Today, Cr is exclusively produced in emulsion, and using free radical initiators.preferred emulsifiers are sodium soaps of rosin acids,and sodium naphthalin sulfonate is frequently added as an additional stabilizer. Redox systems are suitableinitiators,as,for instance,sulfinic acid in the presence of oxygen,or persulfate.In order to prevent the formation of peroxides,small amounts of inhibitors are added,such as tert.-butyl pyrocatechol,but these reduce the rate of monomer conversion.With the so-called sulphur modified CR grades (or thiuram grades),the moleular weight is controlled by adding sulphur,which copolymerizes and forms sx segments in the polymer chain 3.291,3.292,3.320,3.321 these CR grades are stabilized with thiurams,such as TETD.with the so-called mercaptan CR grades,the molecular weight is controlled with n-dodecyl mercaptan [3.287].After reaching the desired degree of monomer conversion,of about 70%,the polymerization reaction is terminated by adding phenothiazine or tert.butyl pyrocatechol.After removing unreacted monomer and adding the stabilizer,the polymer is coagulated on a freezing drum,washed,and dried.
In the production of CR a similar number of parameters have to be considered as in the case of SBR (see page 59),which results in a wide range of commercially available grades.
The important parameters are :
-Sulphur modification (thiurm grades,ability to masticate the rubber);
-Mercaptan modification (mercaptan grades);
-Polymerization temperature (tendency to crystallize);
-Modifier (different Mooney viscosities, processibility);
-Stabilizer (colour and storage stability);
-Copolymerization with other monomers (tendency to crystallize);
-Precrosslinking (processing behavior)
-Reactive goups (ability to crosslink without sulphur and accelerator. Only important for lattices. ).
3.3.4.3 Structure of CR and its influence on properties
Viscosity, The molecular weight distribution, the degree of long chain branching, and the average molecular weight have the same effect on CR as on NBR. The Mooney viscosity has an influence on the ability of the rubber to band on mills, the heat build-up during mixing, the acceptance of filler, the extrudadility, die awell and calenderability, to name a few.
Microstructure. The microstructurr of CR influences the processing behavior and the elastic properties of the rubber, and it depends very much on the polymerization the elastic properties of the rubber, and it depends very much on the polymerization temperature. With increasing temperatures there will be less uniformity in the chain structure due to increasing proportions of 1.2 and 3.4 moieties and different isomers in the monomer sequences [3.313]. This formation of more irregular chain structures reduces the rate of crystallization of the polymers. On the other hand, those CR grades, which have been polymerizdd at low temperatures, have a strong tendency to crystallize at high rates, which is an important requirement for adhesives with good immediate tack. These CR grades are, however, less suited for the production of rubber products, because they harden very rapidly with an attending loss of elasticity. Therefore, CR grades which, on account of their low tendency to crystallize, are useful for the production of rubber goods, are usually polymerized at higher temperatures. The copolymerization of chloroprene with small amounts of 2,3-dichloro butadiene, acrylonitrile, or styrene, also result in the desirable structural irregularity of the polymer chains, and this, therefore reduces the tendency to crystallize [3.293]. Since the rate of vulcanization of CR depends to a great extent on the amount of allylic chlorine in the polymer chains, the higher polymerization temperatures. Have also a beneficial effect in this respect.
As previously mentioned, Sx groups are built into the polymer chains of sulphur modified CR grades. In addition, fragments from the thiuram stabilizers attach to the polymer chains. As a result of these segments, it is possible to depolymerize these CR grades during processing As with NR the molecular weight is reduced during mastication of CR, and thus the initial nerviness of the rubber diminishes with an attending improvement in processing behaviour, such as dieswell. Due to this inherent instability, the viscosity of the rubber does not remain constant and the storage is not very good. On the other hand, the presence of sulphur and thiurams obviates in many cases the need for accelerators for the vulcanization.
The considerably more stable mercaptan modified CR grades have found a much greater market acceptance. As with NBR, the compound viscosity of these CRs is determined by the degree. of polymerization and the type and amount of plasticizer used in the compound. The curing properties of these CRs are adjusted with accelerators.
Pre-crosslinked CR grades, which consist almost completely of gel, can be blended in concentrations between 10 and 50% with conventional CR grades to improvetheir processing properties by reducing nerviness and die swell. This is similar to NBRs(see page 69). These blends have, however, a lower tensile strength.
Chlorine Concentration. CR is a polar rubber because it contains one chlorine atom for every four carbon atoms in the chain of homopolymers. Therefore, by comparison with non-polar diene rubber, CR has a better resistance to swelling in mineral, animal, and vegetable oils and fats. The swelling resistance is, however, less than for NBR. The chlorine atoms also impart to CR a better flame, weather, and ozone resistance, than normally encountered with diene rubbers. These properties are particularly enhanced in copolymers of chloroprene and dichlorobutadiene, because of the even higher chlorine content in the copolymer
3.3.4.4 Compounding of CR
Blends.The typical property spectrum of CRs can be m0dified through blends with other rubbers. NR improves, for instance, the elasticity and low temperature flexibility. BR reduces the brittleness temperature considerably. Blends with NBR improve the swelling resistance in industrial oils With all these blends, it is a problem to adjust the cure system in such a manner, to make it adequate for the individual blend components.
Therefore, frequently used cure systems in these blends are sulphur, and thiourea derivatives, with the addition of thiuram and guanigine accelerators.
Vulcanizing Agents.[3.298-3.304] Contrary to other diene rubbers, the vulcanization of CR compounds is not carried out using sulphur, but metal oxides. In general, the best proven cure systems are combinations of, for instance, 4 phr Mgo with 5 phZnO, or if very low water absorption is required, lead oxides (PbO or Pb2 O4 in concentrations of up to 20 phr or even higher).
With mercaptan CR grades, sulphur can be added to enhance the degree of vulcanization, but this also reduces the heat resistance of the vulcanizate.
The choice of accelerators for CR is also governed by different rules than for other diene rubbers. In general, cure systems that provide faster cure rates tend to be more scorch. Also those, that give a higher degree of vulcanization, i. e. higher tensile strength, lower elongation at break, higher rebound elasticity, and less compression set, tend to have less scorch safety.
As already mentioned, in most instances the thiuram CR grades do not require additional accelerator The presence of metal oxides is by itself already suffient in most cases to achieve a sufficient rate of vulcanization. However, by adding accelerators, the cure rate of these compounds can be even further increased, with an attendant reduction in storage stability and time to completion of the vulcanization reaction.
By contrast, the mercaptan CR grades require accelerators besides MgO and ZnO or lead oxides Most conventionally used accelerators are not very effective in CR, and instead, the most important one is thiourea (ETU). However, in spite of being a good and most effective vulcanizing agent for CR, it is, because of its toxicity, being progressively replaced by DETU, or other recent developments in thioketones and thiadiazines, such as thiadiazole [3.298-3.300,3.304]. A newly adveloped thioketone derivative as well as 3-methyl-thiazolidin-thione-2 appear to surpass even ETU with respect to scorch safety and cure rate, and the obtainable degree of vulcanization [3.300,3.304]
For a good compromise between scorch safety and cure rate on the one hand, and state of cure on the other, combinations of small amounts of ETU or one of the other CR accelerators with thiurams or guanidines should be used. For extremely rapid cure rates (self curing), DPTU in combination with aldehyde amines are employed.
There are no typical vulcanization inhibitors for CR compounds, although MBTS or thiurams are capable of reducing the cure rates somewhat. A cure inhibition, however also reduces the state of cure, which, in turn, can be counteracted by raising the cure temperature, so that cure states obtainable with ETU can be reached.
Peroxide cures are, as a rule, not emploved with CR compounds.
Protective Agents. In spite of the inherently excellent oxidative stability of CR, additional agents are added to protect CR vulcanizates against oxygen ond ozone degradation, to meet particularly stringent requirements for some applications. Such agents are especially aromatic amines, such as IPPD, and diphenyl amine derivatives, like ODPA or SDPA, as well as sterically hindered phenols for light coloured compounds. With the use of MBI, one has to consider its accelerating influence on the cure of CR compounds. Therefore, it is seldomly used. To improve the ozone resistance of back vulcanizates, enol ethers or benzofuran derivatives [1.14]
Fillers. For gum vulcanizates or those formulated with non-reinforcing fillers, the tensile and tear strengths are higher for CR than for corresponding ones based on SBR or NBR. Yet, vulcanizates from CR do not reach the pro