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Introduction
Rubber processing chemicals are used extensively to impart performance and processability to rubber and the products made thereof. These chemicals are typically organic compounds but several inorganic materials are also included under the umbrella of rubber chemicals. The rubber compound is described as a mixture of one or more rubber polymers (elastomers) with a combination of one or more of llers, oils, and rubber chemicals (see RUBBER COMPOUNDING). The compound, once vulcanized, provides technologically useful properties, such as may be applied to tires, hoses, belts, tracks, and a variety of mechanical goods. Vulcanization systems and antidegradants are the two dominant classes of rubber chemicals, given that the largest class of rubbers used in industry (the socalled general-purpose rubbers) require cross-linking by sulfur or other curative to provide meaningful performance, and require protection from oxygen and ozone to provide meaningful service lifetimes (see ANTIOXIDANTS). The present article reviews several recent developments in the eld of rubber chemicals of particular interest to practitioners. These topics include (1) non-nitrosamine curatives as a response to health concerns and legislation (2) reversion-resistance curatives to enhance product durability and support higher temperature cures (3) silica-to-rubber coupling agents to support expanded use of silica ller (4) nonstaining and persistent antidegradants for enhanced performance

Non-Nitrosamine Curatives
General-purpose rubbers are those made from the monomers isoprene, 1,4butadiene, and styrene. Each isoprene and butadiene unit contributes one
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

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carboncarbon double bond to the nal structure, plus a number of allylic hydrogen sites, which are the reactive centers for sulfur vulcanization. In sulfur vulcanization, polymer chains are connected by covalent bonds (cross-linked) of sulfur atoms or chains of sulfur atoms attached to the allylic positions of individual chains. The chemical components necessary for this process include the polymer(s) with allylic hydrogens, elemental sulfur or a source of sulfur, plus chemical promoters called accelerators and activators. In current practice, the curative promoter package typically employs a primary accelerator, one or more secondary accelerators, and zinc oxide and fatty acid (or a zinc fatty acid salt) activator. Several excellent reviews have been written detailing the chemistry involved between these ingredients and the inuence they have on the development of nal vulcanizate properties (19). The benets of an optimized sulfur vulcanization system are several: economical, good kinetics, and good performance. Economical in that sulfur is very inexpensive, and typical accelerators and activators are also low cost commodity chemicals. Good kinetics in that rapid cross-linking is achievable in a matter of a few minutes at usual curing temperatures of 130180 C but that the rubber compound can withstand many minutes at processing temperatures often in the range of curing temperatures (ie, 100140 C) before the onset of cross-linking. The undesirable premature cross-linking of polymer chains in the processing step is called scorch; the ability of the vulcanization system to withstand the heat of processing without premature cross-linking is called scorch safety. This attribute of delayed action (scorch safety) with fast cure is unique to accelerated sulfur vulcanization, and allows for safe and rapid mixing and fabrication of rubber compounds and parts coupled with rapid cure. Good performance derives from the structure of the cross-links as a blend of sulfur chain lengths, from one sulfur atom (monosuldic) to two (disuldic) to three or more, up to eight and more (polysuldic). The differing chain lengths impart differing physical characteristics: shorter chain impart heat stability and resistance to permanent set, longer chain lengths impart tear resistance. The ratio of sulfur to primary accelerator controls cross-link length distribution, and thus can be used to tailor physical properties, even as the concentration of curatives controls cross-link density, itself a dominant contributor to compound properties such as modulus, strength, hardness, and abrasion resistance. Figure 1 illustrates the curing process as measured by a rheometer. The rheometer follows the development of cure state as a function of time. Vulcanization characteristics such as minimum torque M L (a measure of compound green viscosity), onset of cure (T1 pt rise), M H (a measure of maximum cure state reached), and T90% cure (time required to reach 90% cure state) are valuable properties dening cure behavior. Likewise the rheometer cure prole can be broken into three regions of interest, an estimate of scorch safety, an idea of what the cure state development looks like during the cross-linking phase, and how the cross-linked vulcanizate network matures with additional heat. Primary Accelerators. The primary accelerator of choice is a mercaptobenzothiazole sulfenamide of general chemical structure (1). Specic examples of this class are listed in Tables 1 and 2.

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Fig. 1. Example of rheometer cure curve illustrating major cure attributes. To convert dNm to in lb, multiply by 0.885.

The sulfenamide S N bond strength controls the scorch safety and cure rate. The more labile this bond, the more readily the active cure promoter mercaptobenzothiazole is released at the onset of the cross-linking process. A family of sulfenamides has been developed to span a range of cure rates. Common historical members of this class are shown in Table 3, arranged from fast curing to
Table 1. Nitrosamine-Generating Sulfenamides Chemical name 4-Morpholinyl-2-benzothiazole disulde N-Oxydiethylene benzothiazole-2-sulfenamide N,N-Diisopropylbenzothiazole-2sulfenamide Abbreviation MBSS Chemical structure

MBS

DIBS

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Table 2. Non-Nitrosamine-Generating Sulfenamides and Sulfenimides Chemical name N-Cyclohexyl benzothiazole-2-sulfenamide Abbreviation CBS Chemical structure

N-tert-Butyl-2-benzothiazole sulfenamide

TBBS

N-Dicyclohexyl-2-benzothiazole sulfenamide

DCBS

N-tert-Butyl-2-benzothiazole sulfenimide

TBSI

slow, based on primary amines of weakening base strength (ie, a to b to c) and/or increasing steric hindrance (ie, c to d to e) (10). German legislation targeting elimination of stable and volatile nitrosamines as by-products of vulcanization became effective in September 1988 as the Technical Rules for Hazardous Materials TRGS 552 (11,12). It recognized 11 nitrosamines as carcinogenic and set industry limits to exposure. Nitrosamines are potent carcinogens in laboratory animal testing, and are suspect human carcinogens. The amines released from sulfenamide accelerators in the necessary early step of vulcanization can combine with nitrogen oxides (NOx ) in the atmosphere to produce nitrosamines. Primary amines form unstable nitrosamines that immediately decompose and do not constitute a health risk, whereas secondary amines produce stable nitrosamines by this process, (R)2 N N O). The
Table 3. Sulfenamide Structure Inuence or Cure Rate and Scorch Safety

a CBS

b TBBS

c MBS Morpholine Base strength pK a 8.3

d DIBS

e DCBS

Cyclohexlyamine t-Butylamine Base Base strength pK a 10.7 strength pK a 10.5

Diisopropylamine Dicyclohexylamine Base strength Base strength pK a 11.0 pK a 11.3 Steric hindrance predominates Steric hindrance predominates

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Table 4. Comparison of sulfenamide cure properties normalized to MBSa,b Cure time (T90%) Nitrosamine-generating MBS 100 MBSS 27% shorter DIBS 7% longer Non-nitrosamine alternatives CBS 27% shorter TBBS 15% shorter DCBS 31% longer Scorch time 100 45% shorter 10% longer 29% shorter 22% shorter 30% longer

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a Base compound: SBR, 50; polyisoprene, 50; N299 carbon black, 50; naphthenic oil, 28; stearic acid, 1; ZnO, 3; antioxidant, 1; sulfur, 1.75; sulfenamides at an equal molar level (4.74 mmol). b Samples tested at 150 C.

immediate effect of the legislation was thus to target for elimination from vulcanization systems of all sulfenamides made from secondary amines able to form 1 of the 11 listed nitrosamines. The accelerators given in Table 1, MBS and MBSS (derived from morpholine) and DIBS (derived from diisopropyl amine), had to be replaced at least for European markets. Compromise cure systems based on the faster and slower curing nonnitrosamine sulfenamides listed in Table 2 have been recommended as alternatives (1214). The sulfenimide variant N-tert-butyl-2-benzothiazole sulfenimide (TBSI) was also produced to satisfy this need (15). As with DCBS the large steric hindrance associated with the sulfenimide slowed the reaction kinetics, resulting in slower cures and extended scorch safety. Table 4 (16) makes a comparison of cure properties for the sulfenamides listed in Tables 1 and 2 relative to MBS. No exact replacements are available for MBS, MBSS, and DIBS, but DCBS can serve as an alternative for MBS and DIBS and CBS and TBBS can serve as alternatives for MBSS. Proper adjustments in sulfur and sulfenamide levels can provide similar cure performance. CBS and TBBS also satisfy the need in providing rapid curing kinetics where required. Additional scorch protection, if needed, can be obtained by application of the widely used scorch inhibitor N-(cyclohexylthio)phthalimide (17). Secondary Accelerators. Even bigger changes have come to the secondary curative segment. Three classes of chemicals served historically as secondary accelerators, useful in low levels to speed up sulfenamide cures: the thiuram (2) and dithiocarbamate (3) types, and the guanidine type (4). Specic examples for these classes are listed in Tables 5 and 6.

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Table 5. Nitrosamine-Generating Thiurams Chemical name Tetramethylthiuram disulde Abbreviation TMTD Chemical structure

Tetramethylthiuram monosulde

TMTM

Two workhorse members of the thiuram class, particularly active in cure rate as well as economical, are TMTD and TMTM (R= methyl, x = 2 and 1, respectively, in 2). Both TMTD and TMTM are stable nitrosamine generators, as they liberate the secondary amine, dimethyl amine, during vulcanization (12,13). Replacements for these rubber chemicals has been a target of considerable technical effort in the rubber industry. Several candidates have emerged, each with its own attributes. None is a direct substitute for either TMTD or TMTM but several have proven
Table 6. Low or Non-Nitrosamine-Generating Thiurams, Dithiocarbamates, and Guanidines Chemical name N,N,N ,N Tetraisobutylthiuram disulde Abbreviation IBT Chemical structure

N,N,N ,N Tetraisobutylthiuram monosulde

IBM

Tetrabenzylthiuram disulde

TBzTD

Zinc dibenzyldithiocarbamate

ZBEC

Diphenylguanidine

DPG

Di-o-tolylguanidine

DOPG

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Table 7. Comparison of Cure Properties Relative to TMTDa of Non-Nitrosamine Secondary Accelerator Alternativesb,c Cure time (T90%) TBzTD (eq molar, 0.67 phr) IBT (eq molar, 0.47 phr) ZBzDC (eq molar, 0.76 phr)
a At b Base

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Scorch time 33% longer 33% longer Equal

18% longer 18% longer 6% longer

an equal molar level (0.30 phr). compound: SBR, 50; Polyisoprene, 50; N299 carbon black, 50; naphthenic oil, 28; stearic acid, 1; ZnO, 3; antioxidant, 1; sulfur, 1.75; sulfenamides at an equal molar level (4.74 mmol). c Samples tested at 150 C.

useful in non-nitrosamine cure packages. Cure properties of likely replacements are compared to TMTD in Table 7 (16). As secondary curatives, both TBzTD and IBT provide slightly longer cure times but have the advantage of prolonging scorch safety. A much closer match to TMTD is ZBzDC in both cure time and scorch time. When used at equal molar concentrations, signicantly more weight of the non-nitrosamine replacements are required versus TMTD. TBzTD and ZBzTD do, in fact, generate stable nitrosamines from the secondary amine dibenzyl amine; however, this nitrosamine is nonvolatile and is not readily released from the vulcanized product into the atmosphere. It is also considered noncarcinogenic (18). Therefore, these materials are considered nonnitrosamine in usage. IBT likewise generates a stable nitrosamine but its level has been claimed to be 100 times less than TMTD (19). Sulfur Donors. A fourth class of sulfur vulcanization chemicals has been affected by the move to non-nitrosamine generators: the sulfur donors. These are organic chemicals which have a relatively high level by weight of sulfur atoms that are able to be donated in the vulcanization process to create sulfur crosslinks. Elemental sulfur is the material of choice as a source of the sulfur atoms which create these cross-links, but some articles cannot tolerate free sulfur for requirements of color, solubility, or performance. With regard to solubility, compounds which require a very high cure state may require more sulfur than can be supplied as elemental sulfur. Sulfur has a solubility limit of about 1 part per hundred rubber at room temperature (20) and at higher levels will bloom, that is, crystallize out of solution onto the rubber compound surface, where it can be detrimental to processing, particularly to tack, the ability of rubber to stick to itself or other rubber component in the building of a composite product. So-called insoluble sulfur has been developed as an alternative form of elemental sulfur: it has a polymerized long-chain structure ( Sx ) as opposed to crystalline sulfur (S8 rings) (21,22). Insoluble sulfur can be substituted for crystalline sulfur and can be used at levels well above the solubility limits without bloom, in theory. In practice, however, insoluble sulfur will revert to soluble sulfur at the temperatures often attained in mixing and shaping rubber components, and thus can result in bloom in processing (23). Sufce it to say that some alternative forms for sulfur are sometimes needed for processing.

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Table 8. Nitrosamine-Generating Sulfur Donors Chemical name 4,4 -Dithiodimorpholine 4-Morpholinyl-2-benzothiazole disulde N-OxydiethylenethiocarbamoylN -oxydiethylenesulfenamide Tetramethylthiuram disulde Abbreviation DTDM MBSS Chemical structure

OTOS

TMTD

Likewise, for performance, sometimes a sulfur donor is needed as well. Elemental sulfur gives rise to variable cross-link lengths, regulated to some extent by sulfur-to-accelerator ratio. In some applications, particularly those which require very high temperature and or oxidative stability, one may need a preponderance of cross-links of very low rank, mostly monosuldic. For this purpose, organic sulfur donors may be useful (24). Four conventional sulfur donor curatives employed historically are all nitrosamine generators, derived from either morpholine or dimethylamine, as shown in Table 8. The industry has developed non-nitrosamine substitutes, as shown in Table 9. As discussed earlier, TBzTD is used primarily as a secondary accelerator to further accelerate cure while offering good scorch protection. Similarly, IBT performs like TBzTD. CLD appears to be as active as DTDM in donating sulfur evidenced by its ability to generate the same cure state as DTDM when used at equal available sulfur levels. CLD however can introduce more scorch. These attributes are illustrated in Table 10 (16). TESPT has found value as a sulfur donor in what has been described as an equilibrium cure, or EC for short (25). The concept relies on the slow release of sulfur from TESPT during the curing process to control the reversion process illustrated in the rheometer chart of Figure 1. Rhenocure SDT/S is a thiophosphite and thus not amine-based. It can be used where high levels of short cross-links of the mono- and di-type are desirable for long-term heat age stability (26). The Vultac class of Table 9 has found uses in diene rubbers as partial or total replacement for sulfur (27). Benets claimed include improvements in aging properties and promoting covulcanization of blends. Table 10 illustrates the sulfur-donating ability of the Vultac class by showing Vultac 7 provides a similar cure state as sulfur when used as a total replacement. One drawback is the introduction of scorch. The rubber chemist has reacted vigorously to the challenge of eliminating volatile nitrosamine-generating chemicals in the workplace, even though many had been xtures of the sulfur vulcanization process. Non-nitrosamine primary and secondary accelerators and sulfur donors are now available and used extensively.

Table 9. Non-Nitrosamine Sulfur Donors Chemical name Tetrabenzylthiuram disulde Abbreviation TBzTD Chemical structure

N,N,N ,N -Tetraisobutylthiuram disulde

IBT

Caprolactam disulde

CLD

Bis-(3-triethoxysilylpropyl)tetrasulfane

TESPT

585 Bis-(O,O-di-2-ethylhexyl-thiophosphoryl)polysulde Rhenocure SDT/S Alkylphenol disulde oligmer Vultac

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Table 10. Activity of Sulfur Donors Versus Free Sulfur Compared Using a Rheometer Cure Tracea,b Sulfur donor Sulfur donor, phr Available sulfur, phr Delta Tq , dNm (cure state) T90%, min T1 pt rise, min Sulfur 1.0 1.0 19.2 21.7 9.0 DTDM 3.7 1.0 26.4 36.3 12.3 CLD 4.5 1.0 26.6 19.7 5.7

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Vultac 7 3.3 1.0 19.6 21.5 4.0

a Base compound: SBR, 50; polyisoprene, 50; N299 carbon black, 50; naphthenic oil, 28; stearic acid, 1; ZnO, 3; antioxidant, 1; CBS, 1.25. b Samples tested at 150 C.

Reversion-Resistance Curatives
Concomitant with the several benets of sulfur vulcanization described above are certain deciencies owing to the complexity of the formation of, and instability of, the sulfur cross-link system. Reversion is dened as the anaerobic (nonoxidative) degradation of sulfur-cured vulcanizates which results in a loss of compound performance. This phenomenon is generally associated with loss in cross-link density via thermal degradation of sulfur cross-links caused by heat and/or extraneous accelerator fragments (28,29). It occurs during overcure conditions, elevated cure temperatures (30), and severe service conditions (31). Reversion is most pronounced for natural rubber, which tend to lose cross-links and soften with heat and aging, whereas synthetics (polybutadiene, styrene-butadiene copolymers (qv)) tend to add cross-links and harden with heat and aging (see BUTADIENE POLYMERS). Overcure, elevated cure temperatures, and severe service are all growing trends industrially, particularly for large tires as are used in over-the-highway trucks, off-the -road equipment, and aircraft tires, all of which also use a lot of natural rubber. Manufacturing efciencies promote higher temperature cure conditions for better throughput. Tires are cured from heat applied at the outside (mold) and inside (bladder) surfaces. For tires with thick rubber cross sections, and given the poor thermal conductivity of rubber, a temperature gradient is produced from surfaces to interior. The surfaces may see signicantly more total heat history than the interior. This may be so even allowing for slow cooling of the interior and continued cure of the inside after the tire is removed from the mold. Cure systems are tailored for individual components to try to balance the cure prole across the cross section, but a given thick tread may still be subjected to a broad range of heat inputs, so that only a portion of that one component will be optimally cured while a portion will be overcured. (No portion can be undercured without generating a useable product. Indeed, cure conditions are set so as to require all portions of the tire to achieve a minimum acceptable level of cure.) Tires, like other rubber goods, perform to ever higher levels: mileage, service life, and service conditions. Still, high operating temperatures and loads may impart reversion. Thus, there has been a growing interest in chemicals which inhibit the tendency to reversion of sulfur-cured natural rubber.

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Fig. 2. Reversion during cross-link formation.

Reversion can occur during cross-link formation (high temperature cure) and after cross-link formation (overcure or in service). These are shown pictorially in Figures 2 and 3. For processes which contribute to reversion seen during cross-link formation, several pathways can be envisioned contributing to loss in ultimate cure state development. As Figure 4 shows, these pathways most likely involve desulfuration or decomposition of intermediate polythio-sulfurating species or the polythio-benzothiazole cross-link precursor formed by the heat of the curing process. This decomposition pathway effectively reduces the concentration of active cross-linking agents resulting in lower cross-link density. Also at very high temperatures as cross-links are forming, they may, in a similar manner, be immediately desulfurated and decomposed. In the development of maximum cure state, the initial cross-link structure, which may be high in polysuldes, goes through a rearrangement process in which the Zn-accelerator complexes, which promote curing, extrude sulfur from the initial cross-links and reutilize the extruded sulfur to form additional cross-links (29). After the maximum cure state is established with a desired proportion of polysulde, disulde, and monosulde cross-links for compound performance, the network cross-link structures will continue to evolve with additional heat introduced

Fig. 3. Reversion after cross-link formation.

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Fig. 4. Reversion pathways during cross-link Formation.

during an overcure situation (30) or during the service life of the compound (31). Figure 5 shows that this reversion process involves loss of polysulde cross-links with the formation of more mono and disulde types and nally decomposition of the mono and disuldic types yielding modications in the polymer backbone. Modications would include carboncarbon double bond rearrangement, growth of diene and triene structures, and isomerization of existing double bonds. For

Fig. 5. Cross-link network maturation and reversion with heat from curing or high temperature service.

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Fig. 6. Effect of temperature on cure rate and cure state. Base compound: NR, 100; N347 carbon black, 50; naphthenic oil, 8; stearic acid, 1; ZnO, 3; antioxidant, 0.75; sulfur, 3; TBBS, 0.75. To convert dNm to in lb, multiply by 0.885.

natural rubber, this results in creation of some trans double bonds in the otherwise all-cis structure. Additionally, unproductive (nonload bearing) cyclic suldes increase in number in reversion: sulfur attached by both of its valences to neighboring segments of the same polymer chain. Zinc sulde is produced as a stable but inactive by-product of both vulcanization and reversion. All these changes are followed by a drop in cross-link density (3235). The effect of cure temperature on the cure kinetics and cure state prole of a simple carbon black lled, sulfenamide/sulfur cured natural rubber compound is shown in Figure 6 (16). As shown in the growth of the cure state, an article which would require 110 min to cure to its maximum cure state at 125 C can be cured at 135 C in 50 min, at 150 C in 18 min, at 165 C in about 7 min, and at 182 C in about 3 min. However, the maximum state of cure achieved keeps dropping as cure temperature increases. The same process continues beyond optimum or maximum cure state if cure is allowed to continue (overcure). Again, as seen in Figure 6, the cure state now drops from the maximum to attain a lower plateau. This decline is faster and more pronounced as cure temperature increases. The window of time for near-optimum cure narrows, and the regime of overcure grows. Physical manifestations of reversion, beyond loss in cure state, include (1) (2) (3) (4) (5) (6) (7) loss in resilience greater heat buildup loss in abrasion resistanec loss in wire adhesion initial increase then large loss in tear and fatigue resistance loss in modulus and hardness loss in tensile strength

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How much of the decay in properties is due to cistrans isomerization, cyclic suldes, growth of dienes, reduction in sulfur rank, and reduction in total crosslink density is a subject of ongoing research, but all processes likely contribute. Because of the large demands put on rubber compounds to address issues of increased productivity via high cure temperatures or increased service temperatures brought about by overloads and high speeds, reversion-resistance chemicals are now becoming part of the compounders arsenal to combat reversion issues. Reversion-resistance chemicals operate by one of two mechanisms: (1) Relink polymer chains to maintain cross-link density. These may be via sulfur or non-sulfur covalent bonding. (2) Form heat stable cross-links that are more resistant to scission than conventional sulfur cross-links. These may or may not contain sulfur. Several rubber chemicals have been developed to inhibit or compensate for sulfur cross-link reversion. Several of these are shown in Table 11. MPBM operates under the mechanism of forming heat-stable cross-links. It has been reported that the network structures formed with MPBM are not prone to revert (36,37) and offer heat resistance during high temperature curing and overcure. Detailed mechanistic studies have found the major reactions occurring during vulcanization in sulfur-containing systems to be 1,2-cross-linking of the imide double bond across polymer chains generating a heat-stable carbon carbon cross-link. Additional reactions included homopolymerization, copolymerization giving multiple cross-links, and Michael addition reactions with 2mercaptobenzothiazole and amines derived from sulfenamide curatives as well as other extraneous sulfur species formed during cure (38). BCI-MX also provides its heat-resistant performance by the formation of carboncarbon cross-links but does it by the mechanism of relinking polymer chains to maintain cross-link density (38,39). The relinking mechanism takes place only during reversion when sulfur cross-links are broken and in their place cyclic suldes, dienes, and trienes are formed along the polymer backbone (16,35). The structural differences of BCI-MX from MPBM prevent it from undergoing the reactions discussed about MPBM. Instead, the citraconimide group undergoes a DielsAlder addition reaction with these chain modications to relink polymer chains and compensate for the lost, reverted, sulfur cross-links (3941). For BCIMX to be effective, some initial reversion must take place. This is nicely illustrated in Figure 7 (16) which shows the reversion characteristics of BCI-MX versus the same compound with no BCI-MX added. As discussed earlier, TESPT functions as a reversion-resistant chemical by the slow release of sulfur to compensate for cross-links lost (25). It has also been found that TESPT leads to higher levels of monosuldic cross-links (42), which yields improved reversion (thermal aging) resistance (43,44). Both HTS and BDTCH can be classied as proceeding through the mechanism, which forms heat-stable cross-links that are more resistant to scission. The cross-link has been referred to as a hybrid cross-link in which a hexylmethylene dithio group Sn [(CH2 )6 Sx ]k is the bridging group between two polymer chains (4549). In this scheme, k is presumed to be small. At high sulfur

Table 11. Anti-Reversion Agents Chemical name N-N -m-phenylenedimaleimide Abbreviation MPBM Chemical structure

1,3-Bis(citraconimidomethyl) benzene

BCI-MX

Bis(3-triethoxysilylpropyl)tetrasulfane

TESPT

591 Hexamethylene bis-thiosulfate disodium salt dihydrate Mixture of zinc salts of aliphatic and aromatic carboxylic acids HTS Activator 73 R = aliphaticaromatic mix 1,6-Bis(N,N-dibenzylthiocarbamyldithio)hexane BDTCH Trifunctional acrylate coagent Sartomer SR534

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Fig. 7. Example of reversion-resistant agent effect on reversion (cure temperature 165 C). Base compound: NR, 100; N347 carbon black, 50; naphthenic oil, 8; stearic acid, 1; ZnO, 3; antioxidant, 0.75; sulfur, 3; TBBS, 0.75. To convert dNm to in lb, multiply by 0.885.

levels both n and x would be greater than 1. As reversion proceeds, the number of n and x sulfur atoms would be reduced to one resulting in a hybrid cross-link with monosulde linkages for thermal stability and the hexylmethylene bridge to add exibility to the cross-link for improved tear and fatigue properties. Figure 7 illustrates the reversion-resistant capabilities the hybrid cross-link can offer. Since Activator 73 A is a mixture of zinc salts of linear aliphatic and aromatic carboxylic acids (50), it would be expected that the mechanism of action would be similar to zinc stearate, which can extract sulfur from polysuldic cross-links and reuse that sulfur to generate more cross-links (51). Ultimately this would result in a network structure high in monosuldic content (42). Trifunctional acrylates, such as Sartomer SR534, have been found to provide reversion-resistant protection (52). Test results of the three trifunctional acrylate and methacrylate monomers, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate, versus BCI-MX prove interesting (53). Rheometer traces of cure development and reversion characteristics with these trifunctional monomers duplicated BCI-MX behavior even to the point of having initial reversion chemistry occurring before they became active. This would suggest these materials operate by the same mechanism as BCI-MX. To conclude this section, the rubber chemist has vigorously pursued materials and means to inhibit and counteract the tendency to reversion, so as to permit higher temperature cures, buttress rubber goods against overcure, and permit increasingly greater operating conditions and service lifetimes.

Silica-to-Rubber Coupling Agents

Rubber must be cross-linked to be technologically useful, hence the emphasis historically and in the two sections above, on chemicals to facilitate and optimize this process. However, even cured rubber is practically of little value unless the rubber

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is reinforced by a particulate ller (see FILLERS). Cured, unlled (gum) rubber has very low tensile strength, and poor tear and abrasion resistance. Contrast a pencil eraser or a rubber band to a tire tread or transmission belt, for example. The early tires and rubber goods were lled with inert llers such as zinc oxide. The discovery about a century ago that carbon black (qv) greatly enhanced rubber performance began the evolution of tough durable goods made from rubber. It turns out that very few other substances reinforce rubber as does carbon black. None do at the same cost. Hence, even today, carbon black is the dominant reinforcing ller for rubber, even as talc, calcium carbonate, kaolin clay, and other lower cost, nonreinforcing llers retain uses in selected nontire applications. The characteristics shared by reinforcing llers are few but vital: (1) Small hard particles, with diameters upon ultimate dispersion below micron size (2) Ability of said particles to disperse in the rubber medium (3) Ability of said particles to interact with themselves, so as to produce an independent ller network, which interpenetrates with and synergistically supports the polymer network. This attribute is called ller/ller interaction. (4) Ability of said particles to interact with the polymer matrix. This attribute is called polymer/ller interaction.

Carbon Black. Carbon black (qv) has all of these characteristics. Carbon black is amorphous elemental carbon with a graphitic-like microcrystalline substructure (54). The furnace process rubber grades come in a range of particle and aggregate sizes and shapes, with reinforcing grades in the 10100 nm ultimate particle diameters. Carbon black disperses very well in general-purpose rubbers, with which it shares an organic chemical nature. It has a strong self-afnity; once a sufcient loading is achieved in a rubber matrix, it imparts electrical conductivity to the composite via the ller network, for example. This ller network is also responsible for the enhanced low strain dynamic stiffness of lled rubber, and the loss (recoverable upon relaxation) of this stiffness with strain. This phenomenon is called the Payne effect (55). Finally, and most importantly, carbon black has a strong afnity to general-purpose rubbers, as a function of attributes built into the carbon black in its manufacture (surface activity) and the unsaturated organic structures of the polymers, such as carboncarbon double bonds, and styrene units. Much has been written on the nature of the carbon black/rubber interaction, which is still not fully understood (selected references include References 5659). One thing is clear: carbon black has a strong afnity to general-purpose rubbers. It is manifest in the simple experiment called bound rubber or insoluble polymer measurement. A sample of uncured rubber, which may or may not be devoid of rubber chemical additives, is admixed with an amount of reinforcing carbon black. The composite is then immersed in a solvent in which the polymer is soluble. Whereas all, or all save any gelled portion, of the unlled rubber dissolves in the solvent, the same polymer, as a carbon black lled composition, produces only a portion of soluble polymer. For a typical recipe containing 3050 parts by weight

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of carbon black per hundred parts rubber, a typical value for the nondissolved or bound polymer might be 2040%. Empirically, the quantity of bound rubber correlates with abrasion resistance, or tread wear for a (subsequently cured) tire tread compound (60). Bound rubber cannot be measured on cured rubber, of course; all but a fraction of a percent will be bound in that case, regardless of the type or amount of ller. But the phenomenon of polymer/ller interaction, measured in the uncured state, carries forward to the cured compound and product, in many toughness and resilience related properties. The search for alternative reinforcing llers to carbon black has continued for decades, and has recently produced one material which offers in selected applications, even greater performance: precipitated silica. Silica. Silica (a mineral with a repeat unit of SiO2 ) is, in its crystalline form, as quartz and sand/sandstone, the most abundant compound on the earths crust. Synthetic silica can be produced by a fumed process via silicon tetrachloride, SiCl4 , or aqueous process, via sodium silicate, itself made from natural silica. The product of the aqueous process is precipitated in an amorphous form, which provides two of the attributes of a reinforcing ller: small particle size and high degree of self-afnity or networking. The self-afnity is due to hydrogen bonding between surface silanol groups (Si OH), which are present in large amount (57 per nm2 ) on the surface. Fumed silica has much fewer surface silanol groups. A representation of the silica surface is given in Figure 8. In the early 1990s, a new generation of precipitated silicas was developed: the so-called highly dispersable silicas (HDS) (6165). This class provides another vital attribute of a reinforcing ller for rubber: easy dispersability at high loadings to submicron sizes. The remaining attribute, polymer/ller interaction, is inherently missing from silica but can be provided by the use of a specic class of rubber chemicals, the silica-to-rubber coupling agents. Silica-to-rubber coupling agents have been known since the 1960s, and had permitted limited use of silica ller, much of this in nonblack mechanical goods and shoe soles. Use in tires was restricted to low levels in skim compounds for wire adhesion and treads for cut resistance. A good review of the state of the technology in the mid-1970s is given by Wagner (66). With the advent of HDS, the ability to disperse silica to levels equal to that of carbon black is now possible for the creation of highly silica-lled rubber compounds. Thus, there has been a revolution in growing use of silica in place of carbon black in tires since the early 1990s, requiring growing use of specic coupling agents, whose number and chemistries have also expanded in this time period. A description of this class of rubber chemicals follows.

Fig. 8. Silica surface chemistry.

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The predominant chemical class of silica-to-rubber coupling agents are the functionalized silane esters of general structure 5 (where typically R = Me, Et, n = 3; R = propylene [ (CH2 )3 ]; and X is a variable function). Many of these were developed in the mid-1970s (67).

The most commonly used silane coupling agents (qv) for rubber are shown in Table 12. All Silane Coupling Agents (qv) work by a twofold bonding mechanism (6870): (1) The silane ester moiety hydrolyzes because of heat and moisture present on the surface of the silica (RO Si HO Si) and the then-formed silanol condenses with a silanol group on the silica surface to produce a siloxane bond linking coupling agent to silica ( Si O Si ). (2) The functional group (X above) on the other end of the coupling agent reacts directly either with the polymer chain or with the vulcanization system so as to provide a covalent bond between the coupling agent (already attached to silica) and the polymer. Step 1, reaction with silica, occurs in the mixing (with heat) of the silica, rubber, and coupling agent. The polymer is as yet uncured and not bonded to the ller. This step is called hydrophobation: the hydrophilic silanol containing surface is converted to a hydrophobic organic modied surface. The silica loses much of its self-afnity by this process, rendering it more compatible with rubber. The Payne effect is reduced and may be nearly eliminated if hydrophobation is thorough. Step 2, reaction with polymer, occurs in the vulcanization step (with heat, after curatives have been added in a lower temperature stage addition). Figure 9 shows the two-step coupling mechanism in the general case. A subclass of silane rubber chemicals exists in which the X function of structure 5 is replaced by an inert alkyl group, creating a silica-reactive but noncoupling process aid, of the general formula 6 (where R = C1 C18 n-alkyl). These materials can be very effective in reducing compound viscosity and the Payne effect (71) but do not themselves provide cured compound reinforcement. A selected series of alkyl silanes is shown in Table 13. Alkyl silanes may be used in conjunction with coupling agent silanes to balance processability and cured performance.

The nature of function X is dependent on the nature of the cure system. Historically, the methacrylate function was used for peroxide-cured rubber and the mercapto function was rst used for sulfur-cured rubber (see a and b in Table 12). Denitive studies of the role of coupling bonds on physical properties

Table 12. Selected Organofunctional Silane Coupling Agents for Silica-Filled Rubber Chemical name Chloro 3-Chloropropyltriethoxysilane Amino -Aminopropyltriethoxysilane H2 N(CH2 )3 Si(OCH2 CH3 )3 [919-30-2] 96 GE Silicones (A-1100) Degussa (VP Si 251) GE Silicones (A-1110) GE Silicones (A-2120) Polyolen, SBR, BR, NR (peroxide cure) CH2 =CHSi(OCH2 CH3 )3 [78-08-0] 44 GE Silicones (A-151) Degussa (VP Si 225) GE Silicones (A-171) Acrylic, nitrile, polyurethane, SBR CH2 CH(O)CH2 O(CH2 )3 Si(OCH3 )3 [2530-83-8] 110 GE Silicones (A-187) Butyl, polyolen, SBR, BR, NR (peroxide) Formula Cl(CH2 )3 Si(OCH2 CH3 )3 CAS no. [5089-70-3] Flash point, C N/A Supplier (trade name) Degussa (Si 230) Polyamide, epoxy, acrylic Polymer application(s) Polychloroprene

-Aminopropyltrimethoxysilane N--(Aminoethyl)- aminopropylmethyldimethyoxysilane Vinyl 596 Vinyltriethoxysilane Vinyltrimethoxysilane Epoxy

H2 N(CH2 )3 Si(OCH3 )3 H2 N(CH2 )2 NH(CH2 )3 SiCH3 (OCH3 )3

[13822-56-5] [3069-29-2]

82 >93

CH2 =CHSi(OCH3 )3

[2768-02-7]

28

-Glycidoxypropyltrimethoxysilane Methacryloxy

 -Methacryloxypropyltrimethoxysilanea CH2 =C(CH3 )CO2 (CH2 )3 Si(OCH3 )3

[2530-85-0]

108

GE Silicones (A-174) Degussa (VP Si 123) Nitrile, SBR, BR, NR (sulfur cure)

Sulfur

-Mercaptopropyltrimethoxysilaneb

HS(CH3 )3 Si(OCH3 )3

[4420-74-0]

88

Bis-(triethoxysilylpropyl)tetrasuldec

[(CH3 CH2 O)3 Si(CH2 )3 ]2 S4

[40372-72-3]

104

Bis-(triethoxysilylpropyl)disulded

[(CH3 CH2 O)3 Si(CH2 )3 ]2 S2

[56706-10-6]

75

3-Octanoylthio-1-propyltriethoxysilanee CH3 (CH2 )6 (C=O)S(CH2 )3 Si(OCH2 CH3 )3 N/A Thiocyanato 3-Thiocyanatopropyltriethoxysilane Miscellaneous N=C=S(CH2 )3 Si(OCH2 CH3 )3 [34708-08-2]

N/A

GE Silicones (A-189) Degussa (VP Si 163) GE Silicones (A-1289) Degussa (Si 69) GE Silicones (A-1589) Degussa (Si 266, Si 75) GE Silicones (NXT) SBR, BR, NR (sulfur cure)

597

N/A

Degussa (Si 264) Polyurethane, phenolic, ureaformaldehyde

-Ureidopropyltrimethoxysilane -Isocyanatopropyltriethoxysilane
a MAS. b MPTMS. c TESPT. d TESPD. e NXT.

H2 N(C=O)NH(CH2 )3 Si(OCH3 )3 O=C=N(CH2 )3 Si(OCH2 CH3 )3

[23843-64-3] [24801-88-5]

99 77

GE Silicones (A-1524) GE Silicones (A-1310)

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Fig. 9. Silane coupling chemistry.

and tire performance of silica-lled tire rubber compounds was done by Wagner using these two coupling agents (72). Several other silanes were originally used to adhere rubber to glass substrates as well as applied to various rubbers with mineral llers such as clays. Some of these are given in Table 12 as well. Despite the performance benets of mercaptosilane, serious drawbacks limited its use in tires: a strong and bad odor, plus a large reduction in scorch safety, resulting in inability to process the rubber. The mercapto group was simply too reactive to the rubber, when combined with sulfur and curatives. Cross-linking would initiate in mixing or extrusion.

Table 13. Selected Alkyl Silane (Silane Ester) Hydrophobating Agents for Silica-Filled Rubber Flash point, C 29 N/A 41 Supplier (trade name) GE Silicones (A-162) Degussa (VP Si 203) GE Silicones (A-137) Degussa (VP Si 208) GE Silicones (A-1630) Degussa (VP Si 216)

Chemical name Methyltriethoxysilane Propyltriethoxysilane Octyltriethoxysilane

Formula CH3 Si(OCH2 CH3 )3 CH3 (CH2 )2 Si(OCH2 CH3 )3 CH3 (CH2 )7 Si(OCH2 CH3 )3

CAS no. [2031-67-6] [2550-02-9] [2943-75-1]

Methyltrimethoxysilane

CH3 Si(OCH3 )3

[1185-55-3]

12 N/A

Hexadecyltriethoxysilane CH3 (CH2 )15 Si(OCH2 CH3 )3 [16415-13-7]

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In the 1970s, the rst step change improvement in coupling agents for sulfurcured rubber, as used in tires, came with the development of the tetrasulde silane, TESPT (see c in Table 12) (67,68). Now, the mercaptan function was protected in the form of a polysulde. To generate the active mercaptan, a sulfursulfur bond cleavage was needed. By analogy to the generation with scorch safety of mercaptobenzothiazole (MBT) by the cleavage of the disulde MBTS, the tetrasulde silane imparted scorch safety yet retained polymer reactivity of the mercaptosilane. TESPT remained the industry standard coupling agent for sulfur cured rubber into the 1990s. With the development of HDS came expanded applications for silica-based compounds, particularly in high performance passenger tire treads which needed a combination of tread wear, low rolling resistance, and good wet traction (73). This combination of performance attributes can be simultaneously optimized to unique levels with silica. Recipes with 50100 phr silica were now permissible and desirable. As silica technology expanded to meet market performance targets, certain processing deciencies grew in importance, and remedies through materials development emerged and continue to do so presently. First, it became apparent that highly silica-lled compounds, even using HDS, required longer mixing times and processed worse than their carbon black counterparts (extrusion, tire building). It became clear that TESPT itself did not have sufcient scorch safety for all operating conditions; the middle sulfursulfur bonds in the polysulde bridge are relatively weak and can be broken, liberating elemental sulfur to impart scorch. TESPT is a known sulfur donor curative, after all. So, the market for TESPD expanded (see c and d in Table 12). The stronger sulfursulfur bonds in TESPD provided extra processability in production while retaining necessary polymer reactivity. The newest sulfur silane coupling agent, NXT (see e in Table 12) (74,75) carries this approach even further. A substituted carbonyl group is used to protect a mercaptosilane during processing and reaction at the silanol end with the silica (7), deprotection occurs during cure, catalyzed by curatives, to release active mercaptan function (8), which, through reactions with the vulcanization system, bonds to polymer (9), as shown below.

The rubber chemist has recognized and reacted to the growing trend to employ silica as reinforcing ller for rubber with development of multiple silane ester coupling agents and alkyl silane process aids for improved processability and performance.

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Nonstaining and Persistent Antidegradants

General-purpose rubbers are susceptible to degradation by atmospheric oxygen (O2 ) and ozone (O3 ). Chemical antioxidants (qv) act to preserve rubber from degradation by molecular oxygen. This degradation is manifest in hardening (cross-linking) for polybutadiene and SBR and initial softening (chain scission) than hardening for polyisoprene rubber (natural or synthetic). All rubbers lose tensile strength and cut and tear resistance due to oxidation as well. Antioxidants inhibit the free-radical autoxidation cyclic chain reaction process via several mechanistic pathways. The primary antioxidants scavenge polymer carbon and hydroperoxy radicals by donation of an active hydrogen. Secondary antioxidants decompose hydroperoxides. A review is available, with attendant references to the historical development of antidegradants and their mechanisms of action in rubber (76). Autoxidation and antioxidant mechanisms have also been reviewed (77,78). The hydrogen-bonded intermediate complex of a hindered phenolic antioxidant with a stable aminoxyl radical (TEMPO), used as a model for a hydrocarbon oxidant, has been isolated and its structure determined, as conrmation of the radical scavenging mechanism (79). The principal classes of primary antioxidants for rubber remain the phenolics (nonblack articles) and amines (black-lled articles). Among the amine types are the substituted diphenylamines, para-phenylenediamines (PPD, (10), where R,R = alkyl or aryl), and polymeric trimethyl-dihydroquinoline (TMQ). Representative phenolic antioxidants are given in Table 14, and selected amine antidegradants are given in Table 15. The majority of tire and mechanical goods made from general-purpose rubbers are protected by the phenolic and amine antioxidants.

Macroscopically, ozonation leads to cracking of the rubber surface and ultimate product failure. A polar mechanism was proposed by Criegee for ozonation of unsaturated hydrocarbon rubbers, with addition of ozone to the carboncarbon double bond followed by decomposition of the intermediate ozonide leading to cleavage of the polymer chain (80). Polymers without carbon bond unsaturation in the backbone do not crack in the presence of ozone. Zhang recently proposed a free-radical mechanism and attributed PPD antiozonant activity to its low ionization potential and ability to quench polymer radicals (81). The PPD class of antidegradants provides by far the best antiozonant protection (for a review of antiozonants, see Reference 82). PPDs inhibit ozone degradation of rubber by multiple mechanisms (76,8385): (1) Migration to the surface of the rubber article (2) Competitive reaction with and scavenging of ozone at the surface

Table 14. Representative Phenolic Antioxidants Used in Rubber Chemical name a. Styrenated phenol Structure CAS no. [61788-44-1] Supplier (trade name) Akcros Chemical (Akcrostab C53-P) Flexsys (Montaclere SPH) Great Lakes Chemical (Anox G2) Goodyear Chemical (Wingstay S) Harwick Standard (Antioxidant SP) PMS Specialties (Prodox 120) RT Vanderbilt (Wingstay S) Sovereign Chemical (AO 47) Sumitomo Chemical (Sumilizer S) Crompton Uniroyal (Naugard SP) Akrochem (Antioxidant 32, 33, 43) CP Hall (Stabiwhite Powder 49-454) Goodyear Chemical (Wingstay C, T) Great Lakes Chemical (Anox T) Inspec Fine Chemicals (Ionol K65, J65) RT Vanderbilt (Wingstay C, T)

b. Alkylated hindered phenol 601 c. Polybutylated bisphenol A [68610-51-5]

BF Goodrich (Goodrite Superlite) RT Vanderbilt (Agerite Superlite) Sumitomo Chemical (Sumilizer NW)

Table 14. (Continued) Chemical name d. 2,2 -Methylene-bis-(4methyl-6-t-butylphenol) Structure CAS no. [119-47-1] Supplier (trade name) Akrochem (Antioxidant 235) Ashland Chemical (Ashland AO 46) Bayer Corp. (Vulkanox BKF) CP Hall (Cyanox 2246) Chemetall (Naftonox 2246) Cytec Industries (Cyanox 2246) Great Lakes Chemical (Lowinox 22M46) Harwick Standard (Stangard PC) PMC Specialties (CAO-5) RT Vanderbilt (Vanox MBPC) Raschig (Ralox 46) Sumitomo Chemical (Sumilizer MDP-S) Akrochem (Antioxidant 12) Ashland Chemical (Ashland AO CL) Goodyear Chemical (Wingstay L) Great Lakes Chemical (Lowinox CPL) PMC Specialties (Ralox LC LC) Raschig (Ralox LC) RT Vanderbilt (Wingstay L) Sovereign Chemical (AOL 600)

e. Butylated reaction product of p-cresol and dicyclopentadiene

[68610-51-5]

602

f. Mixed methylenic bridged adducts of alkylated phenol and dicyclopentadiene

Goodyear Chemical (Wingstay K) RT Vanderbilt (Wingstay K)

g. Tetrakis methylene (3,5di-t-butyl-4-hydroxyhydro

[6683-19-8]

Akrochem (Antioxidant 1010) Ashland Chemical (Ashland AO 610) Akcros Chemicals (Lankromark LE373) Ciba Specialty Chemicals (Irganox 1010) Dover Chemical (Dovernox 10) Great Lakes Chemical (Anox 20) Mayzo, Inc. (BNX 1010) PMC Specialties (Prodox 1010) Raschig (Ralox 630) Sumitomo Chemical (Sumilizer BP-101) Albemarle Corp. (Ethanox 330) Ciba Specialty Chemicals (Irganox 1330)

h. 1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4hydroxybenzyl)benzene

[1708-70-2]

603

Table 15. Representative Amine Antidegradants Used in Rubber Chemical name (abbreviation) a. para-Styrenated diphenylamine Structure CAS no. [68442-68-2] Supplier (trade name) Akrochem (Antioxidant POSDA) Goodyear Chemical (Wingstay 29) RT Vanderbilt (Wingstay 29) Akrochem (Antioxidant S) BF Goodrich (Goodrite Stalite S) Bayer (Vulkanox OCD/SG) Crompton Uniroyal (Octamine) Flexsys (Permanox ODPA) Harwick Standard (Stangard ODP) RT Vanderbilt (Vanox 12)

b. Octylated diphenylamine (ODPA)

[68411-46-1]

604

c. 2,2,4-Trimethyl1,2-dihydro quinoline, polymerized (TMQ)

26780-96-1

Ashland Chemical (Ashland AO TQ-T) Bayer (Vulkanox HS/LG) BF Goodrich (Goodrite MA, Resin D) Chemetall (Naftonox TMQ) Crompton Uniroyal (Naugard Q) Flexsys (Flectol TMQ) Great Lakes Chemical (Anox HB, HPG) PMC Specialties (Ralox TMQ) RT Vanderbilt (Agerite Resin D) Raschig (Ralox TMQ) Sovereign Chemical (Pilnox TDQ) Sumitomo Chemical (Antigene RD-G) Struktol (Struktol TMQ) Akrochem (Antiozonant MPD-100) Bayer (Vulkanox 3100) Goodyear Chemical (Wingstay 100, 200) Crompton Uniroyal (Novazone AS) RT Vanderbilt (Wingstay 100)

605 d. Mixed diaryl-pphenylenediamine (DPPD) [68953-84-4]

Table 15. (Continued) Chemical name (abbreviation) e. N,N -Bis(1,4dimethylpentyl)-pphenylendiamine (77PD) Structure CAS no. [3081-14-9] Supplier (trade name) CP Hall (UOP 788) Crompton Uniroyal (Flexzone 4L) Flexsys (Santoex 77PD) UOP (UOP 788) Akrochem (Antiozonant PD-2) CP Hall (UOP 588) Chemetall (Naftonox 6PPD) Crompton Uniroyal (Flexzone 7L, 7P) Duslo Sala (Dusantox 6PPD) Bayer (Vulkanox 4020) Flexsys (Santoex 6PPD) RT Vanderbilt (Antozite 67P) Sovereign Chemical (Dusantox 6PPD) Struktol (Struktol 6PPD) Sumitomo Chemical (Antigene 6C) UOP (UOP 588)

f. N-(1,3Dimethylbutyl)N -phenyl-pphenylenediamine (6-PPD) 606

[61931-82-6] [793-24-8]

g. Benzenamine, N-[4-(1,3-dimethyl (butyl)imino]-2,5cyclohexadien-1ylidene (6-QDI) h. 2,4,6-Tris(N-1,4dimethyl-pentyl-pphenylenediamino)1,3,5-triazine (TAPDT)

[52870-46-9]

Flexsys (Q-Flex QDI)

Crompton Uniroyal (Durazone 37)

607

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(3) Formation, through its reaction products with ozone, of a protective lm at the rubber surface (4) Increase in the critical stress of the rubber article. The critical stress is the applied static stress at which ozone cracking appears on the surface of a rubber article exposed to ozone. N-(1,3-dimethylbutyl)-N -phenyl-p-phenylenediamine; abbreviated 6-PPD, is a particularly versatile chemical offering a blend of antioxidant and antiozonant behavior combined with good rubber solubility and modest volatility, although other PPDs have applications as well. The diaryl PPDs have limited rubber solubility but lower volatility than 6-PPD. They provide excellent antioxidant protection and decent persistence with diminished antiozonant protection. All PPDs are highly staining and discoloring. This behavior is not necessarily a problem in carbon black lled articles, but restricts usage in colored goodsor even tires with colored components. Two long-standing deciencies with the PPD antidegradants, lack of persistence and discoloration/staining, have been addressed, respectively, in recent additions to the eld: 6-QDI, a dehydrogenated PPD, and TAPDT, a trimeric, high MW form of PPD. 6-QDI (N-(1,3-dimethylbutyl)-N -phenyl-p-quinonediimine, Table 15) offers improved persistence because of its partial immobilization and binding to the polymer matrix during mixing (86,87). As an efcient radical trap, 6-QDI acts as a chemical peptizer to reduce natural rubber chain length and viscosity in mixing by capping cleaved polymer chain end radicals. 6-QDI still provides chemical antidegradant protection similarly to its hydrogenated parent, 6-PPD, and is considered to be produced in situ from 6-PPD as part of the latters mechanism of action in the cured rubber compound, as shown in equation 1 (88,89). 6-QDI is also reported to preserve sulfur network rank stability better than 6-PPD and impart improved abrasion resistance to a natural rubber tread compound relative to PPD and TMQ antidegradants (90).

(1) TAPDT [2,4,6-tris-(N-1,4-dimethylpentyl-p-phenylenediamino)-1,3,5triazine, Table 15 provides reduced discoloration as a result of its increased molecular size which imparts reduced mobility in the rubber matrix (91). Discoloration results from bloom of ozonation by-products of the antidegradant to the rubber surface. PPD containing compounds will stain adjacent compounds in a composite structure because of migration of the PPD. An example is a black sidewall protected by PPD staining the white sidewall of a tire. TAPDT does not

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migrate like the monomeric PPDs. TAPDT gives excellent static ozone protection, ex resistance, as well as antioxidant behavior, but does not provide the same level of dynamic ozone protection (protection to product under stress, such as in cyclic exing) as the monomeric PPDs (91). Blends of TAPDT and 6-PPD have been shown to give excellent overall protection and durability (91). A new partially graftable, aminic PPD of unspecied structure was recently presented as another means to nonstaining antidegradant protection for rubber (92). In summary, the eld of rubber chemicals is both mature and ever evolving. Recent advances and changes have been prompted by environmental concerns, the move to higher efciency cures and processing, the pursuit of more durable rubber products, and the growth of silica as a reinforcing ller.

BIBLIOGRAPHY
Rubber Chemicals in EPST 1st ed., Vol. 12, pp. 256280, by F. W. Shaver, The B. F. Goodrich Co.; Rubber Chemicals in EPSE 2nd ed., Vol. 14, pp. 716762, by J. A. Kuczkowski, The Goodyear Tire & Rubber Co. 1. P. Ghosh, S. Katare, P. Patkar, J. M. Caruthers, V. Venkatasubramanian, and K. A. Walker, Rubber Chem. Technol. 76, 592 (2003). 2. M. R. Krejsa and J. L. Koenig, Rubber Chem. Technol. 66, 376 (1993). 3. M. Akiba and A. S. Hashim, Prog. Polym. Sci. 22, 475 (1997). 4. M. A. Faith, Rubber World 208(5), 15 (1993). 5. M. A. Faith, Rubber World 209(1), 22 (1993). 6. M. A. Faith, Rubber World 209(3), 17 (1993). 7. M. A. Faith, Rubber World 209(5), 18 (1994). 8. M. A. Faith, Rubber World 210(1), 24 (1994). 9. A. V. Chapman and M. Porter, in A. D. Roberts, ed., Natural Rubber Science and Technology, Oxford University Press, New York, 1988, pp. 512620. 10. J. O. Harris and C. D. Trivette Jr., in G. Alliger and I. J. Sjothum, eds., Vulcanization of Elastomers, Robert E. Krieger Publishing Co., New York, 1978, pp. 174 178. 11. R. H Schuster, Hannover, Sowie F. Nabholz and M. Gmunder, Kautschuk Gummi Kunststoffe 43(2), 95 (1990). 12. W. Hoffmann, GAK 43, 562 (1990). 13. W. Hofmann and J. Diederichsen, Int. Polym. Sci. Technol. 21(8), T/23 (1994). 14. K. M. Davies, D. G. Lloyd, and A. Orband, Kautschuk Gummi Kunststoffe 42(2), 120 (1989). 15. C. J. Hann, A. B. Sullivan, B. C. Host, and G. H. Kuhls Jr., Rubber Chem. Technol. 67(1), 76 (1994). 16. R. M. DSidocky, The Goodyear Tire & Rubber Co., unpublished results, 2004. 17. R. I. Keib, A. B. Sullivan, and C. D. Trivette, Rubber Chem. Technol. 43, 1188 (1970). 18. D. B. Seeberger, Rubber Division, ACS, Detroit, Mich., Paper No. 70, Oct. 1989. 19. D. W. Chasar, Rubber World 22(5), 26 (2002). 20. B. H. To and A. D. Hoog, Rubber Plast. News Sept. 23, 14 (2002). 21. A. A. Kuznetsov and O. A. Kulikova, Prog. Rubber Plast. Technol. 16, 255 (2000).

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MARTIN P. COHEN RICHARD M. DSIDOCKY The Goodyear Tire & Rubber Company