Vulcanisation polysulphides

Figure 11.15. Typical chemical groupings in a sulphur-vulcanised natural rubber network, (a) Monosulphide cross-link (b) disulphide cross-link (c) polysulphide cross-link (j = 3-6) (d) parallel vicinal cross-link (n = 1-6) attached to adjacent main-chain atoms and which have the same influence as a single cross-link (e) cross-links attached to common or adjacent carbon atom (f) intra-chain cyclic monosulphide (g) intra-chain cyclic disulphide (h) pendent sulphide group terminated by moiety X derived from accelerator (i) conjugated diene (j) conjugated triene (k) extra-network material (1) carbon-carbon cross-links (probably absent)...

Early examples of such branched polysulphides, e.g. Thiokol FA, are believed to possess hydroxyl end groups and are coupled by means of zinc compounds such as the oxide, hydroxide, borate and stearate by a mechanism which is not understood. Later elastomers, e.g. Thiokol ST, have been modified by a restricted reductive cleavage (see below) and this generates thiol (mercaptan) end groups. These may be vulcanised by oxidative coupling as illustrated below with lead peroxide ... 

Also known as vulcanite and (mainly in the USA) hard rubber . The hard, horn-like product obtained when natural rubber and some synthetic rubbers such as nitrile (NBR) are vulcanised with a high proportion of sulphur or organic nonsulphur vulcanising agent. Butyl rubber and polysulphide rubber do not form ebonites. Ebullioscopy... 

The hydrogen polysulphides arc miscible with benzene, toluene, chloroform, bromofomi, carbon disulphide, ether and heptane, giving relatively stable solutions,5 and the use of such solutions has been suggested in place of sulphur chloride for the vulcanisation of caoutchouc at the ordinary temperature. The addition of alcohol to the benzene solutions induces rapid decomposition, with formation of nacreous sulphur, which slowly undergoes conversion into ordinary sulphur (p. 25). Ketones, nitrobenzene, aniline and pyridine also catalyse the decomposition. 

A TG-DTA study of the thermochemical processes occurring at vulcanisation temperatures with N-oxydiethylene-2-benzthiazyl sulphenamide and N-cyclohexyl-2-benzthiazyl sulphenamide and their mixtures with sulphur showed the formation of high molecular weight polysulphides [73]. The influence of metallic oxides (Fe203, Sn02) on hot air ageing of one-pack room temperature vulcanised fluorosilicone rubber has been studied by means of TG-DTA [74, 75]. TG-DTA and TG were both applied to study the thermal characteristics of room temperature vulcanised silicone rubber [76]. 

The original crosslinking process for natural rubber, called vulcanisation, involved mixing in 2-3% of sulphur plus an accelerator. On heating to 140 °C the sulphur reacts with C=C bonds on neighbouring polyisoprene chains to form sulphur crosslinks C—(S) —C. Typically, 15% of the crosslinks are monosulphide [n = 1), 15% are disulphide and the rest are polysulphide with n > 2. The polysulphide crosslinks are partially labile, which means that they can break and reform with other broken crosslinks when the applied stresses are high. This leads to permanent creep in compressed rubber blocks. To avoid such permanent set, efficient vulcanisation systems have been developed that produce only monosulphide crosslinks. 

The choice of vulcanisation system for the rubber can have a dramatic effect on adhesion. Typically sulphur cured rubbers are easier to bond to than sulphur-free or peroxide cured rubbers. This is believed to be due to the interaction of sulphur with key curative materials in the adhesive. The more sulphur that is present, the more interactions that are available, and hence the better the chance of getting good adhesion. SEV (semiefficient vulcanisation) and EV (efficient vulcanisation) cure packages are typically more difficult to bond because of their lower free sulphur contents. EV refers to cure systems which give predominantly monosulphidic or disulphidic crosslinks whereas conventional sulphur cure systems produce mostly polysulphidic crosslinks. SEV systems fall somewhere between EV and conventional systems in the type of crosslinks produced. Vulcanisation proceeds at different rates and with different efficiencies in different types of polymers, so the amount of sulphur needed to produce an EV cure system will also vary. For example, in NR, an EV system will generally contain between 0.4 and 0.8 phr of sulphur, while in NBR the sulphur level will generally be less than 0.3 phr of free elemental sulphur. 

It has been demonstrated previously that such additions can increase the strength of rubber-brass adhesion considerably. In this research it was established that polysulphides are only weak crosslinking agents for unsaturated rubber by themselves. In the presence of sulphenamide accelerators, such as OBTS, polysulphides, in amounts of 0.5 - 1 phr, activate the sulphur vulcanisation. However, the reversion process (crosslink breakdown) is not accelerated. A favourable effect on the physicomechanical properties of the vulcanisate was also reported. 

Purified natural rubber (PNR) is of interest because of its potentially lower toxicological effects than whole natural rubber (WNR) due particularly to the reduction in protein content. Improved dynamic mechanical properties have also been reported. Comparison of both gum and filled compounds, vulcanised using conventional cure systems (CV) and efficient vulcanisation systems (EV) prepared from PNR and WNR indicate that generally properties of the PNR are poorer than WNR. The exception is in the flex cracking resistance and the heat build up in the filled samples where PNR shows an improvement. Using the EV cure system on filled PNR gives properties almost comparable to WNR. A study of the distribution of the types of sulphur crosslink in both pNR and WNR vulcanisates indicates a more uniform distribution of monosulphidic (S), disulphidic (S2) and polysulphidic (Sx) crosslinks in the PNR samples (38.7/25/36.4 in PNR compared to 64.1/29.7/6.6 in WNR respectively). This is believed to be the reason for the better dynamic properties of PNR vulcanisates. 7 refs THAILAND... 

PERFORMANCE OF BISAMESE DISULPHIDES AND THIURAM DI- AND POLYSULPHIDE DERIVATIVES AS NON-NITROSAMINE VULCANISING AGENTS... 

For the purpose of developing non-nitrosamine type vulcanising agents, bicyclic amide disulphides, non-nitrosamine bisamine disulphides and non-nitrosamine thiuram di- and polysulphide derivatives were synthesised and their performance in sulphur and EV vulcanisation were investigated. 8 refs. Articles from this journal can be requested for translation by subscribers to the Rapra produced International Polymer Science and Technology. 

Rubber mixtures which can be vulcanised without reversion are disclosed, containing natural and/or synthetic mbber together with (based on the amount of rubber) 0.1-10 wt.% of a dithiophosphoric acid polysulphide with 4-12C alkyl groups, 0.5-8 wt.% metal alkyl dithiophosphate and/or mercaptobenzthiazole and optionally conventional additives. 

Rhenocure SDT (Rhein Chemie), a dialkyl dithiophosphate polysulphide sulphur donor, was evaluated in curing systems for the vulcanisation of thick NR parts. It was found that a curing system based on a dithiophosphate accelerator and the dithiophosphate sulphur donor was superior to a system based on a sulphenamide and dithiodimorpholine. A substantially higher amount of short sulphur bridges was generated, leading to improved reversion resistance and superior heat... 

It is shown that the role of zinc stearate in vulcanisation formulations is to promote the reaction of accelerator terminated polysulphidic pendant groups with neighbouring polymer chains, thereby resulting in higher crosslink densities. Cyclisation reactions may also be reduced, thus increasing stress induced crystallisation under load and thereby further enhancing the physical properties of the vulcanisate. 6 refs. 

Reversion of sulphur-based crosslinks continues to a problem for NR compounders. Reversion is the thermal degradation of polysulphidic crosslinks leading to a reduction of crosslink density and an introduction of main chain modifications. In practice, reversion leads to a decline in compound physical properties. Reversion occurs when compounds are overcured or when vulcanisates are exposed to anaerobic ageing. Ideally, a... 

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