate.

3 R2N.CS.S.S.C.S.NR2

Zinc Oxide 2 R2N.CS.S.Zn.S.CS. NR2 + ? Rubber

The network structures of sulfurless systems are similar to those obtained from accelerated sulfur systems discussed in the preceding section. It has been suggested that thiuram disulphides function during cure by decomposition to yield active sulfur and ZDC, which together constitute an accelerated sulfur system. In the past the opinion has been that TMTD vulcanizes via the intermediate formation of TMTM and active sulfur83 and later the reverse had been suggested84 ie., TMTM vulcanizes in the presence of sulfur via the intermediate formation of TMTD. Another approach for sulfur donor vulcanization was the use of model compounds. This study by Gregg and Lattimer85 used the cyclic tetramer shown in Figure 7 to model cis-polybutadiene. Their conclusions were similar to previous findings and they elaborate about an ionic mechanism involved in the process.

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FIG. 7. Complex formed in the presence of sulfur donors.

Another technique for analysis of sulfurless vulcanization has been the use of DSC coupled with chemical probe/equilibrium swelling.86 The results of this work indicated that zinc oxide dramatically increases the efficiency of vulcanization, but is not required for sulfurization. The advantage of sulfurless cure using TMTD is that the vulcanizates have low sulfur content and excellent ageing properties. Furthermore the curing is more efficient than the normal efficient vulcanization (EV). VII. INFLUENCE OF FILLERS Reinforcing and non-reinforcing fillers are used in rubbers. Fillers are known to influence crosslinking reaction during vulcanization. Channel blacks retard cure when compared to furnace blacks, some silicas when compared to silicates and hard clay when compared to whiting. This behavior depends on particle size. In most cases the cause of this retardation is due to the greater or lesser acidity of the filler, which influences the kinetics of the crosslinking reaction. Fillers contribute to crosslinking by adsorption of the molecules on their surface and appear to be capable of modifying the course and efficiency of vulcanization reactions either directly or through adsorption of curatives. Studies by Kraus87 have shown that regardless of the nature of the apparent filler contribution it is desirable to have the 'filler effect' included in the degree of cure. Carbon black contains not only carbon atoms but also a number of other elements such as hydrogen, oxygen, nitrogen and sulfur.88 These heteroatoms belong to the carboxyl, lactones, phenols and quinones present on the surface of the black.89 The physical and chemical interactions between the black and the other ingredients can influence the chemistry of curing and reinforcement due to the fillers. Porter reported90 that the crosslink density of a black reinforced vulcanization system increased about 25% compared to the corresponding unfilled one. Carbon black also increases the rate of vulcanization and improves the reversion resistance.91 The degree of improvement depends largely on the size of the carbon black particles. Structurally the black filled vulcanizate is found to contain fewer polysulphidic linkages than the corresponding

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unfilled vulcanizate.92 However, the structural changes appearing will be small when compared with the large effects of the fillers on the physical-mechanical properties of the vulcanizates. Black filled vulcanizates, generally have a faster rate of cure and better reversion resistance.93 This has been related to the formation of trans-methine structure in the vulcanizates in the reversion process. In the presence of carbon black trans-methine content is decreased. This may be attributed to two reasons: (i) polymer-filler interaction; or (ii) the improved crosslinking efficiency. The trans-methine structure of the main chain modification is formed from the thermal instability of the polysulphidic linkages through a desulfurization process.94 The amount of trans-methine formation is a function of the initial concentrations of polysulphidic crosslinks. If the polymer-filler interaction exerts a binding effect on the double bond migration, some polysulphidic linkages, which would otherwise break up through desulfurization in the unfilled systems, may survive in the black filled vulcanizates. Thus, in the reversion stage, the filled sample, in general would be expected to contain more polysulphidic linkages than the unfilled one. As the polysulphidic linkages have greater thermal stability in the black filled sample, the trans-methine formation is reduced and the reversion resistance is improved.93 VIII. BINARY ACCELERATOR SYSTEMS The use of binary accelerator system is an aspect of vulcanization that has been generating increased interest in recent years. Due to the increased complexity of these systems only recently have papers begun to probe the intricacies of binary system. A binary accelerator system refers to the use of two accelerators in a given formulation. Several authors have studied the synergistic behavior of these systems.95-100 Technically the use of binary accelerators is quite old. Many amines such as diphenyl guanidine (DPG) are used in combination with other accelerators such as MBT or sulphenamides to activate the vulcanization reaction. However, present day binary accelerators usually consist of benzothiazole and thiocarbamate derivatives. Additionally MBT and sulphenamides are often added to thiuram systems to increase the scorch delay of these systems. There have been several approaches analyzing the vulcanization behavior of binary accelerators. It is believed that the improved properties of binary systems resulted from the formation of combination accelerator complexes. One way to illustrate this effect is to measure mechanical or physical properties as a function of accelerator ratio and correlate the optimum property with the complex formation as shown in Figure 8.100 The effect of binary accelerator combination in natural rubber and butyl rubber, on the modulus is given in the Figure 8.

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FIG. 8. Effect of binary accelerator systems in mechanical properties of vulcanizates OTOS- N-oxydiethylenethiocarbamyl-Noxydiethylene-2-benzothiazole sulphenamide, OBTS- N-oxydiethylene-2-benzothiazole sulphenamide.

In both the rubbers synergism in modulus is observed for the accelerator combinations. It is observed from the figure that for the same accelerators synergism is observed at different compositions. It means that optimum concentration (complex formation) is attained at different composition of accelerator for different rubbers. Today, binary accelerators are widely used in industry. They are becoming increasingly popular due to the fact that such mixed systems (i) permit vulcanization to be carried out at lower temperature in lesser time, (ii) produce vulcanizate with superior physical and mechanical properties compared to those of a stock cured with a single accelerator. Though a great deal of work has been done on elucidating the mechanism of vulcanization by single accelerators, little attention has been paid so far to the chemistry of vulcanization with binary accelerator systems. Dogadkin and co-workers101 and Skinner and Watson102,103 investigated a number of popular accelerator combinations and found mutual activation with many of them. Depending on the experimental results obtained in the vulcanization with various combinations of most generally used accelerators, Dogadkin and co-workers104 classified the various binary accelerators into the following three different groups.

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1. Systems with synergistically active accelerators. This group consists of disulphides or mercaptans with nitrogen containing organic bases and disulphides, e.g. MBTS TMTD/MBT with MBS/CBS, etc. 2. Systems in which the mutual activity of the pair does not exceed the activity of the most active accelerator used. This group consists of sulphenamides with nitrogen containing organic bases. 3. Systems with an additive action of the accelerators. They include sulphenamides in combination with TMTD and those containing combination of accelerators belonging to the same class. Based on these observations, Dogadkin and coworkers104 suggested that in the initial stage of vulcanization, the accelerators interact with one another to form an active complex, which then disintegrate with the formation of active free radicals responsible for initiating the interaction of rubber with sulfur. Though the above classification of binary accelerator systems is very useful, the mechanism suggested cannot explain all the facts exhibited by the mixed accelerator systems. The schematic representation of the action of binary accelerator proposed by Dogadkin is shown in Scheme 16. But it could not fully explain all the observed properties shown by binary accelerator vulcanization. Studies are going on in search of more details about the mechanism of acceleration performed by binary systems.

SCHEME 16. Schematic representation of the action of binary accelerators.

The synergistic activity of two or more different accelerators arise from the interaction of the accelerators to form new intermediate compounds which again actively take part in the vulcanization reaction leading to enhancement of crosslink density and the rate of vulcanization reaction.105 Further investigations106-115 with binary accelerator systems have provided more valuable information regarding the mechanism of their action. Moore et al.116 made investigations on the TMTD-TU binary accelerator system. A novel mechanism was suggested (Scheme 17) to explain the synergistic activity. This theory recognizes the importance of the polysulphidic intermediates (A) formed during the vulcanization process, which subsequently react with the rubber chain to yield further intermediates (B). These intermediates finally react to yield sulfurated crosslinks. XSm X + (m 1)XSSX ZnO
ZnO

m2 (XO)2 Zn + (XS)2 Zn 2 1 (XS)2 Zn + H 2 O 2 1 (XS)2 Zn + H 2 O 2

(1)

RH + XSm X RSm-1X + RH + RSm-1X RSm-2 R +

ZnO

(2) (3)

SCHEME 17. Mechanism of the action of TMTD-Thiourea binary system.116

In the above mechanism, X represents (CH3) 2 N-C = S) and RH is the rubber hydrocarbon. The crosslinking reaction shown in Step 3 follows from the products of Step 2 which itself

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requires the thiuram polysulphides (A) produced in reaction Step 1. Hence, it follows that any acceleration of the latter must also lead to a corresponding increase in the overall vulcanization rate. Thiourea and its derivatives have been used as accelerators in dry rubber and lattices. In the works of Mathew et al.110-115 the accelerating activity of several thiourea derivatives were compared. Dithiobiurets of varying nucleophilicity were synthesized and compared. Mini et al.115 has used amidino thiourea as a binary accelerator. In these studies attempts have been made to optimize the amount of the new accelerator based on the physical properties of the resulting vulcanizates. The nucleophilic nature of thiourea and its derivatives is suggested as responsible for the cure activating nature of those binary accelerators. Binary accelerators are expected to improve the cure rate by improving the crosslinking in rubber. This could be responsible for the improvement in mechanical properties. In our studies we have investigated the accelerating effect of 1-phenyl- 2, 4- dithiobiuret (DTB) as a binary accelerator with sulphenamides in Natural Rubber.117-119 From our studies we found that an optimum concentration exists in the binary accelerator combination. Excellent mechanical properties are shown at this concentration. Based on the observed cure activation and enhancement in properties we have proposed a mechanistic pathway for the action of this binary accelerator combination in NR, SBR and their blends.120-122 In the proposed pathway the nucleophilic character of DTB facilitates the breakage of Zn-S bond of the zincperthiomercaptide complex.

SCHEME 18. Proposed mechanism showing the curing in presence of DTB.120

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The modulus and strength of materials with flexible chain polymers can be increased by orientation and crystallization of polymer chains. In plastics and fibers, molecular chain orientation is maintained after processing as the chains are frozen by glassy state or crystallization. On the other hand, in rubbers, orientation produced during simple processing will decay after processing. Double network rubber refers to an elastomer that has been crosslinked twice, the second time while in a deformed state. The deformation employed is simple tension, (it doesnt have to be) resulting in a rubber whose final length exceeds the length after the initial, isotropic crosslinking. The ratio of these two lengths, referred to as residual strain, does not uniquely define a double network elastomer. A given residual strain can be achieved with different combinations of strain and crosslinking apportionment between the two networks.123 Double network rubbers offer a route to obtain superior mechanical properties, in that they may allow circumvention of the usual compromise between stiffness and strength. Santangelo and Roland123 have shown that gum natural rubber double network crystallizes at lower strain and can have enhanced tensile strength and fatigue life compared to conventional single networks. Preparing double networks or composite networks could produce rubber vulcanizates with permanent chain orientation. Double networks can be viewed as interpenetrating networks in which the same chain segments belong to both networks and more importantly the component networks are oriented. It is this orientation that gives rise to enhancement and anisotropy in properties.124-126 The expectation, borne out by experiment is that the modulus of a double network rubber will differ from the modulus of the compounding isotropic elastomer. At higher residual strains, the equilibrium modulus is higher. Mott and Roland126 have studied mechanical and optical behavior of doublenetworked rubbers. The network formed when a rubber is crosslinked will have an equilibrium set of chain configurations. These configurations are usually associated with a macroscopic state of zero strain, since this corresponds to a condition of zero stress.127 When the rubber is cured away from elastic equilibrium, configurations prevailing during crosslinking will shift the subsequent equilibrium state away from zero strain.128,129 However, when the crosslinking reaction takes place in a deformed state, an anisotropic crosslink network will be produced.130 The properties of elastomeric network depend not only on the density of junctions but also on the distribution and orientation of the chains when the junctions are formed. Double networks can also arise spontaneously via chain scission131 and via strain-induced crystallization132 or in the presence of reinforcing fillers.133,134 The strength of oriented networks is found to depend on the extent of orientation and crosslinking. The strain-induced crystallization of natural rubber imparts the superior strength to it. This is accomplished by the crystallization induced due to orientation. Studies have to be made in order to find whether any effect of crosslinking would help to improve the strength of double networks. X. CHARACTERIZATION OF NETWORKS Different methods are available for characterization of rubber networks. The important methods are: (i) swelling method; (ii) freezing point depression method; (iii) stress-strain method; and (iiii) NMR measurements. Swelling of vulcanizates in solvents has been proved to be an effective method to determine the chemical crosslink density. Flory-Rehner theory135 is used for the determination of molecular weight between crosslinks. Flory Rehner equation can be applied to the results of swelling of

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rubber in suitable solvents. -[ln(1-Vr) + Vr + Vr2] = [Vs (Vr)1/3]/ Mc (4)

where Vr is the equilibrium volume fraction of rubber in swollen gel, the density of rubber, an interaction constant characteristic of rubber and swelling liquid and Vs the molar volume of the swelling liquid and Mc is the molecular weight between crosslinks.136 Interpretation of crosslink density with this equation requires the interaction parameter. This parameter is influenced by factors which affect chain configuration. Treatment of the vulcanizates with different thiols137 cleave the mono, di and polysulphidic crosslinks preferentially. This helps to find the relative proportion of crosslinks. It has long been known that an anomalous freezing point depression of the swelling solvent in swollen gels was observed and that the magnitude of the depression was closely related to the degree of crosslinking and or the structure of swollen gels.138 The stress-strain behavior of rubber like networks is influenced by contributions of constraints caused by the uncrossability of the network chains. Using theoretical results based on the tube approach to polymer melts and networks,139 a well-founded separation of crosslink and constraint contributions to the stress-strain behavior can be achieved and a reliable method for the evaluation of the network parameters can be developed. The Mooney equation140 is used for calculating the crosslink density from stress-strain data. It was then modified by Rivlin and Saunders.141 = [RTA0]/Mc {-1/2} (5)

where '' is the force to extend a sample of cross-sectional area 'A0' to extension ratio '',(ratio of extended to original length of the sample specimen) '' is the density, 'R' is the gas constant and 'T' is the absolute temperature. A recent promising approach to direct analysis of the crosslink structure and distribution in sulfur vulcanizates was the application of solid-state C13 NMR spectroscopy.61,142-147 In a work on unaccelerated sulfur vulcanization, a number of signals were also assigned to monosulphidic crosslinks on the basis of calculated chemical shifts of proposed structures.148 Chemical shifts differences between disulphidic and trisulphidic crosslinks are of the order of 0.1 ppm. Crosslinking results in broadening of the peaks. Recent studies149,150 have shown that C13 highresolution solid state NMR spectroscopy is a valuable method to analyze the formation of polysulphidic and monosulphidic crosslinks at various sites on the monomer unit in NR. XI. CONCLUSIONS A detailed survey on the crosslinking in elastomers has been made in this review. The different methods of crosslinking have been thoroughly reviewed giving special attention to accelerated sulfur vulcanization. Mechanisms put forward to explain the vulcanization process are discussed. The role of activators and the effect of fillers are discussed. The property of vulcanizates depends mainly on the number and type of crosslinks present in it. The different types of crosslinks formed during the vulcanization process and their behavior with respect to the amount of accelerator and sulfur present are discussed. Binary accelerators are widely used in industries so as to obtain better end-use properties and to reduce the time required for vulcanization. The mechanism of some binary accelerator systems found in literature is discussed. Formation of double networks in elastomers helps to preserve the orientation of hydrocarbon chains. This method could revolutionalize the elastomer technology since this method offers better strength and modulus to the resulting vulcanizates. Various methods available for characterization of networks formed and estimation of crosslink density are also discussed.

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