Natural polyisoprene vulcanization

Rubber tyres are by far the most visible of rubber products. Identification is trivial and collection is well organized. Recycling and disposal, however, are less evident. A major route for tyres is their use as a supplemental fuel in cement kilns. Major compounds in tyres are styrene-butadiene rubber (SBR), synthetic and natural polyisoprene rubber, steel cord, carbon black, zinc oxide, sulphur and vulcanization-controlling chemicals. Tyres can be retreaded, which is economic for large sizes (truck tyres), or ground to crumb or powder (cryogenic grinding). Such materials have some limited market potential as an additive in asphalt, and in surfaces for tennis courts or athletics. 

This (synthetical) elastomer is analogous to the (natural) polyisoprene and can also be vulcanized to make rubber (see Chapter 1, Section 4.4). 

The above discussion relates to the "drying of oils by oxygen. Materials like natural rubber (see Natural Polyisoprenes section) are vulcanized with sulfur. The unsaturated oils can be made to undergo a similar set of reactions (48). Brown factice is made by first blowing a drying oil, then reacting it with 5-30% of sulfur at 250-350°F for 1-2 hours. 

They are also natural polyisoprenes and are isomers of natural rubber. They are extracted from sheets of plants in the family of sapotaceae (Southeast Asia and Equatorial America). The polymer chains are constructed from repeating units of 1,4-trans isoprene structure. Contrary to natural rubber, they partially crystallize spontaneously according to two conformations one is 2i helical (a-form), the other one is totally transplanar and is equivalent to a li helix ( -form). The mechanical properties of these materials are determined by the values of the transition temperatures. Amorphous zones undergo a glass transition at —60 C and the two crystalline forms (a and P) melt at 64°C. The corresponding polymers are thus thermoplastics and acquire (after vulcanization) a highly elastic behavior beyond 70°C. 

Natural rubber, cis-1,4-polyisoprene, cross-linked with sulfur. This reaction was discovered by Goodyear in 1839, making it both historically and commercially the most important process of this type. This reaction in particular and crosslinking in general are also called vulcanization. 

Polyisoprene is a synthetic polymer (elastomer) that can he vulcanized hy the addition of sulfur. cis-Polyisoprene has properties similar to that of natural ruhher. It is characterized hy high tensile strength and insensitivity to temperature changes, hut it has low abrasion resistance. It is attacked hy oxygen and hydrocarbons. 

Very frequent are the cases of stress-induced crystallizations. A typical case is that of slightly vulcanized natural rubber (1,4-m-polyisoprene) which, under tension producing a sufficient chain orientation, is able to crystallize, while it reverts to its original amorphous phase by relaxation [75],... 

FIGURE 19.17 The gray cylinders in the small inset represent polyisoprene molecules, and the beaded yellow strings represent disulfide (—S—S—) links that are introduced when the rubber is vulcanized, or heated with sulfur. These cross-links increase the resilience of the rubber and make it more useful than natural rubber. Automobile tires are made of vulcanized rubber and a number of additives, including carbon. 

An example of a nonlinear polymer derived by cross-linking an initially linear polymer is afforded by vulcanized natural rubber. In the usual vulcanization procedure involving the use of sulfur and accelerators, various types of cross-linkages may be introduced between occasional units (about one in a hundred) of the polyisoprene chains. Some of these bonds are indicated to be of the following type ... 

Thermodynamic Analysis. As reported previously, the storage modulus G of PDMS networks with tetrafunctional crosslinks is independent of frequency between 10 3 and 1 Hz (21). This behaviour which is entirely different from that of vulcanized natural rubber or synthetic polyisoprene networks, was attributed to the lack of entanglements, both trapped and untrapped, in these PDMS networks. Figure 4 shows that G of a network with comb-like crosslinks is also frequency independent within an error of 0.5%. For comparison, two curves for PDMS having tetrafunctional crosslinks are also shown. The flat curves imply that slower relaxations are highly unlikely. Hence a thermodynamic analysis of the G data below 1 Hz can be made as they equal equilibrium moduli. 

Improvement in the processing and vulcanized qualities of a range of systems have been reported over the past decades. Modification of natural rubber, due to work in the British Rubber Producers Research Association, yields some of the most striking applications of microgel. A detailed study at the MV Lomonosov Institute of Fine Chemical Technology, in Moscow, on the effect of microgels on mechanical properties of cis-polyisoprene and butadiene-styrene rubbers extensively illustrates the properties of blends from latex combination of microgel and conventional or linear systems.(31)... 

Note 2 A classic example of vulcanization is the crosslinking of c/s-polyisoprene through sulfide bridges in the thermal treatment of natural rubber with sulfur or a sulfur-containing compound. 

Sulfur vulcanization leads to a variety of cross-link structures as shown in Figure 1. All the sulfur does not result in cross-links some of it remains as pendent accelerator polysulfide groups and internal cyclic polysulfides. These alternative structures do not contribute to load bearing or strength properties and are more prevalent in unaccelerated or weakly accelerated vulcanization systems. Additional heating can also reduce the polysulfide rank of the cross-links. In some elastomers, this leads to a larger number of cross-links. However, in natural mbber or its synthetic polyisoprene equivalent, the overall result is a loss of cross-links, especially at temperatures over 160°C. 

The search for a lightweight, nonbreakable, moldable material began with the invention of vulcanized rubber. This material is derived from natural rubber, which is a semisolid, elastic, natural polymer. The fundamental chemical unit of natural rubber is polyisoprene, which plants produce from isoprene molecules, as shown in Figure 18.5. In the 1700s, natural rubber was noted for its ability to rub off pencil marks, which is the origin of the term rubber. Natural rubber has few other uses, however, because it turns gooey at warm temperatures and brittle at cold temperatures. 

Natural rubber is a polymer of isoprene- most often cis-l,4-polyiso-prene - with a molecular weight of 100,000 to 1,000,000. Typically, a few percent of other materials, such as proteins, fatty acids, resins and inorganic materials is found in natural rubber. Polyisoprene is also created synthetically, producing what is sometimes referred to as "synthetic natural rubber". Owing to the presence of a double bond in each and every repeat unit, natural rubber is sensitive to ozone cracking. Some natural rubber sources called gutta percha are composed of trans-1,4-poly isoprene, a structural isomer which has similar, but not identical properties. Natural rubber is an elastomer and a thermoplastic. However, it should be noted that as the rubber is vulcanized it will turn into a thermoset. Most rubber in everyday use is vulcanized to a point where it shares properties of both, i.e., if it is heated and cooled, it is degraded but not destroyed. 

A good elastomer should not undergo plastic flow in either the stretched or relaxed state, and when stretched should have a memory of its relaxed state. These conditions are best achieved with natural rubber (ds-poIy-2-methyl-1,3-butadiene, ds-polyisoprene Section 13-4) by curing (vulcanizing) with sulfur. Natural rubber is tacky and undergoes plastic flow rather readily, but when it is heated with 1-8% by weight of elemental sulfur in the presence of an accelerator, sulfur cross-links are introduced between the chains. These cross-links reduce plastic flow and provide a reference framework for the stretched polymer to return to when it is allowed to relax. Too much sulfur completely destroys the elastic properties and produces hard rubber of the kind used in cases for storage batteries. 

Natural Rubbers (NR). The chemical name for NR is polyisoprene, which is a homopolymer of isoprene. It has the cis-1,4 configuration. In addition, the polymer contains small amounts of non-rubber substances, notably fatty acids, proteins, and resinous materials that function as mild accelerators and activators for vulcanization. Raw materials for the production of NR must be derived from trees of the Hevea Brasiliensis species. NR is available in a variety of types and grades, including smoked sheets, air-dried sheets, and pale crepes. 

Unsaturated and Vulcanized Rubbers. Oxidation occurs most readily at polymers with structural double bonds, such as natural rubber, polybutadiene, or polyisoprene. Aromatic amines and sterically hindered phenols are effective antioxidants. From the rubber antioxidants, 96.8 million pounds were amines, and 20 million pounds were phenols. Amines act also as antiozonants whereas phenols are not effective. Furukawa shows that amines have a lower oxidation potential which is a prerequisite for antiozonant action. 

On the other hand, if the cross-link density is low (the length of the chains between cross-links is large) and the mobility of the chains is high, the cross-linked material is called an elastomer. An example of a typical elastomer is cw-l,4-polyisoprene (natural rubber), which, by means of a cross-linking reaction with sulfur (vulcanization), gives rise to a network structure (see Fig. 1.4). 

Figure 1.4 (a) cis-1,4-Polyisoprene (natural rubber), (b) Cross-linking reaction with sulfur (vulcanization). 

---