Curing polychloroprene rubber

Ethvlenethiourea (2-mercaptoimidazolinej imidazolidine-2-thione imidazoline-2-thiol, VIII) is a water-soluble white crystalline solid used extensively in curing elastomers (rubbers, e.g., polychloroprenes, polyacrylates, etc.) It is also present as an impurity in the ethylene bisdithiocarbamates widely used as fungicides. When the fungicides are present as a contaminant in heated foods, they may be converted to the ethylenethiourea (ref. 

Solvents produce different effects than do corrosive chemicals. Both silica and carbon black filled natural rubbers were more resistant to solvents than unfilled rubber. Also, the cure time was important, indicating that the bound rubber plays a role in the reduction of a solvent sorption. The diffusion coefficient of solvents into rubbers decreases with longer cure times and higher fillers loadings. Polychloroprene rubber swollen with solvent has a lower compression set when it is filled with carbon black. 

The curing of CR adhesives is different from that for most rubber-based adhesives as it involves the labile chlorine atoms. This is reflected in the compounding ingredients. The most common room curing agent is zinc oxide, but isocyanates are also very common. Further discussion is given in Polychloroprene rubber adhesives modifiers and additives. 

Most Rubber-based adhesives may be cured by a sulphur-based vulcanizing system (see Rubber-based adhesives compounding), however, as mentioned in Polychloroprene rubber adhesives applications and properties, CR adhesives are cross-linked by various reactions involving the labile chlorine atoms in the repeat unit. This is reflected in the additives used, as discussed below. ... 

Delayed action sulfenamide accelerator for natural and synthetic rubbers. It provides better scorch resistance than thiazoles and can be accelerated by thiurams and dithiocarbamates to give shorter cure times. It can also be used as a retarder for ETU-cured polychloroprene and high thiuram cures. 

The close structural similarities between polychloroprene and the natural rubber molecule will be noted. However, whilst the methyl group activates the double bond in the polyisoprene molecule the chlorine atom has the opposite effect in polychloroprene. Thus the polymer is less liable to oxygen and ozone attack. At the same time the a-methylene groups are also deactivated so that accelerated sulphur vulcanisation is not a feasible proposition and alternative curing systems, often involving the pendant vinyl groups arising from 1,2-polymerisation modes, are necessary. 

Resin cures utilise phenol-formaldehyde resins with reactive methylene groups and a small added amount of either a chlorinated rubber, e.g., polychloroprene, or stannous chloride. If halogenated phenolic resins are used the additional source of a halogen may not be required. Resin cures give butyl compounds excellent heat stability and are used to good effect where this is required, e.g., in tyre curing bags which have to resist service at 150 °C in a steam atmosphere. 

Resin cures utilise the same resins that are used for butyl rubber, but more resin (ca. 10-12 phr) and a halogen donor (10 phr), typically bromobutyl, or polychloroprene, are required. Although heat stability is slightly improved by resin curing when compared to sulphur cures, the effect is not as marked as in the resin curing of butyl. 

The costs, as for all plastics, fluctuate highly with the crude oil price. Most common TPE/PVCs are cheaper than SEES, TPVs and general-purpose cured rubbers such as EPDMs and polychloroprenes but are more expensive than TPOs and SES. 

Other Accelerators. Amine isophthalate and thiazolidine thione, which are used as alternatives to thioureas for cross-linking polychloroprene (Neoprene) and other chlorine-containing polymers, are also used as accelerators. A few free amines are used as accelerators of sulfur vulcanization these have high molecular weight to minimize volatility and workplace exposure. Several amines and amine salts are used to speed up the dimercapto thiadiazole cure of chlorinated polyethylene and polyacrylates. Phosphonium salts are used as accelerators for the bisphenol cure of fluorocarbon rubbers. 

Ethylenethiourea has a wide variety of uses in addition to vulcanization, a principal application since 1948. The curing process converts most of the ETU to other compounds, but traces of it are still found in the rubbers. Neoprene (polychloroprene) is found largely in automotive parts, wire and cable insulation, construction and adhesives. Consumer products containing neoprenes include container seals (e.g., aerosol dispensers) and shoes. It is also an intermediate in the manufacture of antioxidants, dyes, fungicides, insecticides, pharmaceuticals, synthetic resins, and a constituent of plating baths. 

The best known examples of these rubbers with limited cure functionality are EPDM and butyl rubbers where a small amount of a diene is copolymerised with the main monomers. Polychloroprene also behaves as a member of this class, when cured with diamines and thioureas. In this case the cure functional group occurs as a result of a small fraction of 1— 2 polymerised units among the predominant 1—4 polymerised chloroprene. 

Examples of the use of blocked diisocyanates for rubber-fabric adhesion are as follows vulcanized polychloroprene and SBR can be adhered strongly to nylon and polyester fibre fabric by means of aqueous adhesive systems (Table 8.4). This combination is spread or roller coated on to the fabric which is then allowed to dry. Bonds to sheet rubber stock can be made immediately after the treated fabric is dried or at any time thereafter. When the sheet rubber is applied it should be held under moderate pressure to provide intimate contact with the treated fabric and to prevent lifting if any gases are emitted during cure. Press cures of 20-40 min at 140°C are sufficient to cure the adhesive and most elastomer compositions being adhered. If a latex film is applied to the treated fabric, the assembly can be cured in a hot-air oven at 120"C. A chemical bond results between fabric and the diphenylmethane-/7,/ -diisocyanate generated on the thermal cleavage of the blocked diisocyanate. 

The critical links between the raw polymer and finished vulcanized product used by the global consumer involve the compounding, processing, and curing or vulcanization. There are several major considerations in designing a rubber composition based on polychloroprene dry polymers (Table 5). 

Several rubbers may be crosslinked using divalent metal oxides, usually zinc oxide. There are a limited number of polymers that utilise this method, which is used with halogenated polymers such as polychloroprene [8], chloro- and bromobutyl, and chlorosulfonated polyethylene and carboxylated nitrile rubbers. The system may utilise the metal oxide alone or in combination with the organic accelerators used with sulfur-curing systems. In the case of halogenated polymers, magnesium oxide may be added to act as an acid scavenger. 

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